KR20140098679A - Curable resin composition, and resin composition for optical semiconductor sealing - Google Patents
Curable resin composition, and resin composition for optical semiconductor sealing Download PDFInfo
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- KR20140098679A KR20140098679A KR1020140004839A KR20140004839A KR20140098679A KR 20140098679 A KR20140098679 A KR 20140098679A KR 1020140004839 A KR1020140004839 A KR 1020140004839A KR 20140004839 A KR20140004839 A KR 20140004839A KR 20140098679 A KR20140098679 A KR 20140098679A
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- Prior art keywords
- resin composition
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- carbon atoms
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- 239000011342 resin composition Substances 0.000 title claims abstract description 242
- 230000003287 optical effect Effects 0.000 title claims abstract description 103
- 239000004065 semiconductor Substances 0.000 title claims abstract description 102
- 238000007789 sealing Methods 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 216
- 239000003822 epoxy resin Substances 0.000 claims abstract description 163
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 163
- -1 aluminum compound Chemical class 0.000 claims abstract description 143
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 86
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 54
- 125000003118 aryl group Chemical group 0.000 claims abstract description 37
- 125000003277 amino group Chemical group 0.000 claims abstract description 34
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 24
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 12
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 91
- 239000003566 sealing material Substances 0.000 claims description 77
- 239000004593 Epoxy Substances 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 59
- 238000005538 encapsulation Methods 0.000 claims description 51
- 125000002723 alicyclic group Chemical group 0.000 claims description 48
- 229920000058 polyacrylate Polymers 0.000 claims description 47
- 229920001296 polysiloxane Polymers 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 16
- 239000008393 encapsulating agent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 28
- 239000003795 chemical substances by application Substances 0.000 abstract description 26
- 238000003860 storage Methods 0.000 abstract description 24
- 150000003377 silicon compounds Chemical class 0.000 abstract description 12
- 238000001723 curing Methods 0.000 description 117
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 40
- 239000000047 product Substances 0.000 description 35
- 239000000203 mixture Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 23
- 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 21
- 125000002091 cationic group Chemical group 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 239000013522 chelant Substances 0.000 description 15
- 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 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 125000000962 organic group Chemical group 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000002834 transmittance Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 150000002430 hydrocarbons Chemical group 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 239000005011 phenolic resin Substances 0.000 description 10
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 125000003700 epoxy group Chemical group 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 125000004430 oxygen atom Chemical group O* 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- MQQXUGFEQSCYIA-OAWHIZORSA-M aluminum;(z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-] MQQXUGFEQSCYIA-OAWHIZORSA-M 0.000 description 5
- 239000002216 antistatic agent Substances 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000003944 tolyl group Chemical group 0.000 description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 5
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 4
- 125000003566 oxetanyl group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 3
- PCGYNXNSBCFBSU-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)-phenylborane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=CC=CC=C1 PCGYNXNSBCFBSU-UHFFFAOYSA-N 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000002845 discoloration Methods 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000001029 thermal curing Methods 0.000 description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 2
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- 125000004185 ester group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- TWNOVENTEPVGEJ-UHFFFAOYSA-K europium(3+);trifluoromethanesulfonate Chemical compound [Eu+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F TWNOVENTEPVGEJ-UHFFFAOYSA-K 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- RTKCPZYOLXPARI-UHFFFAOYSA-N magnesium;2-methylpropan-2-olate Chemical compound [Mg+2].CC(C)(C)[O-].CC(C)(C)[O-] RTKCPZYOLXPARI-UHFFFAOYSA-N 0.000 description 1
- WXPNTKUIDRYHOP-UHFFFAOYSA-L magnesium;3-oxobutanoate Chemical compound [Mg+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O WXPNTKUIDRYHOP-UHFFFAOYSA-L 0.000 description 1
- HXLZJCNKEKRQKH-UHFFFAOYSA-L magnesium;3-oxohexanoate Chemical compound [Mg+2].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O HXLZJCNKEKRQKH-UHFFFAOYSA-L 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- ORPJQHHQRCLVIC-UHFFFAOYSA-N magnesium;propan-2-olate Chemical compound CC(C)O[Mg]OC(C)C ORPJQHHQRCLVIC-UHFFFAOYSA-N 0.000 description 1
- BZQRBEVTLZHKEA-UHFFFAOYSA-L magnesium;trifluoromethanesulfonate Chemical compound [Mg+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F BZQRBEVTLZHKEA-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- XZVCKKPHOJCWME-UHFFFAOYSA-N penta-1,3-diene phenol Chemical compound CC=CC=C.Oc1ccccc1 XZVCKKPHOJCWME-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-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
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- GJOGTGLNIWPDPF-UHFFFAOYSA-N trifluoromethyl hydrogen sulfite Chemical compound OS(=O)OC(F)(F)F GJOGTGLNIWPDPF-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- POHPFVPVRKJHCR-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)alumane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Al](C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F POHPFVPVRKJHCR-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/70—Chelates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/295—Organic, e.g. plastic containing a filler
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Led Device Packages (AREA)
Abstract
Description
The present invention relates to a curable resin composition and a resin composition for optical semiconductor encapsulation. More specifically, the present invention relates to a resin composition that can be cured by heat, a photo-semiconductor sealing material, and a resin composition for optical-semiconductor encapsulation that is preferably used in an optical semiconductor device.
The curable resin composition is a resin composition that can be cured by heat, light, or the like, and is expected to be applied to various fields in recent years. Specifically, for example, various applications such as electric and electronic members, optical members, molding materials, and the like for various applications such as paints and adhesive materials have been studied in various ways, and curable resins Development of a composition is desired. Among them, the curable resin composition is preferably used as a material for a sealing material for an optical semiconductor such as an LED (Light Emitting Diode) and a photodiode, because the cured product (molded article) may exhibit transparency (light transmittance) useful. The optical semiconductor sealing material is a member formed so as to cover an LED element or a photodiode element constituting an optical semiconductor device, and sealing the element. When a curable resin composition is used as the material of the optical semiconductor sealing material, a cured product (molded product) of the curable resin composition is excellent in transparency (light transmittance), and is excellent in long-time exposure to short wavelength light of high energy such as blue light or violet light Heat discoloration such that it is not colored even if it is put under a high temperature over a long period of time due to heat generation of the element at the time of light emission is demanded.
As a conventional curable resin composition, for example, a resin composition containing an epoxy resin, an organic silicon compound, and an organoaluminum compound is disclosed for the purpose of obtaining a resin composition having excellent storage stability (for example, , Patent Documents 1 to 3).
An epoxy resin modified silicone resin has been studied as a conventional curable resin composition for the purpose of obtaining a cured product (molded article) excellent in mechanical strength, adhesive property, heat resistance, electrical characteristics, moisture resistance, and the like See, for example, Patent Document 4). It has also been studied to use a curable resin composition as a material of the optical semiconductor sealing material (see, for example, Patent Documents 5 and 6).
In addition, in order to obtain an optical semiconductor sealing material excellent in light transmittance, light resistance, and heat discoloration resistance, for example, an epoxy resin has been studied (see, for example, Patent Documents 7 and 8).
Patent Documents 1 and 2 disclose a resin composition comprising an epoxy resin, an organic silicon compound, and an organoaluminum compound. Such a resin composition has good curability at a relatively low temperature. However, And as a result, there is a problem that workability is deteriorated, and storage stability at room temperature is not yet sufficient. Patent Document 3 discloses a resin composition comprising a reaction product of an organosilicon compound and an epoxy resin, an organoaluminum compound, and an amine compound. However, such a resin composition is not cured by heating for a long time at a high temperature of 170 ° C or higher need. On the other hand, in order to lower the temperature condition at the time of curing and to increase the addition amount of the organoaluminum compound, or to improve the heat resistance and light resistance of the cured product, the blending amount of the organosilicon compound containing a silanol group or an alkoxysilane group And when it is used as a curing agent for an epoxy resin, it is difficult to secure sufficient storage stability at room temperature. The cured product (molded article) of such a resin composition has a problem that it is left under high temperature or is colored when exposed to high-energy short-wavelength light such as blue light or violet light. In addition to the storage stability at room temperature, The discoloration resistance and the light resistance are not yet sufficient and can not be said to be sufficient for application to optical semiconductor sealing materials and the like which are used under strict use conditions.
Patent Document 4 discloses a resin composition containing an epoxy resin, a polysiloxane compound, and an organoaluminum compound, but it is difficult to store such a resin composition stably at room temperature for a long time.
Patent Document 5 discloses a thermosetting resin composition comprising an epoxy resin, an organic silicon compound, and an organoaluminum compound. However, such a resin composition is difficult to be stably stored at room temperature for a long period of time. Further, when such a cured product (molded product) of the resin composition is used for the LED sealing material, cracks and coloring tend to occur with time due to heat generation from the element at the time of light emission. As a result, And the heat resistance of the molded article is not sufficient.
Patent Document 6 discloses a resin composition containing a polysiloxane compound and an organoaluminum compound, but such a resin composition is difficult to be stably stored at room temperature for a long period of time. In order to cure such a resin composition, it is necessary to heat the resin composition at a high temperature of 180 DEG C or more for a long time. When the cured product (molded product) of such a resin composition is used as an LED sealing material, the permeability of water vapor or corrosive gas is high, and the luminance retention rate in continuous light emission of the LED is lowered in the presence of sulfur dioxide and the like at high temperature and high humidity There is a challenge. As described above, the curable resin composition used for the material of the conventional optical semiconductor sealing material can not be said to have sufficient storage stability, heat resistance of the molded body, and long-time luminance retention property when used for the LED sealing material, There was room for review.
In Patent Document 7, a composition containing an epoxy resin and a (meth) acrylic polymer is cured using a curing agent. However, it has been difficult to maintain a high luminance in a long-time use of a sealing material formed in this way. In Patent Document 8, a composition containing an epoxy resin and a silicone resin is cured using a curing agent, but there is a fear that the sealing material thus formed is peeled off from an adherend (a substrate, a reflector, a lead frame, and the like) . From the above, there has been room for research in order to obtain a resin composition capable of producing an optical semiconductor sealing material having excellent properties in the prior art.
The present invention has been made in consideration of the above-described circumstances, and it is an object of the present invention to provide a curable resin composition which is excellent in storage stability at room temperature and can be cured at a relatively low temperature. In the case where the obtained molded article is excellent in heat resistance, It is an object of the present invention to provide a curable resin composition capable of maintaining a high luminance even in long-term use, and a cured product obtained by curing the curable resin composition.
The present invention also relates to a resin composition for optical semiconductor encapsulation which is excellent in adhesion to the surface of an adherend and can obtain an optical semiconductor encapsulant that maintains a high luminance in long-term use, an optical semiconductor encapsulant obtained by curing the resin composition And an optical semiconductor device which is sealed with the optical semiconductor sealing material.
The inventors of the present invention have conducted extensive studies on a resin composition having excellent properties and a cured product obtained by curing the resin composition. As a result, it has been found that the resin composition contains an epoxy resin, a specific organosilicon compound, an organoaluminum compound, It is preferable that the resin composition contains a compound having one hindered amine group so that the resin composition is excellent in storage stability at room temperature and can be cured at a relatively low temperature and that the resulting molded article is excellent in heat resistance, , It has been found that even when used for a long time, a high luminance is maintained. The present inventors have also found that such a resin composition contains an epoxy resin, a specific polysiloxane compound, an organoaluminum compound, and a compound having at least one hindered amine group in one molecule, and the amount of the epoxy resin and the polysiloxane compound , It was found that the resin composition was also excellent in storage stability.
Further, the inventors of the present invention have conducted extensive studies on a resin composition (particularly, an epoxy resin composition) which can obtain a sealing material that does not peel off from an adherend well and maintains a high luminance in a long time of use, (Meth) acrylic polymer, and a curing catalyst, the resulting sealing material has heat resistance (soldering heat resistance), adhesion to the surface of the adherend is excellent, and in the case of using for a long time High luminance is maintained, and the present invention has been reached.
That is, the present invention provides a resin composition having curability,
(A) an epoxy resin,
(B) an Si-OR group wherein R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl substituted aryl group having 7 to 22 carbon atoms, An aralkyl group having a carbon number of 1 to 22,
(C) an organoaluminum compound,
(D) a compound having at least one hindered amine group in one molecule as an essential component.
The present invention also provides a curable resin composition comprising 100 parts by mass of the above epoxy resin (A)
As the (B) organosilicon compound, the following average compositional formula (1):
R 1 a (OR 2 ) b SiO (4-a-b) / 2 (1)
(Wherein R 1 is the same or different and is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl substituted aryl group having 7 to 22 carbon atoms, R 2 is the same or different and represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, a monovalent organic group having an epoxy group or a monovalent organic group having an oxetanyl group, An alkyl substituted aryl group having 7 to 22 carbon atoms or an aralkyl group having 7 to 22 carbon atoms, a and b are numbers of 1.0? A? 1.7 and 0.05? B? 1.0, 1.05? a + b < / = 2.0) is contained in an amount of 10 to 900 parts by mass.
The present invention also provides a resin composition for use as a sealing material for an optical semiconductor, wherein the resin composition comprises an epoxy compound, a polysiloxane compound, a (meth) acrylic polymer, and a curing catalyst It is also.
Hereinafter, the present invention will be described in detail.
It is also a preferred embodiment of the present invention that two or more of the respective preferred embodiments of the present invention described below are combined.
Hereinafter, the curable resin composition of the present invention will be described first, and then the resin composition for optical semiconductor encapsulation of the present invention will be described.
[Curable resin composition]
The curable resin composition of the present invention comprises (A) an epoxy resin, (B) a specific organosilicon compound, (C) an organoaluminum compound, and (D) a compound having at least one hindered amine group in one molecule Is required.
The organosilicon compound and the organoaluminum compound act as curing accelerators (catalysts) for the epoxy resin. However, in the case of only the organosilicon compound and the organoaluminum compound, since the curing of the epoxy resin proceeds excessively, the composition exhibits sufficient storage stability I can not. The addition of a compound having at least one hindered amine group in one molecule in addition to the three components of an epoxy resin, an organic silicon compound and an organoaluminum compound improves the effect of the epoxy resin contained in the organosilicon compound and the organoaluminum compound as a curing accelerator And thus the composition can be made excellent in storage stability.
The organosilicon compound also functions as a curing agent for curing the epoxy resin by reacting with the epoxy resin, in addition to acting as a curing accelerator (catalyst) for the epoxy resin. In short, in the curable resin composition of the present invention, the organosilicon compound acts also as a curing accelerator (catalyst) of an epoxy resin and also as a curing agent.
The curable resin composition of the present invention comprises (A) an epoxy resin, (B) a specific organic silicon compound, (C) an organoaluminum compound, and (D) a compound having at least one hindered amine group in one molecule as an essential component . These components may be reacted in advance with at least two kinds of components to be reacted and contained in the curable resin composition. That is, the curable resin composition containing the reactant in which at least two or more components of the above components (A) to (D) have reacted and the remaining components as essential components is also one of the preferred embodiments of the present invention.
Concretely, for example, as a resin composition having curability,
(A) an epoxy resin, and (B) a Si-OR group wherein R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, An aryl group, or an aralkyl group having 7 to 22 carbon atoms)
(C) an organoaluminum compound,
(D) a curable resin composition characterized by containing, as an essential component, a compound having at least one hindered amine group in one molecule is also one of the preferred embodiments of the present invention.
Further, as the resin composition having curability,
(A) an epoxy resin,
(B) an Si-OR group wherein R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl substituted aryl group having 7 to 22 carbon atoms, An aralkyl group having a carbon number of 1 to 22,
(C) an organoaluminum compound, and (D) a reaction product of a compound having at least one hindered amine group in one molecule as an essential component is also one of the preferred embodiments of the present invention.
The curable resin composition of the present invention comprises (A) an epoxy resin, (B) an organosilicon compound, (C) an organoaluminum compound, and (D) a compound having at least one hindered amine group in one molecule as an essential component However, other components may be contained within a range not hindering the effect of the present invention, and these components may be used alone or in combination of two or more.
≪ (A) Epoxy resin >
The epoxy resin (A) contained in the curable resin composition of the present invention is not particularly limited as long as it is a resin having an epoxy group in the structure, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, Novolak type epoxy resins such as resin and cresol novolak type epoxy resin; Alicyclic epoxy resins; Nitrogen-containing cyclic epoxy resins such as triglycidyl isocyanurate and hydantoin epoxy resin; Hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol F type epoxy resin; Aliphatic epoxy resins; Glycidyl ether type epoxy resin; Bisphenol S type epoxy resin; Biphenyl type epoxy resins; Dicyclocyclic epoxy resin; Naphthalene type epoxy resins and the like. These epoxy resins may be appropriately selected depending on the application, and they may be used alone or in combination of two or more.
However, in order to make both the storage stability at room temperature and the curing property at the time of heat curing compatible, the epoxy resin (A) contained in the curable resin composition of the present invention preferably contains an alicyclic epoxy resin. The content of the alicyclic epoxy resin in the curable resin composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more, based on 100 parts by mass of the total of (A) And most preferably 100 parts by mass, that is, all alicyclic epoxy resins.
When the alicyclic epoxy resin is used, the curable resin composition of the present invention is more excellent in heat resistance.
When the curable resin composition of the present invention is used in applications such as optical semiconductor encapsulants which require high light resistance and heat resistance coloring property, it is preferable to use (A) an epoxy resin containing an alicyclic epoxy resin, a hydrogenated bisphenol A type epoxy resin, It is preferable to use an epoxy resin which does not have any aromatic structure such as bisphenol F type epoxy resin or has an aromatic structure with relatively little aromatic structure. Of these, alicyclic epoxy resins are preferably used, particularly in view of compatibility between storage stability at room temperature and curing at the time of heat curing.
That is, it is preferable that the component (A) of the curable resin composition of the present invention contains a component comprising an alicyclic epoxy resin (hereinafter this component is also referred to as (A-1)), It is one.
The component (A-1) is a compound represented by the following general formula (1):
[Chemical Formula 1]
(Wherein, X 1 and X 2 are the same or different, represents an epoxy-cyclohexane which may have a substituent. R 3 and R 4 are the same or different and represents a divalent organic group having a carbon number of 1 ~ 20. M and n is the same or different and represents an integer of 0 to 10).
If the alicyclic epoxy resin is represented by the general formula (1), the molded article obtained by curing the curable resin composition is more excellent in adhesion. This is presumably due to the fact that both of the ether bond (derived from an epoxycyclohexane group) and the ester bond exist in the molded article, and that the molded article contains a cyclohexane ring.
In the general formula (1), X 1 and X 2 are the same or different and each represents an epoxy cyclohexane group which may have a substituent. The substituent is not particularly limited, but is preferably a hydrocarbon group. The hydrocarbon group is preferably an alkyl group, an aryl group or an aralkyl group. The hydrocarbon group may be an unsubstituted group or a group in which one or two or more hydrogen atoms have been replaced by another hydrocarbon group. Examples of other hydrocarbon groups in this case include an alkyl group (when the hydrocarbon group is an alkyl group, the hydrocarbon group as a whole is an unsubstituted alkyl group), an aryl group, an aralkyl group, and an alkenyl group.
The position of the epoxy group in the epoxycyclohexane group is not limited, and can be formed at an arbitrary position. The position of the substituent group in the form in which the epoxycyclohexane group has a substituent is also not limited.
In the general formula (1), R 3 and R 4 are the same or different and each represents a divalent organic group having 1 to 20 carbon atoms. The organic group is not particularly limited as long as the carbon number is generally 1 to 20, and organic groups including aliphatic hydrocarbon groups and aliphatic hydrocarbons can be mentioned. The organic group containing an aliphatic hydrocarbon refers to an organic group having an aliphatic hydrocarbon and a non-hydrocarbon moiety such as an ether bond (-O-) or an ester bond (-OC (= O) -) in the structure. The aliphatic hydrocarbon includes both of a chain structure and a ring structure.
The organic group is preferably an aliphatic hydrocarbon group having 1 to 18 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
In the general formula (1), m and n are the same or different and each represents an integer of 0 to 10. m and n are not particularly limited as long as they are within the above range, but when m and n are both 0, the other is preferably 1 or more. That is, it is preferable that m + n > = 1.
Specific examples of the component (A-1) include alicyclic epoxy resins represented by the following formulas (2-1) to (2-5). The form in which the component (A-1) is at least one resin selected from the group consisting of these resins is also one of the preferred forms of the present invention.
(2)
In the above formula (2-4), p represents an integer of 1 to 3.
As the above-mentioned components, a compound in which an ester group is directly bonded to a cyclohexane ring, that is, a form in which m = 0 in the general formula (1) is used as in the formulas (2-1) to (2-4) Is more preferable. With such a form, the resulting cured product is excellent in durability. Particularly preferably, it is a resin represented by the formula (2-1).
Specific examples of the above-mentioned alicyclic epoxy resin include, for example, Celloxide 2021P (manufactured by Daicel Chemical Industries, Ltd.) as the compound represented by the formula (2-1) and Celloxide 2081 , Celloxide 2083 and Celloxide 2085 (both manufactured by Daicel Chemical Industries, Ltd.) are preferable.
As the component (A-1), a more polyfunctional alicyclic compound such as 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) Epoxy resins can also be preferably used. The form of such an alicyclic epoxy resin is also one of the preferred forms of the present invention.
Specific examples of the more multifunctional alicyclic epoxy resin include EHPE 3150 (manufactured by Daicel Chemical Industries, Ltd.) and the like.
The weight average molecular weight of the alicyclic epoxy resin is preferably less than 1,500. When the weight average molecular weight of the alicyclic epoxy resin is less than 1,500, the viscosity of the curable resin composition can be prevented from becoming too high, and handling is facilitated. When the curable resin composition is used as a material for the optical semiconductor sealing material, it is possible to prevent the occurrence of air bubbles at the interface between the sealing material and the adherend (substrate, reflector, lead frame, etc.) And the light transmittance and sealing performance of the sealing material obtained from the curable resin composition can be made sufficiently high. The weight average molecular weight of the alicyclic epoxy resin is more preferably 50 or more and less than 1,000, and still more preferably 80 or more and less than 800. The alicyclic epoxy resin preferably has a weight average molecular weight of less than 500, more preferably 50 or more and less than 450. Particularly preferably not less than 80 and not more than 400.
The weight average molecular weight in this specification can be measured by gel permeation chromatography (column: two TSKgel SuperMultipore HZ-N 4.6 * 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard).
When the curable resin composition of the present invention is used for applications requiring high light resistance and heat resistance coloring properties such as optical semiconductor encapsulants and optical members such as lenses, the content of the alicyclic epoxy resin in the curable resin composition of the present invention, It is preferably 5 to 100 parts by mass based on 100 parts by mass of the total amount of the epoxy resin (A). When the content of the alicyclic epoxy resin is within the above range, the storage stability at room temperature is excellent, and curing at a relatively low temperature is possible for a short time. The content of the alicyclic epoxy resin is more preferably 10 to 100 parts by mass, and still more preferably 15 to 100 parts by mass based on 100 parts by mass of the total amount of the epoxy resin (A). From the viewpoint that the molded article obtained from the curable resin composition can further increase the light resistance and heat resistance, it is more preferably 30 to 100 parts by mass, particularly preferably 50 to 100 parts by mass. The content of the alicyclic epoxy resin is preferably higher in the molded article formed from the curable resin composition of the present invention, and the content of the alicyclic epoxy resin (A) is preferably 70% More preferably 90 to 100 parts by mass, and most preferably 100 parts by mass, that is, the curable resin composition of the present invention contains only (A) an alicyclic epoxy resin as the epoxy resin, will be.
When the curable resin composition of the present invention is used in applications such as optical semiconductor encapsulants which require high light resistance and heat resistance coloring property, the epoxy resin (A) further contains a component comprising a hydrogenated epoxy resin May also be referred to as (A-2)). When the curable resin composition contains such components, the obtained molded article has excellent heat cycle resistance.
The hydrogenated epoxy resin is preferably a polyfunctional glycidyl ether compound having an average of 2 or more glycidyl ether groups directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton. Such a hydrogenated epoxy resin is preferably a complete or partial hydrogenated product of an aromatic polyfunctional epoxy compound, and more preferably a hydrogenated product of an aromatic polyfunctional glycidyl ether compound. Concretely, hydrogenated bisphenol A type epoxy compounds represented by the following formula (3-1) and hydrogenated bisphenol F type epoxy compounds represented by the following formula (3-2) are preferable. If the component (A-2) is a hydrogenated bisphenol A-type epoxy compound and / or a hydrogenated bisphenol F-type epoxy compound, the molded article is more excellent in resistance to heat cycles.
In the formulas (3-1) and (3-2), a hydrogen atom of a part of a hydrocarbon such as a cyclohexyl ring or a methylene chain may be substituted. The substituent is preferably a halogen atom such as fluorine, chlorine or bromine, or a hydrocarbon group which may have a substituent. Among the hydrocarbon groups, an alkyl group is preferable, and a methyl group and an ethyl group are more preferable.
(3)
Q represents an integer of 1 or more.
When the hydrogenated epoxy resin is a hydrogenated bisphenol A type epoxy compound and / or hydrogenated bisphenol F type epoxy compound, the hydrogenation ratio of the epoxy resin is preferably greater than 95%. If the hydrolysis rate is higher than 95%, the aromatic ring-like structure contained in the component (A-2) is sufficiently reduced, so that the coloration (yellowing) caused by heat or light of the resulting cured product can be sufficiently suppressed. More preferably, the hydrogenation rate is greater than 98%, and more preferably the hydrogenation rate is 100%.
Specific examples of the hydrogenated bisphenol A type epoxy compound include those obtained by hydrogenating a bisphenol A type epoxy compound. Examples thereof include YX-8040 (manufactured by Mitsubishi Chemical Corporation, weight average molecular weight 3831), ST-4000D Shin-Nittsu Chemical Co., Ltd.).
As the hydrogenated bisphenol F type epoxy compound, specifically, those obtained by hydrogenating a bisphenol F type epoxy compound can be used.
The weight average molecular weight of the hydrogenated epoxy resin is preferably 1,000 or more. More preferably 1,500 or more and less than 8,000, and even more preferably 2,000 or more and less than 6,000.
The weight average molecular weight of the hydrogenated epoxy resin can be measured by the same method as the weight average molecular weight of the alicyclic epoxy resin described above.
The hydrogenated epoxy resin preferably has an epoxy equivalent of 500 or more. As a result, the molded article is further excellent in the heat cycle resistance. The epoxy equivalent is more preferably 800 or more. The epoxy equivalent is preferably 4,000 or less. More preferably 2,000 or less.
The components (A-1) and (A-2) may contain aromatic rings in the structure within a range that does not impair the light resistance and heat resistance of the molded article. In this case, the content of the aromatic ring is preferably 20 parts by mass or less in the proportion of the aromatic ring contained in the structure, when the total amount of the components (A-1) and (A-2) is 100 parts by mass. More preferably not more than 10 parts by mass, more preferably not more than 5 parts by mass, most preferably not more than 0 parts by mass, i.e., does not include an aromatic ring.
The epoxy resin (A) may contain an epoxy resin other than the above-mentioned components (A-1) and (A-2), but may contain only the component (A- A-2).
Examples of the epoxy resin other than the above components (A-1) and (A-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin or cresol novolak type epoxy resin , Nitrogen-containing cyclic epoxy resins such as triglycidyl isocyanurate and hydantoin epoxy resin, aliphatic epoxy resins, glycidyl ether type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins Epoxy resin, dicyclocyclic epoxy resin, and naphthalene-type epoxy resin.
Specific examples of the bisphenol A epoxy compound include a basic liquid epoxy resin Grade 828 (manufactured by Mitsubishi Chemical Corporation) and the like.
The compounding ratio of the component (A-1) to the component (A-2) is preferably 100/0 to 50/50 in terms of the mass ratio (component (A-1) / component (A-2)). By adjusting the compounding ratio to such a range, the molded article obtained from the curable resin composition is excellent in transparency, heat resistance, light resistance, adhesion, resistance to heat, and the like. The mass ratio is more preferably 55/45 or more, still more preferably 65/35 or more, and most preferably 71/29 or more. As a result, the viscosity of the curable resin composition can be prevented from becoming excessively high, and the occurrence of bubbles can be suppressed, so that the molded article obtained from the curable resin composition can have sufficiently high light transmittance and sealing performance. Particularly, when the mass ratio is 90/10 or less, the molded article obtained from the curable resin composition has better heat cycle resistance.
When the curable resin composition of the present invention is used for applications requiring heat resistance and light resistance, and electrical characteristics under heat and humidity, the total amount of chlorine in the epoxy resin (A) And preferably 1,000 ppm or less.
Particularly, when the curable resin composition of the present invention is used in the optical semiconductor sealing material, the total chlorine content in the epoxy resin (A) is preferably 200 ppm or less. When the total amount of chlorine in the epoxy resin (A) is 200 ppm or less, the molded article obtained from the curable resin composition can be used for an LED sealing material to maintain a higher luminance in a long-term use. The total amount of chlorine in the epoxy resin (A) is more preferably 100 ppm or less, and still more preferably 50 ppm or less.
The total chlorine content in the epoxy resin can be measured based on JIS K 7243-3.
≪ (B) Organosilicon compound >
The curable resin composition of the present invention comprises a Si-OR group wherein R is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl substituted aryl group having 7 to 22 carbon atoms, Or an aralkyl group having 7 to 22 carbon atoms). In the curable resin composition, the organosilicon compound having an Si-OR group functions as an excellent curing accelerator of an epoxy resin in the presence of an organoaluminum compound. Furthermore, depending on the number and the amount of Si-OR groups contained in the organosilicon compound, not only as a curing accelerator but also as a curing agent for an epoxy resin, a cured product having superior heat resistance and crack resistance is given, It is possible to maintain initial characteristics over a long period of time even under strict use conditions such as a sealing material, a semiconductor sealing material, and a wiring board.
Specific examples of the alkyl group having 1 to 22 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, . Specific examples of the alkenyl group having 2 to 22 carbon atoms include a vinyl group, an allyl group, a cyclohexenyl group and a norbornyl group. Specific examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a tolyl group, a p-hydroxyphenyl group, and a naphthyl group. Specific examples of the alkyl-substituted aryl group having 7 to 22 carbon atoms include a methylphenyl group, an ethylphenyl group, a t-butylphenyl group, and an n-octylphenyl group. Specific examples of the aralkyl group having 7 to 22 carbon atoms include a 1- (p-hydroxyphenyl) ethyl group, a 2- (p-hydroxyphenyl) ethyl group, and a benzyl group.
Examples of the organosilicon compound having the Si-OR group include a polysiloxane compound including silsesquioxane and silicone elastomer obtained by hydrolysis and condensation of a low molecular weight compound and a low molecular weight organosilicon compound or a mixture of a low molecular weight compound and a polysiloxane compound . However, when the organosilicon compound is used not only as a curing accelerator for an epoxy resin but also as a curing agent, it is preferable to use an organosilicon compound having two or more Si-OR groups in one molecule as an essential component.
The low-molecular organosilicon compound is preferably a compound represented by the following general formula (4):
SiR 5 a (OR 6 ) 4-c (4)
(Wherein R 5 is the same or different and is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl substituted aryl group having 7 to 22 carbon atoms, A monovalent organic group having an epoxy group, or a monovalent organic group having an oxetanyl group, R 6 is independently the same as R defined above, and c is an integer of 1 to 3.) Can be preferably used.
Specific examples of the low molecular weight organosilicon compound represented by the general formula (4) include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n- N-hexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, 3-glycidoxypropyl tri Methoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, But are not limited to, phenyl trimethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, dimethyl dimethoxysilane, dimethyl diethoxysilane, diisopropyl dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, cyclohexylmethyldimethoxysilane, Ethoxy silane, and the like. These compounds may be used alone or in combination of two or more.
Examples of the low molecular weight organosilicon compound include compounds represented by the following general formula (5):
Si (OR < 7 >) 4 (5)
(Wherein R 7 is independently the same as R defined above) can also be preferably used.
Specific examples of the low molecular weight organosilicon compound represented by the general formula (5) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetraisobutoxysilane. These compounds may be used alone or in combination of two or more.
Examples of the polysiloxane compound include compounds represented by the following average formula (6):
R 8 d (OR 9 ) e SiO (4-de) / 2 (6)
(Wherein R 8 is the same or different and is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl substituted aryl group having 7 to 22 carbon atoms, A monovalent organic group having an epoxy group, or a monovalent organic group having an oxetanyl group, R 9 is the same or different and represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, An alkyl substituted aryl group having 7 to 22 carbon atoms or an aralkyl group having 7 to 22 carbon atoms, d and e are numbers of 1.0? D? 1.7 and 0.05? E? 1.0, 1.05? D + e ≪ / = 2.0). Since the curable resin composition contains the polysiloxane compound represented by the average composition formula (6), the molded article obtained from the curable resin composition is superior in heat resistance and crack resistance, and can maintain a higher luminance in long- have.
Specific examples of the alkyl group having 1 to 22 carbon atoms in the average composition formula (6) include methyl, ethyl, n-propyl, isopropyl, n-butyl, Hexyl group, and n-decyl group. Specific examples of the alkenyl group having 2 to 22 carbon atoms include a vinyl group, an allyl group, a cyclohexenyl group and a norbornyl group. Specific examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a tolyl group, a p-hydroxyphenyl group, and a naphthyl group. Specific examples of the alkyl-substituted aryl group having 7 to 22 carbon atoms include a methylphenyl group, an ethylphenyl group, a t-butylphenyl group, and an n-octylphenyl group. Specific examples of the aralkyl group having 7 to 22 carbon atoms include a 1- (p-hydroxyphenyl) ethyl group, a 2- (p-hydroxyphenyl) ethyl group, and a benzyl group. Specific examples of the monovalent organic group having an epoxy group include 2-glycidoxyethyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclo Hexyl) propyl group and the like. Specific examples of the monovalent organic group having an oxetanyl group include 3-methyl-3-n-propoxymethyloxetanyl group, 3-ethyl-3-n-propoxymethyloxetanyl group, n-butoxymethyloxetanyl group and the like.
The polysiloxane compound represented by the average composition formula (6) can be produced by a known method. For example, the polysiloxane compound represented by the following general formula (7):
SiR 10 f (OR 11 ) 4-f (7)
Hydrolysis of a silane compound represented by (wherein, R 10 is the same as R 8 in the average composition formula (6). R 11 is the same as R 9 in the average composition formula (6). F is an integer of 1 to 3.) (7) and a silane compound represented by the following general formula (8): < EMI ID =
Si (OR 12) 4 (8 )
(Wherein R 12 is the same as R 9 in the average composition formula (6)).
Specific examples of the silane compound represented by the general formula (7) include the same specific examples as the specific examples of the low molecular weight organosilicon compound represented by the general formula (4). These compounds may be used alone or in combination of two or more.
Specific examples of the alkyl silicate represented by the general formula (8) include the same specific examples of the low molecular weight organosilicon compound represented by the general formula (5). These compounds may be used alone or in combination of two or more.
The weight average molecular weight of the polysiloxane compound in terms of polystyrene is preferably 500 to 20,000. When the weight average molecular weight of the polysiloxane compound is within the above range, the viscosity of the curable resin composition can be prevented from becoming excessively high, and handling during molding can be facilitated. Further, it is possible to make the cured product obtained from the curable resin composition sufficiently high in heat resistance, crack resistance, resistance to heat cycle, and the like, and to prevent the occurrence of air bubbles at the interface between the sealing material and the sealing material and the adherend And the light transmittance, heat resistance, crack resistance, and sealing performance of the sealing material obtained from the curable resin composition can be sufficiently high.
The weight average molecular weight of the polysiloxane is more preferably 1,000 to 15,000, still more preferably 1,500 to 10,000, and particularly preferably 2,000 to 10,000.
The weight average molecular weight of the polysiloxane compound can be measured by the same method as the weight average molecular weight of the alicyclic epoxy resin described above.
The organic silicon compound may be a liquid at 25 占 폚 or a solid. When the polysiloxane compound is a liquid at 25 占 폚, it is preferable that the viscosity at 25 占 폚 is 1 to 8,000 Pa 占 퐏. With such a viscosity, the viscosity of the curable resin composition can be prevented from becoming excessively high, and handling becomes easy. The viscosity at 25 캜 is more preferably from 5 to 5,000 Pa · s, and still more preferably from 10 to 3,000 Pa · s.
The viscosity in the present specification can be measured by an R / S rheometer (manufactured by Brookfield).
The content of the organosilicon compound (B) in the curable resin composition differs depending on the amount of the -OR group contained in the organosilicon compound, when mainly used as the curing accelerator for the epoxy resin (A) ) Epoxy resin is preferably from 0.05 to 10 parts by mass, more preferably from 0.1 to 8 parts by mass, and still more preferably from 0.2 to 5 parts by mass, based on 100 parts by mass of the total amount of the epoxy resin.
When the content of the organosilicon compound (B) in the curable resin composition is to act not only as a curing accelerator but also as a curing agent, the content of the organosilicon compound in the curable resin composition depends on the epoxy equivalent of the epoxy resin (A) and the number of epoxy groups in one molecule , And further can be appropriately selected according to the target properties of the cured product, but it is preferably 10 to 900 parts by mass when the total amount of the epoxy resin (A) is 100 parts by mass. When the content of the organosilicon compound (B) is within the above range, the organosilicon compound can exert a satisfactory function as a curing agent for curing the epoxy resin by reacting with the epoxy resin, in addition to the function of the curing accelerator have. In addition, the formed body formed from the curable resin composition has excellent heat resistance, light resistance and crack resistance, and can exhibit good luminance retention when used in an LED sealing material. More preferably 10 to 500 parts by mass, still more preferably 15 to 300 parts by mass, and particularly preferably 20 to 150 parts by mass.
≪ (C) Organoaluminum compound >
The curable resin composition of the present invention contains an organoaluminum compound. Since the curable resin composition contains the organoaluminum compound, the curing reaction between the epoxy resin and further the epoxy resin and the organosilicon compound can be promoted under relatively mild conditions in the presence of the organosilicon compound, A cured product can be obtained. Thus, when the adherend is made of a resin material having a lower heat resistance as compared with an inorganic material, it is possible to reduce the influence on the adherend by heating in the heat curing step.
The organoaluminum compound is not particularly limited, but is preferably a compound having good compatibility with the inert component of the curable resin composition of the present invention. Specifically, it is preferably an aluminum chelate compound or aluminum alkoxide, more preferably an aluminum chelate compound. By using an aluminum chelate compound as the organoaluminum compound, a molded article obtained from the curable resin composition of the present invention is excellent in heat resistance, light resistance and moisture resistance, and is used as a light semiconductor sealing material or an optical member, , It is possible to maintain initial characteristics in long-term use under a high-temperature and high-humidity environment.
Examples of the aluminum chelate compound and the aluminum alkoxide include compounds represented by the following general formula (9):
[Chemical Formula 4]
(Wherein R 13 is the same or different and represents an alkyl group or an alkoxyl group having 1 to 22 carbon atoms, R 14 is the same or different and represents an alkyl group having 1 to 12 carbon atoms, and g denotes a valence of Al ion. and h represents a number of 0 to 3. The dotted line between the oxygen atom and Al in the formula means that the oxygen atom is coordinated to Al. The two oxygen atoms coordinated to Al and the three carbon atoms between the two oxygen atoms The arc of the dotted line of the structure part to be formed indicates that at least one pair of atoms of the structural part is connected by a double bond and the double bond may be conjugated with the ring structure forming the arc part of the dotted line) Can be preferably used. The expression " R 13 is the same or different and represents an alkyl group or an alkoxyl group having 1 to 22 carbon atoms " means that when there are a plurality of structural moieties in () to which h is assigned, the structure of R 13 May be the same or may be different from each other. The same applies to R 14.
Specific examples of the aluminum chelate compound represented by the general formula (9) include, for example, aluminum ethyl acetoacetate diisopropylate, aluminum ethylacetoacetate di-n-butoxide, aluminum methyl acetoacetate, (Ethyl acetoacetate), aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum tris (ethyl acetoacetate), aluminum triacetate, diisobutoxide, (Trade name, manufactured by Kawaken Fine Chemicals Co.), aluminum tris (ethyl acetylacetonate), aluminum tris (octadecyl acetoacetate), aluminum tris (hexadecyl acetoacetate), aluminum tris Acetoacetate), aluminum tris (dodecyl acetoacetate Tate), aluminum bisethyl acetate monoacetylacetonate, and the like. These compounds may be used alone or in combination of two or more.
Among the compounds represented by the general formula (9), the aluminum alkoxide is represented by the following general formula (10):
[Chemical Formula 5]
(Wherein R 15 represents an alkyl group, and three R 15 may be the same alkyl group or may be different alkyl groups). That is, it is a compound represented by h = 0 in the general formula (9).
In the general formula (10), R 15 represents an alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n- butyl group, , A cyclohexyl group, and an n-decyl group.
R 15 in the general formula (10) is preferably an alkyl group having 1 to 22 carbon atoms.
Specific examples of the aluminum alkoxide represented by the general formula (10) include aluminum triethoxide, aluminum triisopropoxide, aluminum tri-sec-butoxide, aluminum tri-tert-butoxide and the like.
The content of the organoaluminum compound (C) in the curable resin composition is preferably 0.05 to 5 parts by mass based on 100 parts by mass of the total of the epoxy resin (A) and the organosilicon compound (B). By setting the content of the organoaluminum compound in such a range, the curing rate can be sufficiently increased, and the curing of the cured product under the use environment can be sufficiently suppressed. The content of the organoaluminum compound is more preferably 0.075 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass.
≪ (D) Compound having hindered amine group >
The curable resin composition of the present invention contains a compound having at least one hindered amine group in one molecule. When the curable resin composition contains a compound having at least one hindered amine group in one molecule, the curable resin composition is excellent in storage stability. Thus, after the curable resin composition is compounded, In the optical semiconductor encapsulation, a sufficient time can be secured until the completion of the work, or the resin can be used for a long time after the compounding. In addition, in a typical amine compounding, the epoxy resin of the component component may be altered at relatively low temperatures, a reaction other than the desired curing reaction may be caused, or the curing may be carried out at a high temperature of 170 캜 or higher, It is possible to suppress these problems by using a compound having a hindered amine group. Further, by using a compound having a hindered amine group, curing can be completed in a short time under relatively mild conditions of about 120 deg. C, for example, about 120 deg. C to about 150 deg. . Further, the compound having a hindered amine group does not generate a coloring material well even in the presence of oxygen as compared with a conventional amine compound. Therefore, when the above curable resin composition is used for optical members such as optical semiconductor encapsulants and lenses, Coloration is less likely to occur compared with a molded article obtained from a composition using the above-mentioned composition, and an excellent light transmittance (brightness retentivity) can be exhibited.
Examples of the compound having a hindered amine group include compounds represented by the following general formula (11):
[Chemical Formula 6]
(Wherein, R 16 represents a hydrogen atom, an aralkyl group, an acyl group, an oxy radical group having 1 to 18 alkyl group, having from 6 to 20 carbon atoms an aryl group, having 7 to 12 of, or OR 21. R 21 is hydrogen An alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, R 17 to R 20 are the same or different and each represents an alkyl group having 1 to 6 carbon atoms, Or are bonded to each other to form an aliphatic ring having 4 to 12 carbon atoms) is preferred. Accordingly, as the compound having a hindered amine group, a piperidine compound having a structure represented by the general formula (11) or a compound having a piperidine ring represented by the general formula (11) as a part of the structure is preferable .
Specific examples of the compound having at least one hindered amine group in the molecule include 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 2 , 2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl benzoate, N- (2,2,6,6- Tetramethyl-4-piperidyl) dodecylsuccinic acid imide, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butane tetracarboxylate, bis (1,2,2,6,6- 6,6-pentamethyl-4-piperidyl) di (tridecyl) butane tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetra Methyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,3 , 4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4-piperidinyl), bis (2,2,6,6-tetra La-methyl-1-undecanoic -1,3 As and the like can be mentioned 4-yl) carbonate. Of these, compounds having two or more hindered amine groups in one molecule are preferable because they are excellent in compatibility with epoxy resins and have an effect of enhancing storage stability. Specific examples of the compound having two or more hindered amine groups in one molecule include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) sebacate, 1,2,3,4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) 2,3,4-butanetetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid tetrakis ( 2,2,6,6-tetramethyl-4-piperidinyl), and the like.
The content of the compound having at least one hindered amine group in one molecule (D) in the curable resin composition is preferably 0.05 to 5 parts by mass per 100 parts by mass of the total of the epoxy resin (A) and the organosilicon compound (B) It is desirable to be wife. By containing a compound having at least one hindered amine group in one molecule in such a ratio, the curable resin composition can have better storage stability. The content of the compound having at least one hindered amine group in one molecule is more preferably 0.075 to 4 parts by mass, still more preferably 0.1 to 3 parts by mass, and particularly preferably 0.1 to 2 parts by mass.
The curable resin composition of the present invention comprises (A) an epoxy resin, (B) a specific organic silicon compound, (C) an organoaluminum compound, and (D) a compound having at least one hindered amine group in one molecule as an essential component And may contain an acid anhydride, an aromatic amine compound, a phenol resin, or the like as a component having a function as a curing agent for curing the epoxy resin by reacting with the epoxy resin, and these components may be used alone or in combination of two or more. Can be used. That is, a mode comprising at least one compound selected from the group consisting of an acid anhydride, an aromatic amine compound, and a phenol resin as a curing agent is also a preferable form of the present invention.
<Acid anhydride>
When the curable resin composition contains an acid anhydride, specific examples of the acid anhydride include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride and methylnadic acid . These compounds may be used alone or in combination of two or more.
<Aromatic amine compound>
When the curable resin composition contains an aromatic amine compound, the aromatic amine compound is an amine compound having an aromatic ring skeleton in its structure, and includes primary amine compounds, secondary amine compounds, tertiary amine compounds, and the like However, it is preferable to use a primary amine compound and / or a secondary amine compound. The number of amino groups in one molecule is not particularly limited, but is preferably 1 to 10, for example. More preferably 2 to 4 carbon atoms.
Examples of the aromatic amine compound include methaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, bis (4-aminophenoxy) phenylsulfone, 1,3- Bis (4-aminophenoxy) phenyl) propane, 2,7-diaminofluorene, 9,9-bis (4-aminophenoxy) Oren and the like. These compounds may be used alone or in combination of two or more.
<Phenolic resin>
When the curable resin composition contains a phenol resin, the phenol resin is not particularly limited as long as it acts as a curing agent for the epoxy resin, and examples thereof include phenol novolak resins, cresol novolak resins, bisphenol A novolac resins, Various phenol resins such as pentadiene phenol resin, phenol aralkyl resin and terpene phenol resin; Various phenol resins such as polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde and glyoxal can be used.
The curable resin composition of the present invention is preferably used as a sealing material for optical semiconductors.
Further, such a curable resin composition for optical semiconductor encapsulation may further contain a (meth) acrylic polymer, and such a curable resin composition is also one of preferred embodiments of the present invention. The (meth) acrylic polymer is preferably the same as the (meth) acrylic polymer contained in the resin composition for optical semiconductor encapsulation of the present invention to be described later, and the blending ratio in the resin composition is preferably, Is preferably the same as the blending ratio in the resin composition.
[Resin composition for optical semiconductor encapsulation]
The resin composition for optical semiconductor encapsulation of the present invention may contain other components as long as it contains an epoxy compound, a polysiloxane compound, a (meth) acrylic polymer and a curing catalyst.
The epoxy compound, polysiloxane compound, (meth) acrylic polymer and curing catalyst may be used alone or in combination of two or more.
<Epoxy Compound>
The epoxy compound contained in the resin composition for optical semiconductor encapsulation of the present invention is not particularly limited as long as it has an epoxy group in the structure, and an alicyclic epoxy compound, a hydrogenated epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound, And one kind or two kinds or more of them may be used, and among them, an alicyclic epoxy compound is preferable.
That is, it is one of the preferred embodiments of the present invention that the epoxy compound contained in the resin composition for optical semiconductor encapsulation of the present invention comprises a component comprising an alicyclic epoxy compound (hereinafter also referred to as component (A1)).
When the alicyclic epoxy compound is used, the resin composition for optical semiconductor encapsulation of the present invention is more excellent in heat resistance.
The component (A1) is preferably a compound represented by the above-mentioned general formula (1). The specific examples of the compound represented by the general formula (1) and the preferable structure among the compounds represented by the general formula (1) are also the same as those described above. The same effects are obtained by using a compound represented by the general formula (1) or a compound having a preferred structure among them.
The weight average molecular weight of the alicyclic epoxy compound is preferably the same as the weight average molecular weight of the alicyclic epoxy compound in the curable resin composition of the present invention described above, and the effect obtained thereby is also the same.
The content of the component (A1) in the resin composition for optical semiconductor encapsulation of the present invention is preferably 30 to 100 parts by mass when the total amount of the epoxy compound is 100 parts by mass. When the content of the component (A1) is within the above range, the light resistance and heat resistance of the sealing material obtained from the resin composition for optical semiconductor encapsulation can be further increased. The content of the component (A1) is more preferably from 50 to 100 parts by mass when the total amount of the epoxy compound is 100 parts by mass. It is preferable that the molded article formed from the resin composition for optical semiconductor encapsulation of the present invention has a higher content of component (A1) than that of the epoxy compound, More preferably 90 to 100 parts by mass, and most preferably 100 parts by mass, that is, the resin composition for optical semiconductor encapsulation of the present invention contains only an alicyclic epoxy compound as an epoxy compound .
The epoxy compound may further contain a component comprising a hydrogenated epoxy compound (hereinafter also referred to as component (A2)). When the resin composition for optical semiconductor encapsulation contains such a component, the obtained sealing material has excellent heat-cycle resistance.
The hydrogenated epoxy compound may be the same as the hydrogenated epoxy resin in the above-mentioned curable resin composition of the present invention, and the preferable form (preferred structure, weight average molecular weight, and epoxy equivalent) is the same. The effect obtained by using the hydrogenated epoxy resin or its preferable form is also the same as that of the curable resin composition of the present invention described above.
The components (A1) and (A2) may contain an aromatic ring in the structure within a range that does not impair the light resistance and heat resistance of the sealing material. In this case, the content of the aromatic ring is preferably the same as the content of the aromatic ring in the structures of (A-1) and (A-2) in the curable resin composition of the present invention described above.
The epoxy compound may contain an epoxy compound other than the above-mentioned components (A1) and (A2), but it is preferable that the epoxy compound is composed only of the component (A1) and / or the component (A2).
When the epoxy compound contains both of the components (A1) and (A2), the blending ratio of the component (A1) and the component (A2) is 40/60 to 90 / 10 < / RTI > By adjusting the compounding ratio to such a range, the sealing material obtained from the resin composition for optical semiconductor encapsulation has excellent transparency, heat resistance, light resistance, adhesion, resistance to heat, and the like. The mass ratio is more preferably 50/50 or more, still more preferably 65/35 or more, and most preferably 71/29 or more. As a result, the viscosity of the resin composition for optical semiconductor encapsulation can be prevented from becoming excessively high, and the occurrence of bubbles can be suppressed, so that the light transmissivity and sealing performance of the sealing material obtained from the resin composition for optical semiconductor encapsulation can be made sufficiently high. The mass ratio is preferably 85/15 or less. As a result, the sealing material obtained from the resin composition for optical semiconductor encapsulation is further excellent in resistance to heat cycles.
The content of the epoxy compound is preferably 10 to 90 parts by mass when the total amount of the resin composition for optical semiconductor encapsulation is 100 parts by mass. More preferably from 20 to 80 parts by mass, and still more preferably from 30 to 70 parts by mass.
The epoxy compound contained in the resin composition for optical semiconductor encapsulation may contain an epoxy compound other than the above-mentioned components (A1) and (A2), but is preferably composed only of the component (A1) and / or the component (A2).
<Polysiloxane Compound>
The resin composition for optical semiconductor encapsulation of the present invention contains a polysiloxane compound. Since the resin composition for optical semiconductor encapsulation contains a polysiloxane compound, the sealing material obtained from the resin composition for optical semiconductor encapsulation can maintain a high luminance in long-term use.
The production method of the polysiloxane compound is not particularly limited, but the following general formula (12)
SiR 22 i R 23 j (OR 24 ) 4- (i + j) (12)
(Wherein, R 22 and R 23 are each the same or different, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a (meth) group having an acrylic, or represents a group having a fluorine atom, R 24 is an alkyl group, an aryl An aralkyl group or an alkenyl group, and i and j are each 0 or 1, and 1 < i + j < 2 is satisfied) is preferably a polysiloxane compound obtained by hydrolyzing and condensing a silane compound.
Wherein the general formula (12), R 22 and R 23 are each the same or different, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a (meth) group having an acrylic, or represents a group having a fluorine atom, R 24 Represents an alkyl group, an aryl group, an aralkyl group, or an alkenyl group. These groups may have a substituent or may be an unsubstituted group having no substituent.
Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) ethyl group, 3-methylcyclopropyl group, Hexyl) propyl group and the like. Specific examples of the aryl group include a phenyl group, a tolyl group, a p-hydroxyphenyl group, and a naphthyl group. Specific examples of the aralkyl group include a 1- (p-hydroxyphenyl) ethyl group, a 2- (p-hydroxyphenyl) ethyl group, and a benzyl group. Specific examples of the alkenyl group include a vinyl group and an allyl group. Specific examples of the group having a (meth) acryl group include a 3-acryloxypropyl group and a 3-methacryloxypropyl group. Specific examples of the group having a fluorine atom include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a 3,3,3-trifluoropropyl group.
Specific examples of the silane compound represented by the general formula (12) include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the low-molecular compound represented by the general formula (4) Specific examples of the organosilicon compound may be mentioned. These compounds may be used alone or in combination of two or more.
As the silane compound represented by the general formula (12), methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, (3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxy Silane, cyclohexylmethyldimethoxysilane, methylphenyldimethoxysilane, and more preferably methyltrimethoxysilane, methyltriethoxysilane, n-hexyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, Cyclohexylmethyldimethoxysilane, and methylphenyldimethoxysilane.
The weight average molecular weight and viscosity of the polysiloxane compound are preferably the same as the weight average molecular weight and viscosity of the polysiloxane compound used in the curable resin composition of the present invention described above and the reason and the measurement method are the same, The molecular weight is preferably in the range of 800 to 10,000 or 1,000 to 8,000.
The content of the polysiloxane compound is preferably 10 to 80 parts by mass when the total amount of the resin composition for optical semiconductor encapsulation is 100 parts by mass. More preferably from 20 to 70 parts by mass, and still more preferably from 30 to 60 parts by mass.
<(Meth) acrylic polymer>
The resin composition for optical semiconductor encapsulation of the present invention contains a (meth) acrylic polymer. Since the resin composition for optical semiconductor encapsulation contains the (meth) acrylic polymer, the sealing material obtained from the resin composition for optical semiconductor encapsulation can have excellent adhesion to the surface of the adherend.
The (meth) acrylic polymer is preferably a copolymer of (meth) acrylic acid and / or (meth) acrylate. As the (meth) acrylate, it is preferable to contain (meth) acrylate having a hydroxyl group in the molecule. By containing the (meth) acrylate having a hydroxyl group, the resin composition for optical semiconductor encapsulation of the present invention is further excellent in adhesion to the surface of the adherend.
Specific examples of the (meth) acrylate having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, Methyl (meth) acrylate, ethyl (α-hydroxymethyl) acrylate, butyl (α-hydroxymethyl) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol mono . Among these, 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate are preferable, and 2-hydroxyethyl acrylate and hydroxypropyl acrylate are more preferable.
The content of the (meth) acrylate having a hydroxyl group in the molecule is preferably from 0.5 to 60 parts by mass when the total amount of the monomer components constituting the raw material of the (meth) acrylic polymer is 100 parts by mass. If the content of the (meth) acrylate having a hydroxyl group in the molecule is less than 0.5 part by mass, the introduction ratio of the hydroxyl group becomes small, and the sealing material obtained from the resin composition for optical semiconductor encapsulation becomes turbid and the light transmittance may deteriorate. When the content of the (meth) acrylate having a hydroxyl group in the molecule exceeds 60 parts by mass, the viscosity of the resin composition for optical semiconductor encapsulation may become excessively high. The content of the (meth) acrylate having a hydroxyl group in the molecule is more preferably 5 to 50 parts by mass, and still more preferably 10 to 40 parts by mass.
Specific examples of the (meth) acrylate other than the (meth) acrylate having a hydroxyl group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylate, lauryl (meth) acrylate, propyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate such as 3,4-epoxycyclohexylmethyl (meth) acrylate and 4-hydroxybutyl acrylate glycidyl ether.
The content of the (meth) acrylate other than the (meth) acrylate having a hydroxyl group in the molecule is preferably 30 to 90 parts by mass based on 100 parts by mass of the total amount of the monomer components as raw materials of the (meth) acrylic polymer . By including (meth) acrylate other than (meth) acrylate having a hydroxyl group at such a ratio, the viscosity of the resin composition for optical semiconductor encapsulation can be prevented from becoming excessively high, and handling is facilitated. More preferably 40 to 80 parts by mass.
The proportion of the (meth) acrylic acid in the monomer component as a raw material of the (meth) acrylic polymer is preferably 0 to 30 parts by mass when the total amount of the monomer components constituting the raw material of the (meth) acrylic polymer is 100 parts by mass . More preferably 0 to 20 parts by mass.
In the above, the preferable ratio of the (meth) acrylate having a hydroxyl group in the monomer component as a raw material of the (meth) acrylic polymer, the (meth) acrylate other than the (meth) acrylate having a hydroxyl group, (Meth) acrylate and (meth) acrylic acid other than the (meth) acrylate having a hydroxyl group and the (meth) acrylate having a hydroxyl group, It is preferable to include them in a preferable ratio of each component described.
The weight average molecular weight of the (meth) acrylic polymer is preferably 1,000 to 200,000. If the weight average molecular weight of the (meth) acrylic polymer is less than 1,000, the crack resistance of the sealing material obtained from the composition for optical semiconductor sealing material may be lowered. When the weight average molecular weight of the (meth) acrylic polymer is more than 200,000, the viscosity of the composition for optical semiconductor encapsulant is increased, and the workability may be lowered. The weight average molecular weight of the (meth) acrylic polymer is more preferably 5,000 to 100,000.
The content of the (meth) acrylic polymer is preferably 5 to 60 parts by mass when the total amount of the resin composition for optical semiconductor encapsulation is 100 parts by mass. More preferably 10 to 50 parts by mass, and still more preferably 15 to 40 parts by mass.
<Curing Catalyst>
The curing catalyst is preferably a cationic curing catalyst. If the curing catalyst is a cationic curing catalyst, the cationic curing method can be employed as the curing method, and compared with the case of employing the above-described curing method using the acid anhydride, The sealing material has better heat cycle resistance. Further, by cationically curing the epoxy compound containing the component (A) comprising the alicyclic epoxy compound, the main chain skeleton of the cured product can contain more ether bonds as compared with the ester bond, Durability such as moisture resistance, heat resistance and light fastness of the sealing material obtained from the resin composition for use in the present invention can be improved.
The catechin curing catalyst is not particularly limited as long as it is a compound capable of generating a cationic species for initiating polymerization by photo-excitation or heat, but it is more preferably a cationic cation curing catalyst or a thermal cation curing catalyst. By using a photocathode curing catalyst, a compound containing a cationic species is excited by light to cause a photodecomposition reaction, and the photocuring proceeds. Further, by using a thermal cationic curing catalyst, a compound containing a cationic species is excited by heating to cause a thermal decomposition reaction, and thermal curing proceeds. Among them, it is more preferable to use a thermal cationic curing catalyst. That is, the form in which the cationic curing catalyst is a thermal cationic curing catalyst is one of the preferred embodiments of the present invention.
The photo cationic curing catalyst is also called a photo cationic polymerization initiator and exhibits a substantial function as a curing agent by light irradiation.
Examples of the photocathion curing catalyst include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- ((phenylthio) phenyl) phenyldiphenylsulfonium hexafluorophosphate, (Diphenylsulfonium) phenyl] sulfide bis hexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, (2,4-cyclopentadiene- Yl) [(1-methylethyl) benzene] -Fe-hexafluorophosphate, diallyl iodonium hexafluoroantimonate and the like are preferable.
The thermal cationic curing catalyst is also referred to as a thermal acid generator, a thermosetting agent, a thermal cation generator, and a cationic polymerization initiator. When the composition for a sealing material has a curing temperature, it exhibits a substantial function as a curing agent.
As the above-mentioned thermal cation curing catalyst, for example, a compound represented by the following general formula (13):
(R 25 t R 26 u R 27 v R 28 w Z) + s (AX y ) -s (13)
(Wherein Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and halogen elements.) R 25 , R 26 , R 27 and R 28 U, v and w are 0 or a positive number, and the sum of t, u, v and w is equivalent to the valence of Z. The cation (R 25 t R 26 u R 27 v R 28 w Z) + s represents the onium salt. a represents a metal element or a metalloid elements (metalloid) central atom of the halide complex, B, P, As, Sb , Al, Ca, in, Ti X is at least one element selected from the group consisting of Zn, Sc, V, Cr, Mn, and Co, X is a halogen element, s is the charge of a halide complex ion, y is a halide complex ion Is the number of halogen elements in the compound (I).
The anion of formula (13) (AX y) - s in a specific example, a borate (BF 4-), hexafluoro-tetrafluoro phosphate (PF 6 -), anti-hexafluoro-Mo carbonate (SbF 6 - ), Hexafluoroarsenate (AsF 6 - ), and hexachloroantimonate (SbCl 6 - ).
It may be also represented by the anion - also the general formula AX y (OH). Examples of other anions include perchlorate ion (ClO 4 - ), trifluoromethyl sulfite ion (CF 3 SO 3 - ), fluorosulfonate ion (FSO 3 - ), toluenesulfonate ion, trinitrobenzenesulfonate ion, .
In addition, various Lewis acids can also be used as a thermal cationic curing catalyst. Examples of the Lewis acid include transition metal elements, rare earth elements, halides and organic salts of Mg, Zn, P, As, Sb, Sn, B and Al, and organometallic compounds. Specific examples thereof include iron chloride, copper chloride, palladium chloride, scandium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate, europium trifluoromethanesulfonate, magnesium acetate, magnesium trifluoromethanesulfonate, zinc chloride, zinc acetate, tri (Pentafluorophenyl) borane, bis (pentafluorophenyl) phenylborane, bis (pentafluorophenyl) borane, bis (pentafluorophenyl) phenylborane, triphenylborane, triphenylborane, tris (4-fluorophenyl) borane, aluminum chloride, trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylaluminum, triphenylaluminum, tris (pentafluorophenyl) borane, Aluminum and the like. Of these, boron trifluoride, tributylborane, triphenylborane, tris (pentafluorophenyl) borane, bis (pentafluorophenyl) phenylborane, pentafluorophenyldiphenylborane, tris (4-fluorophenyl) Boron compounds such as borane and aluminum compounds such as aluminum chloride, trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylaluminum, triphenylaluminum and tris (pentafluorophenyl) aluminum are preferable.
As the thermal cationic curing catalyst, metal chelate compounds or metal alkoxides can also be preferably used. Examples of the metal chelate compound or metal alkoxide include compounds represented by the following general formula (14):
[Chemical Formula 4]
(Wherein, M is Al, Mg, Ti, or any of the Zr indicates. R 25 may be the same or different and each represents an alkyl group or an alkoxyl group having 1 to 6. R 26 are the same or different, 1 to 12 carbon atoms G represents a valence of an ion of a metal atom represented by M. h represents a number of 0 to 3. A dotted line between an oxygen atom and M in the formula indicates that an oxygen atom is coordinated to M. M The arc of the dotted line of the structural part formed by two oxygen atoms and three carbon atoms between the two oxygen atoms indicates that at least one pair of atoms in this structural part is connected by a double bond, May be conjugated with the ring structure forming the arc portion of the dotted line).
Further, "R 25 are the same or different and each having 1 to 6 carbon alkyl group, or represents an alkoxyl group," the structure of the column, to give the h () if the plurality of the structural part in, in the art in a plurality structure part of R 25 May be the same or may be different from each other. The same is true for R 26 .
Specific examples of the metal chelate compound represented by the general formula (14) include the same ones as the specific examples of the aluminum chelate compound represented by the general formula (9) in the curable resin composition of the present invention described above, Magnesium chelate compounds such as acetate monoisopropylate, magnesium bis (ethyl acetoacetate), magnesium acetoacetate monoisopropylate, and magnesium bis (acetylacetonate); Zirconium tris (acetylacetonate), and titanium bis (acetoacetate) dibutyrate.
Among the compounds represented by the general formula (14), the metal alkoxide is represented by the following general formula (15):
[Chemical Formula 5]
(Wherein M represents any one of Al, Mg, Ti and Zr, and R 27 represents an alkyl group). That is, it is a compound represented by h = 0 in the general formula (14).
Wherein in the formula (15), R 27 is to indicate an alkyl group, specific examples of the alkyl groups for example are methyl group, ethyl group, n- propyl group, isopropyl group, n- butyl group, a t- butyl group, a n- hexyl group , A cyclohexyl group, and an n-decyl group.
In the general formula (15), R 27 is preferably an alkyl group having 1 to 22 carbon atoms.
Specific examples of the metal alkoxide represented by the general formula (15) include aluminum alkoxides such as aluminum triethoxide, aluminum triisopropoxide, aluminum tri-sec-butoxide and aluminum tri-tert-butoxide; Aluminum alkoxides such as magnesium diethoxide, magnesium diisopropoxide and magnesium di-tert-butoxide; Titanium tetraisopropoxide, and the like.
When a metal chelate compound or metal alkoxide is used as the thermal cationic curing catalyst in the present invention, among the metal chelate compounds or metal alkoxides represented by the general formula (14), an aluminum chelate compound or aluminum alkoxide wherein M is Al is preferable Among them, an aluminum chelate compound is more preferable. By using such an aluminum chelate compound as the thermal cationic curing catalyst, the sealing material obtained from the composition of the present invention can sufficiently exhibit the characteristic capable of maintaining high luminance even in use under a high temperature environment.
As the curing adjuster, compounds such as amine compounds, phosphine compounds, polyalcohols and polyethers can also be used. Specific examples of the compound include triethylamine, tributylamine, diisopropylamine, diethanolamine, triethanolamine, 2,2,6,6-tetramethylpiperidine, 1,2,2,6, Pentamethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl- ) Sebacate, 1,2,3,4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxyl Tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl), bis (2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl) carbonate ; Phosphine compounds such as triphenylphosphine, trimethylphosphine, tritolylphosphine and methyldiphenylphosphine; Polyalcohols such as ethylene glycol, propylene glycol, glycerin, diethylene glycol and triethylene glycol; And polyethers such as polyethylene glycol and polypropylene glycol.
It is preferable that the above-mentioned thermal cation curing catalyst can exert its function as a curing agent at a relatively low temperature. Concretely, it is preferable that it can be cured at 180 占 폚 or lower. Thus, even when the adherend is made of a resin material having a lower heat resistance as compared with an inorganic material, it is possible to reduce the influence on the adherend by heating in the heat curing step. More preferably, it functions as a curing agent at 160 캜 or lower.
The content of the cationic curing catalyst is preferably 0.001 to 10 parts by mass in terms of the amount of the nonvolatile content as the amount of the effective component not containing a solvent and the like, when the total amount of the resin composition for optical semiconductor encapsulation is 100 parts by mass. By setting the content of the cationic curing catalyst within this range, the curing rate can be sufficiently increased and the curing of the cured product under the use environment can be sufficiently suppressed. The content of the cationic curing catalyst is more preferably 0.01 to 5 parts by mass. More preferably 0.05 to 3 parts by mass.
≪ Other components >
The curable resin composition of the present invention comprises (A) an epoxy resin, (B) a specific organic silicon compound, (C) an organoaluminum compound, and (D) a compound having at least one hindered amine group in one molecule as an essential component However, other components may be included within the range not hindering the effect of the present invention.
The resin composition for optical semiconductor encapsulation of the present invention may also contain other components as long as it contains an epoxy compound, a polysiloxane compound, a (meth) acrylic polymer and a curing catalyst as essential components.
The other components may be used alone or in combination of two or more. Examples of the other components include a solvent component and other polymer components (such as oxetane resin, vinyl monomer, etc.), polymer components, and various additives such as an epoxy resin for the resin composition for optical semiconductor encapsulation of the present invention And the like.
When the curable resin composition of the present invention is used as a matrix resin for a composite material, a coating film forming resin, or a sealing material having a small thickness, a solvent may be added for the purpose of adjusting the viscosity of the composition. The solvent may be included as necessary for the purpose of adjusting the viscosity of the composition. The solvent is not particularly limited and any organic solvent can be used, but it is preferable to dissolve essential components of the curable resin composition of the present invention or the resin composition for optical semiconductor encapsulation described above. Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Hydrocarbons such as toluene and xylene; Alcohols such as butanol and 2-ethylhexyl alcohol; (Di) ethylene glycol methyl ether, diethylene glycol ethyl ether, (di) ethylene glycol acetate, (di) ethylene glycol diacetate, (di) ethylene glycol methyl ether acetate, propylene glycol, Glycols such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate and derivatives thereof (ether, ester); Esters such as ethyl acetate and butyl acetate are preferable.
The solvent is a cause of bubbles in the molded product when the curable resin composition or the resin composition for optical semiconductor encapsulation is cured to form a molded product (for example, a sealing material having a small thickness), and the solvent has a low adhesive strength, heat resistance, moisture resistance, There is a possibility of deterioration of the apparatus. In addition, when used in a large amount, the viscosity of the composition becomes too low, which causes the controllability of the shape of the formed article (such as a sealing material) to deteriorate. Therefore, when a molded article is obtained without using a drying step or when a solvent is used for a thin sealing material, the amount of the solvent is preferably 30 parts by mass or less based on 100 parts by mass of the total amount of the curable resin composition or the resin composition for optical semiconductor encapsulation More preferably 15 parts by mass or less, further preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, further preferably 1 part by mass or less. Particularly preferably 0.1 part by mass or less, and most preferably 0 part by mass, that is, no solvent is used.
Particularly, in the case of photo-curing, it is preferable that a solvent is not used or a trace amount is used even if it is used.
Examples of the other components include inorganic cracking agents such as polyalkyl glycols, polyester polyols, polycarbonate polyols and poly (meth) acrylates, inorganic or organic fine particles, reactive diluents, and saturated compounds having no unsaturated bond , Adhesion promoters such as pigments, dyes, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, nonreactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers and coupling agents, Antistatic agent, thickener, anti-flow agent, color non-uniformity agent, emulsifier, slip, anti-scratch agent, antistatic agent, drying agent, antifouling agent, antistatic agent, antistatic agent, antibacterial agent, antiseptic agent, flame retardant, An antistatic agent, a conductive agent (electrostatic assistant), and the like.
By curing the curable resin composition of the present invention or the resin composition for optical semiconductor encapsulation, a cured product can be obtained. Thus, the curable resin composition of the present invention or the cured product obtained by curing the resin composition for optical semiconductor encapsulation is also one of the present invention.
Such a cured product has excellent transparency and is excellent in adhesion to an adherend, heat resistance, light resistance, heat cycle resistance, resistance to humidity and humidity, etc. Therefore, a cured product of an optical semiconductor sealing material such as an LED sealing material and a photodiode sealing material, And can be suitably used for forming an optical semiconductor device which is sealed with the optical semiconductor sealing material. The optical semiconductor sealing material is a member formed so as to cover an LED element or a photodiode element constituting an optical semiconductor device, and sealing the element. When the curable resin composition or the resin composition for optical semiconductor encapsulation of the present invention is used for forming an optical semiconductor sealing material such as an LED sealing material or a photodiode sealing material, it is possible to provide a resin composition which has high transparency and is excellent in adhesiveness to an adherend, It is possible to obtain an optical semiconductor sealing material excellent in heat cycle resistance, moisture resistance and the like.
The optical semiconductor sealing material obtained by curing the curable resin composition of the present invention or the resin composition for optical semiconductor sealing as described above is also one of the present invention and the optical semiconductor device sealed with such optical semiconductor sealing material is also one of the present invention .
As the curing resin composition of the present invention or the curing method of the resin composition for optical semiconductor encapsulation, it is preferable to employ photo curing or thermal curing. Among them, it is more preferable to employ thermal curing.
When the curable resin composition of the present invention or the cured product obtained from the resin composition for optical semiconductor encapsulation is used for the optical semiconductor sealing material, it is preferable that the glass transition temperature (Tg) is 170 캜 or less. As a result, when a cured product is used as a sealing material, the sealing material is excellent in resistance to heat cycle. The glass transition temperature is more preferably 150 DEG C or lower, and further preferably 130 DEG C or lower. On the other hand, when a cured product obtained by curing the curable resin composition of the present invention or the resin composition for optical semiconductor encapsulation is used for a semiconductor encapsulant, a wiring board and an optical member, the glass transition temperature is preferably 150 ° C or higher, And more preferably not less than 180 캜.
The glass transition temperature of the sealing material for optical semiconductor or the cured product can be measured by the temperature at which the maximum value of tan? Of dynamic viscoelasticity is exhibited.
When the cured product is used as the optical semiconductor sealing material or the optical member, the cured product preferably has a visible light transmittance of 80% or more. Concretely, it is preferable that the parallel ray transmittance at 400 nm is 80% or more. This makes it possible to realize high light transmittance and transparency required for the LED sealing material application. The parallel line transmittance at 400 nm is more preferably 85% or more, and even more preferably 90% or more.
The transmittance can be measured using a sample having a thickness of 1 mm by means of a UV-VIS spectrophotometer (Agilent 8453, manufactured by Agilent Technologies).
Since the curable resin composition of the present invention has the above-described constitution, the resin composition is excellent in storage stability at room temperature, can be cured at a relatively low temperature, and the resulting molded article is excellent in heat resistance, It is possible to maintain a high luminance even in use for a long time. The curable resin composition of the present invention can be used as a sealing material for semiconductors or optical semiconductors, a sealing material for light receiving sensors or solar cells, a pickup lens for optical recording, a lens for imaging devices, a gap filling material for organic EL or liquid crystal display devices, An interlayer insulating material of a multilayer wiring board, a matrix material of a composite material, and the like.
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise stated, " part " means " part by mass ".
In the following examples, various physical properties were measured by the following methods.
≪ Weight average molecular weight &
The weight average molecular weight was measured by gel permeation chromatography (column: 2 TSKgel SuperMultipore HZ-N 4.6 * 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard).
<Viscosity>
The viscosity was measured using a R / S rheometer (manufactured by Brookfield, USA) at 25 DEG C and a rotation speed D = 1 / s. A RC25-1 measuring jig was used when the viscosity was 20 Pa · s or more, and a jig of RC50-1 was used when the viscosity was less than 20 Pa · s. When the viscosity at the rotational speed D = 1 / s was not measurable, the value of the rotational speed D = 5 to 100 / s was extrapolated to evaluate the viscosity.
≪ Synthesis of organosilicon compound (polysiloxane compound) >
Synthesis Example 1
208 g of methyltrimethoxysilane (Z-6366, manufactured by Toorra Dow Corning), 57.4 g of methyl isobutyl ketone and 21.1 g of formic acid were charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a stirrer, 44.2 g of water was added while stirring at an internal temperature of 35 占 폚, and the mixture was stirred for 10 minutes. Thereafter, the temperature inside the reaction system was raised with stirring using an oil bath at 90 캜, and reflux was started. After one hour from the start of the reflux, the cooling tube for reflux was removed from the separable flask, and the mixture was heated and stirred to distill off the solvent at atmospheric pressure. When the amount of the effluent reached 117.4 g, the oil bath was removed to stop the distillation removal and the temperature was reduced. After reaching an inner temperature of 53 캜, the solvent was distilled off under reduced pressure at 10 캜 for 1 hour while heating and stirring with an oil bath at 53 캜. Then, the solvent was distilled off under reduced pressure at 53 캜 for 1 hour while stirring. Further, the solvent was distilled off under reduced pressure at 80 DEG C for 1 minute while stirring at elevated temperature to obtain 115.7 g of the organosilicon compound (1). The weight average molecular weight of the resulting organosilicon compound (1) (polysiloxane compound (1)) was 4,101 and the viscosity at 25 캜 was 1630 Pa 占 퐏.
Synthesis Example 2
99.1 g of phenyltrimethoxysilane (KBM-103 manufactured by Shin-Etsu Chemical Co., Ltd.), 24.8 g of methyl isobutyl ketone, 0.23 g of formic acid and 18.1 g of water were used as a silane monomer, and the amount of outflow of the end point of the atmospheric distillation removal was 38.4 g , The reaction was carried out in the same manner as in Synthesis Example 1 to obtain 74.0 g of the organosilicon compound (2) (polysiloxane compound (2)). The weight-average molecular weight of the obtained organosilicon compound (2) was 868 and the viscosity at 25 캜 was 15 Pa s.
Synthesis Example 3
44.6 g of methyltriethoxysilane (Z-6383, manufactured by Toray-Dow Corning) as a silane monomer, 51.6 g of n-hexyltrimethoxysilane (Z-6583 manufactured by Toray Dow Corning Toray Co., Ltd.) and methyl isobutyl ketone 24.0 g, formic acid (1.15 g) and water (22.6 g) and the amount of distillate at the end point of the atmospheric distillation was changed to 42.0 g, to obtain 56.2 g of the organosilicon compound (3) Polysiloxane compound (3)). The weight average molecular weight of the obtained organosilicon compound (3) was 1,859 and the viscosity at 25 캜 was 16 Pa s.
Synthesis Example 4
53.5 g of methyltriethoxysilane (Z-6383 manufactured by Toray Dow Corning) as a silane monomer, 56.5 g of cyclohexylmethyldimethoxysilane (Z-6187 manufactured by Toray Dow Corning Toray Co., Ltd.) and 30 g of methyl isobutyl ketone , 1.38 g of formic acid and 27.2 g of water were used and the amount of outflow at the end point of the atmospheric distillation removal was changed to 48.5 g to obtain 68.8 g of an organosilicon compound (4) (polysiloxane Compound (4)). The organosilicon compound (4) thus obtained had a weight average molecular weight of 862 and a viscosity at 25 캜 of 34 Pa 占 퐏.
<Synthesis of (meth) acrylic polymer>
Synthesis Example 5
332.0 parts of isopropanol was poured into a reactor equipped with a thermometer, a cooling tube, a gas introducing tube, a dropping device and a stirrer, and nitrogen replacement was carried out. After the temperature was raised to 80 ° C, a mixed solution of 464.8 parts of butyl acrylate, 199.2 parts of hydroxyethyl acrylate, and 2.0 parts of dilauryl peroxide (manufactured by PEROIL L, NICHI K.K.) was added dropwise over one hour. Thereafter, 2.0 parts of dilauryl peroxide (manufactured by PEROIL L, NICHIKI) was added, and the reaction was carried out for 3 hours. Isopropanol was distilled off under reduced pressure to obtain an acrylic polymer (1). The weight average molecular weight of the obtained acrylic polymer (1) was 31,500.
Synthesis Example 6
In the same manner as in Synthesis Example 5, 332.3 parts of isopropanol was charged, and after the temperature was raised to 80 ° C, 398.7 parts of 2-ethylhexyl acrylate, 265.8 parts of hydroxyethyl acrylate, and distearoyl peroxide (peroyl L, Ltd.) was added dropwise over 1 hour. Thereafter, 1.6 parts of dilauryl peroxide (manufactured by PEROIL L, NICHIKI CHEMICAL CO., LTD.) Was added and the reaction was carried out for 3 hours. Isopropanol was distilled off under reduced pressure to obtain an acrylic polymer (2). The weight average molecular weight of the resulting acrylic polymer (2) was 28,800.
Synthesis Example 7
In the same manner as in Synthesis Example 5, 321.2 parts of isopropanol was poured, and after the temperature was raised to 80 ° C, 481.8 parts of butyl acrylate, 160.6 parts of hydroxyethyl acrylate, 32.1 parts of acrylic acid, and distearoyl peroxide Prepared in a similar manner) was added dropwise over 1 hour. Thereafter, 2.1 parts of dilauryl peroxide (manufactured by PEROIL L, NICHI CORPORATION) was added and the reaction was carried out for 3 hours. Isopropanol was distilled off under reduced pressure to obtain an acrylic polymer (3). The weight average molecular weight of the obtained acrylic polymer (3) was 24,600.
Synthesis Example 8
In the same manner as in Synthesis Example 5, 332.1 parts of isopropanol was poured, and the mixture was heated to 80 DEG C, and then 464.9 parts of butyl acrylate, 199.2 parts of 2-ethylhexyl acrylate, 10 parts of dilauryl peroxide (Perooyl L, 1.9 parts of a mixed solution was added dropwise over 1 hour. Thereafter, 1.9 parts of dilauryl peroxide (manufactured by PEROIL L, NICHI CORPORATION) was added and the reaction was carried out for 3 hours. Isopropanol was distilled off under reduced pressure to obtain an acrylic polymer (4). The weight average molecular weight of the obtained acrylic polymer (4) was 25,500.
Synthesis Example 9
332.0 parts of isopropanol was poured in the same manner as in Synthesis Example 5, and after raising the temperature to 80 캜, 597.5 parts of butyl acrylate, 66.4 parts of hydroxyethyl acrylate, 2.0 parts of dilauryl peroxide (manufactured by PEROIL L, Was added dropwise over 1 hour. Thereafter, 2.0 parts of dilauryl peroxide (manufactured by PEROIL L, manufactured by NICHI CHEMICAL CO., LTD.) Was added and the reaction was carried out for 3 hours. Isopropanol was distilled off under reduced pressure to obtain an acrylic polymer (5). The weight average molecular weight of the resulting acrylic polymer (5) was 29,100.
Synthesis Example 10
331.7 parts of isopropanol was poured in the same manner as in Synthesis Example 5, and after the temperature was raised to 80 ° C, a mixed solution of 530.8 parts of butyl acrylate, 132.7 parts of acrylic acid, and 2.4 parts of di rauroyl peroxide (manufactured by PEROIL L, Over a period of time. Thereafter, 2.4 parts of dilauryl peroxide (manufactured by PEROIL L, NICHIKI) was added and the reaction was carried out for 3 hours. Isopropanol was distilled off under reduced pressure to obtain an acrylic polymer (6). The weight average molecular weight of the obtained acrylic polymer (6) was 33,000.
<Preparation of Curing Catalyst>
Preparation Example 1
274.3 mg of diisopropoxy aluminum ethylacetoacetate (ALCH, manufactured by Kawaken Fine Chemicals) and 1 kg of 1,2,3,4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4- (LA57, manufactured by ADEKA) were weighed and added with 4.78 g of Celloxide 2021P (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) as a solvent, and the mixture was heated to 60 DEG C for 30 minutes Were mixed to prepare a curing catalyst (1). This was used for the preparation of the resin composition so as to have a predetermined content in terms of the solid content of the aluminum-amine compound.
Preparation example 2
274.3 mg of diisopropoxy aluminum ethylacetoacetate (ALCH, manufactured by Kawaken Fine Chemicals), and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) (Tinuvin 765, Except that 5.45 g of Celloxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin) was added as a solvent and weighing 330.9 mg of the curing catalyst 2 Lt; / RTI > This was used for the preparation of the resin composition so as to have a predetermined content in terms of the solid content of the aluminum-amine compound.
Preparation Example 3
274.3 mg of diisopropoxy aluminum ethylacetoacetate (ALCH, manufactured by Kawaken Fine Chemicals Co., Ltd.) and 183.6 mg of 2,2,6,6-tetramethylpiperidine were weighed, and thereto was added Celloxide 2021P Curing agent 3) was prepared in the same manner as in Preparation Example 1 except that 4.12 g of alicyclic epoxy resin (manufactured by Shell Chemical Co., Ltd., alicyclic epoxy resin) was added. This was used for the preparation of the resin composition so as to have a predetermined content in terms of the solid content of the aluminum-amine compound.
Preparation Example 4
274.3 mg of diisopropoxy aluminum ethylacetoacetate (ALCH, manufactured by Kawaken Fine Chemicals Co., Ltd.) and 131.5 mg of triethylamine were weighed, and thereto was added Celloxide 2021P (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) Except that 3.65 g was added to the curing catalyst (4), a curing catalyst (4) was prepared. This was used for the preparation of the resin composition so as to have a predetermined content in terms of the solid content of the aluminum-amine compound.
Preparation Example 5
274.3 mg of diisopropoxy aluminum ethylacetoacetate (ALCH, manufactured by Kawaken Fine Chemicals Co., Ltd.) and 136.7 mg of diethanolamine were weighed, and thereto was added Celloxide 2021P (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) Was prepared in the same manner as in Preparation Example 1, except for adding 3.7 g of a curing catalyst (5). This was used for the preparation of the resin composition so as to have a predetermined content in terms of the solid content of the aluminum-amine compound.
≪ Preparation of Resin Composition >
Example 1
90 parts of Celllock 2021P (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) and 10 parts of the organosilicon compound (1) were weighed and placed in a reactor equipped with a stirrer, a thermometer and a stirrer. After cooling to room temperature, 0.3 part of the curing catalyst (1) was added and mixed for 15 minutes to obtain a resin composition (1). The blending amounts of the epoxy resin, the organic silicon compound and the curing catalyst are shown in Table 1.
Examples 2 to 4, 6 to 7, and Comparative Examples 1, 3 to 4
(2) to (4), (6) to (7) were prepared in the same manner as in Example 1, except that the epoxy resin, the organosilicon compound and the curing catalyst were mixed in the kind and the blending amount shown in Tables 1 and 2, , (Comparative Example 1), (Comparative Example 3) to (Comparative Example 4) were obtained.
Example 5
A thermometer and a stirrer was charged with 20 parts of Celllock 2021P (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.), 70 parts of a basic liquid epoxy resin Grade 828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin) 10 parts of the organosilicon compound (1) were weighed, and the mixture was heated to 60 占 폚 and mixed for 30 minutes. After cooling to room temperature, 0.3 part of the curing catalyst (1) was added and mixed for 15 minutes to obtain a resin composition (5).
Example 8
40 parts of Celllock 2021P (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) and 20 parts of YX-8040 (manufactured by Mitsubishi Chemical Corporation, solid hydrogenated bisphenol A type epoxy resin) were weighed and placed in a reactor equipped with a thermometer and a stirrer , And the mixture was heated to 140 DEG C in a nitrogen atmosphere and mixed for 1 hour. After cooling to 70 캜, 40 parts of the organosilicon compound (1) was added and mixed for 30 minutes. After cooling to room temperature, 0.3 part of the curing catalyst 3 was added and mixed for 30 minutes to obtain a resin composition (8).
Example 9
The resin composition (9) was obtained in the same manner as in Example 8, except that the epoxy resin, the organosilicon compound and the curing catalyst were mixed in the amounts shown in Table 2 using the curing catalyst (1) instead of the curing catalyst (3) .
Comparative Example 2
A resin composition (Comparative Example 2) was obtained in the same manner as in Example 5 except that the curing catalyst (4) was used in place of the curing catalyst (1).
<Evaluation of Curing Rate>
The resin compositions (1) to (9) and (Comparative Examples 1) to (Comparative Example 4) obtained in Examples 1 to 9 and Comparative Examples 1 to 4 were weighed and weighed 1 cc on a hot plate adjusted to each temperature, The time until disappearance was measured. The results are shown in Tables 1 and 2.
≪ Evaluation of storage stability (viscosity) >
The resin compositions (1) to (5) and the resin compositions (comparative examples 1 to 2) obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were stopped for one day under an environment of 25 ° C. The viscosity of each resin composition immediately after preparation and after 1 day was measured as follows. Table 1 shows the measured viscosity.
≪ Evaluation of storage stability (time) >
The resin compositions (1), (6) to (9) and the resin compositions (Comparative Examples 3) to (Comparative Example 4) obtained in Examples 1, 6 to 9 and Comparative Examples 3 to 4 were allowed to stand at 25 ° C, The time until fluidity was lost was measured. The results are shown in Table 2.
<Heat resistance test>
Resin compositions (1), (6) to (9) and resin compositions (Comparative 3) to (Comparative Example 4) obtained in Examples 1, 6 to 9 and Comparative Examples 3 to 4 were placed in a mold The mixture was injected between two glass plates and cured to prepare a plate-like sample having a thickness of 1 mm. The obtained sample was subjected to a test in which the sample was allowed to stand in an oven at 100 캜 for 500 hours, and the degree of coloration or degree after the test was evaluated.
Specifically, the rate of change (? T) of the transmittance to 400 nm light before and after the test was measured and evaluated according to the following criteria. The results are shown in Table 2. The transmittance was measured by a UV-VIS spectrophotometer (Agilent 8453, manufactured by Agilent Technologies).
∘: ΔT <5%
?: 5%??? T <10%
×: ΔT ≥ 10%
<High temperature lighting test>
The resin compositions (1), (6) to (9) and the resin compositions (Comparative Example 3) to (Comparative Example 4) obtained in Examples 1, 6 to 9 and Comparative Examples 3 to 4 were laminated on a blue LED chip × 600 μm) was poured into an LED package (external dimension: 5 mm × 5 mm) having three chips mounted thereon so as to be filled with the package, and then heated and cured in an oven at 150 ° C. for one hour to prepare a sample. The obtained sample was placed in an oven maintained at 85 캜, a current of 60 mA was passed to turn on the LED, and the test was performed for 500 hours. Then, the retention ratio of the luminance after the test was evaluated. The results are shown in Table 2.
The luminance was measured by a light source distribution measuring system (IS-LI-TE-1, manufactured by Radiant Imaging).
<Preparation of Seal Material Composition>
Example 10
, 20 parts of an organosilicon compound (1) (polysiloxane compound (1)) and 20 parts of an acrylic polymer (1) were added to a reactor equipped with a thermometer and a stirrer, 30 parts were weighed, and the mixture was heated to 70 占 폚 and mixed for 30 minutes. After cooling to room temperature, 0.3 part of Curing Agent 1 was added and mixed for 30 minutes to obtain Resin Composition (10). The blending amounts of the epoxy compound, polysiloxane compound, acrylic polymer and curing catalyst are shown in Table 3.
Examples 11 to 13
Resin compositions (11) to (13) were obtained in the same manner as in Example 10 except that the epoxy compound, the organosilicon compound (polysiloxane compound), the acrylic polymer and the curing catalyst were mixed in the kind and blending amount shown in Table 3 .
Example 14
40 parts of Celllock 2021P (alicyclic epoxy resin, manufactured by Daicel Chemical Industries, Ltd.) and 20 parts of YX-8040 (manufactured by Mitsubishi Chemical Corporation, solid hydrogenated bisphenol A type epoxy resin) were weighed and placed in a reactor equipped with a thermometer and a stirrer , And the mixture was heated to 140 DEG C in a nitrogen atmosphere and mixed for 1 hour. After cooling to 70 캜, 30 parts of the organosilicon compound (1) (polysiloxane compound (1)) and 10 parts of the acrylic polymer (5) were added and mixed for 30 minutes. After cooling to room temperature, 0.3 part of Curing Agent 1 was added and mixed for 30 minutes to obtain Resin Composition (14).
Example 15
An epoxy compound, an organosilicon compound (polysiloxane compound), an acrylic polymer and a curing catalyst were mixed with each other using the type and amount of compound shown in Table 3 by using Celloxide 2081 (an alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.) as an epoxy compound In the same manner as in Example 10 except for the above, a resin composition (15) was obtained.
Example 16
An epoxy compound, an organosilicon compound (polysiloxane compound), an acrylic polymer and a curing catalyst were mixed in the amounts shown in Table 3 using SI-100L (a thermal latent cationic curing catalyst (antimony type) Except that the components were mixed in the same manner as in Example 10, to obtain a resin composition (16).
Comparative Example 5
A resin composition (Comparative Example 5) was obtained in the same manner as in Example 16 except that the epoxy compound, the acrylic polymer and the curing catalyst were mixed at the blending amounts shown in Table 3.
≪ Preparation and evaluation of sealing material >
The resin compositions (10) to (16) and the resin composition (Comparative Example 5) obtained in Examples 10 to 16 and Comparative Example 5 were laminated on a three-chip blue LED chip (chip size 300 μm × 600 μm) 5 mm x 5 mm in outer dimensions), and the sample was heated and cured in an oven at 150 deg. C for one hour to prepare a sample. A solder heat resistance test (reflow test) and a high temperature lighting test were performed on the obtained samples by the following methods and evaluated.
≪ Soldering heat resistance test >
The above samples were prepared for each 10 samples and put in an oven for 3 minutes at 260 캜 for 3 minutes. After the test, peeling between the sealing material and the package was observed, and the number of peeling-off samples was counted. The results are shown in Table 3.
<High temperature lighting test>
Was carried out by the same method as the high temperature lighting test described above. The results are shown in Table 3.
From Examples 1 to 9 and Comparative Examples 1 to 4, it was confirmed that the resin compositions containing the epoxy resin, the specific organic silicon compound, the organoaluminum compound, and the compound having at least one hindered amine group in one molecule were used, 9, all of the resin compositions are excellent in storage stability and can be cured at a relatively low temperature. Further, in Examples 1, 6 to 9, it was found that all of the molded articles obtained were excellent in heat resistance and in luminance when used for a long time.
On the other hand, in Comparative Examples 1 to 4 using a resin composition containing no hindered amine group-containing compound, it is found that the storage stability is inferior. Further, in Comparative Examples 3 and 4, it was found that all of the molded bodies obtained were inferior in heat resistance and in luminance when used for a long period of time.
In Examples 2 and 6 in which a resin composition containing a compound having four or more hindered amine groups in one molecule was used in the comparison between Example 2 and Example 4 and the comparison between Example 6 and Example 7, It can be seen that the resin composition is superior in storage stability.
In addition, in the comparison between Examples 6 to 7 and Examples 8 to 9, it was found that when only alicyclic epoxy resin was used as the epoxy resin, the resulting molded article was particularly excellent in heat resistance, and as a result, It can be seen that it is excellent.
In Examples 2 and 3 in which the content of the organosilicon compound was 0.05 to 10 parts by mass based on 100 parts by mass of the total amount of the epoxy resin in Examples 1 and 2 to 3, It can be seen that this is more excellent in storage stability.
Further, when the content of the organosilicon compound is 15 to 300 parts by mass relative to 100 parts by mass of the total amount of the epoxy resin in Examples 6 to 9 and Example 1, the resulting molded article is particularly excellent in heat resistance, As a result, it can be seen that this is excellent in the luminance when used for a long time.
From Examples 10 to 16 and Comparative Example 5, in Examples 10 to 16 using the resin composition containing the epoxy compound, the organic silicon compound (polysiloxane compound), the (meth) acrylic polymer and the curing catalyst, The solder heat resistance, the adhesion to the surface of the adherend, and the brightness when used for a long period of time. In particular, from Examples 10 to 16 and Comparative Example 5, it was confirmed that good adhesion to the surface of an adherend can be maintained even after a high temperature process such as a reflow process is performed, and even when used under a high- It can be seen that the luminance can be maintained.
On the other hand, in Comparative Example 5 using a resin composition not containing an organosilicon compound (polysiloxane compound), although the obtained sealing material is excellent in solder heat resistance and adhesion to the surface of an adherend, .
In addition, in the comparison between Examples 10 to 15 and Example 16, it is found that the obtained sealing material is superior in luminance when used for a long time by using an aluminum-based curing catalyst as a curing catalyst.
Further, in the comparison of Examples 10 to 12, 14, 15 and Example 13, it was found that acrylic polymer obtained by using a monomer having a functional group capable of forming a hydrogen bond as a raw material is more excellent in adhesion Able to know.
Furthermore, in the comparison between Examples 10 to 13, 15 and Example 14, it can be seen that by using only the alicyclic epoxy compound as the epoxy compound, the resulting sealing material is more excellent in luminance when used for a long time.
Claims (13)
(A) an epoxy resin,
(B) an Si-OR group wherein R represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl substituted aryl group having 7 to 22 carbon atoms, An aralkyl group having a carbon number of 1 to 22,
(C) an organoaluminum compound,
(D) a compound having at least one hindered amine group in one molecule as an essential component.
The curable resin composition contains 100 parts by mass of the epoxy resin (A)
As the (B) organosilicon compound, the following average compositional formula (1):
R 1 a (OR 2 ) b SiO (4-a-b) / 2 (1)
(Wherein R 1 is the same or different and is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkyl substituted aryl group having 7 to 22 carbon atoms, R 2 is the same or different and represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, An alkyl substituted aryl group having 7 to 22 carbon atoms, or an aralkyl group having 7 to 22 carbon atoms, a and b are numbers of 1.0? A? 1.7 and 0.05? B? 1.0, 1.05 ? A + b? 2.0) is contained in an amount of 10 to 900 parts by mass based on 100 parts by mass of the polysiloxane compound.
Wherein the content of the organoaluminum compound (C) in the curable resin composition is 0.05 to 5 parts by mass based on 100 parts by mass of the total of the epoxy resin (A) and the organosilicon compound (B).
The content of the compound having at least one hindered amine group in one molecule (D) in the curable resin composition is preferably 0.05 to 5 parts by mass per 100 parts by mass of the total of the epoxy resin (A) and the organosilicon compound (B) Wherein the curable resin composition is a curable resin composition.
Wherein the compound (D) having at least one hindered amine group in one molecule has at least two hindered amine groups in one molecule.
Wherein the epoxy resin (A) comprises an alicyclic epoxy resin.
Wherein the content of the alicyclic epoxy resin in the curable resin composition is 5 parts by mass or more based on 100 parts by mass of the total of (A) the epoxy resin.
Wherein the curable resin composition is used as a sealing material for an optical semiconductor.
Wherein the curable resin composition for optical semiconductor encapsulation further contains a (meth) acrylic polymer.
Wherein the resin composition comprises an epoxy compound, a polysiloxane compound, a (meth) acrylic polymer, and a curing catalyst.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2013-017670 | 2013-01-31 | ||
| JP2013017668A JP2014148595A (en) | 2013-01-31 | 2013-01-31 | Resin composition for sealing optical semiconductor, optical semiconductor sealing material, and optical semiconductor device |
| JPJP-P-2013-017669 | 2013-01-31 | ||
| JP2013017670A JP6148870B2 (en) | 2013-01-31 | 2013-01-31 | Curable resin composition and cured product |
| JP2013017669A JP6077321B2 (en) | 2013-01-31 | 2013-01-31 | Curable resin composition, optical semiconductor sealing material, and optical semiconductor device |
| JPJP-P-2013-017668 | 2013-01-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20140098679A true KR20140098679A (en) | 2014-08-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140004839A KR20140098679A (en) | 2013-01-31 | 2014-01-15 | Curable resin composition, and resin composition for optical semiconductor sealing |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20140098679A (en) |
| CN (1) | CN103965581B (en) |
| TW (1) | TW201431945A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016148004A1 (en) | 2015-03-18 | 2016-09-22 | デクセリアルズ株式会社 | Method for manufacturing light emitting device |
| JP2017122144A (en) * | 2016-01-05 | 2017-07-13 | デクセリアルズ株式会社 | Adhesive composition |
| WO2020003122A1 (en) * | 2018-06-27 | 2020-01-02 | 3M Innovative Properties Company | Curable compositions and related methods |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000007882A (en) * | 1998-06-25 | 2000-01-11 | Toray Ind Inc | Emulsion composition |
| JP4347103B2 (en) * | 2004-03-22 | 2009-10-21 | 信越化学工業株式会社 | Curable silicone composition |
| US20070142573A1 (en) * | 2005-12-19 | 2007-06-21 | Shin-Etsu Chemical Co., Ltd. | Epoxy/silicone hybrid resin composition and cured part |
| JP2011127006A (en) * | 2009-12-18 | 2011-06-30 | Tosoh Corp | Aromatic-alicyclic copolymerized petroleum resin composition and method for producing the same |
-
2014
- 2014-01-02 TW TW103100035A patent/TW201431945A/en unknown
- 2014-01-15 KR KR1020140004839A patent/KR20140098679A/en not_active Application Discontinuation
- 2014-01-27 CN CN201410039679.5A patent/CN103965581B/en active Active
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| TW201431945A (en) | 2014-08-16 |
| CN103965581B (en) | 2017-09-15 |
| CN103965581A (en) | 2014-08-06 |
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