CN103210041A - Thermosetting silicone resin composition, and silicone resin-containing structure and optical semiconductor element encapsulant obtained using same - Google Patents
Thermosetting silicone resin composition, and silicone resin-containing structure and optical semiconductor element encapsulant obtained using same Download PDFInfo
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- CN103210041A CN103210041A CN2011800541967A CN201180054196A CN103210041A CN 103210041 A CN103210041 A CN 103210041A CN 2011800541967 A CN2011800541967 A CN 2011800541967A CN 201180054196 A CN201180054196 A CN 201180054196A CN 103210041 A CN103210041 A CN 103210041A
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 49
- 239000011342 resin composition Substances 0.000 title claims abstract description 32
- 239000004065 semiconductor Substances 0.000 title claims description 67
- 230000003287 optical effect Effects 0.000 title claims description 65
- 229920001187 thermosetting polymer Polymers 0.000 title abstract 4
- 239000008393 encapsulating agent Substances 0.000 title 1
- -1 silane compound Chemical class 0.000 claims abstract description 145
- 229910000077 silane Inorganic materials 0.000 claims abstract description 73
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 52
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 51
- 125000005372 silanol group Chemical group 0.000 claims abstract description 30
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 85
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 125000003545 alkoxy group Chemical group 0.000 claims description 42
- 238000007789 sealing Methods 0.000 claims description 33
- 239000003566 sealing material Substances 0.000 claims description 20
- 150000002363 hafnium compounds Chemical class 0.000 claims description 18
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 239000004332 silver Substances 0.000 claims description 18
- 150000003755 zirconium compounds Chemical class 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 10
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000003752 zinc compounds Chemical class 0.000 abstract 3
- 239000000203 mixture Substances 0.000 description 72
- 239000002253 acid Substances 0.000 description 47
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 40
- 150000001875 compounds Chemical class 0.000 description 37
- 239000002585 base Substances 0.000 description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 25
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- 229910052726 zirconium Inorganic materials 0.000 description 22
- 150000002148 esters Chemical group 0.000 description 18
- 239000011701 zinc Substances 0.000 description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 125000000962 organic group Chemical group 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 14
- 229910052735 hafnium Inorganic materials 0.000 description 14
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 14
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 10
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 10
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 8
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 description 7
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229940125904 compound 1 Drugs 0.000 description 7
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 125000002252 acyl group Chemical group 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000003751 zinc Chemical class 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- OFEVLLPPRKRSAN-UHFFFAOYSA-N formic acid;hexane Chemical compound OC=O.CCCCCC OFEVLLPPRKRSAN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000009434 installation Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 3
- ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 2-ethylhexanoic acid;zinc Chemical compound [Zn].CCCCC(CC)C(O)=O ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 0.000 description 3
- NZNMSOFKMUBTKW-UHFFFAOYSA-N Cyclohexanecarboxylic acid Natural products OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- PGKIRTSAOUCMCT-UHFFFAOYSA-N [O]C(=O)C1CC1 Chemical compound [O]C(=O)C1CC1 PGKIRTSAOUCMCT-UHFFFAOYSA-N 0.000 description 3
- UWOWCDDRXIAJHQ-UHFFFAOYSA-N [O]C(=O)C1CCCC1 Chemical compound [O]C(=O)C1CCCC1 UWOWCDDRXIAJHQ-UHFFFAOYSA-N 0.000 description 3
- FJPVCKDSPVJGFE-UHFFFAOYSA-N [O]C(=O)C1CCCCC1 Chemical compound [O]C(=O)C1CCCCC1 FJPVCKDSPVJGFE-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- YPULQVCWMGTRGV-UHFFFAOYSA-N benzoic acid;hafnium Chemical compound [Hf].OC(=O)C1=CC=CC=C1 YPULQVCWMGTRGV-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical class CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- GLGSZERYOLHNML-UHFFFAOYSA-N $l^{1}-oxidanyl(phenyl)methanone Chemical compound [O]C(=O)C1=CC=CC=C1 GLGSZERYOLHNML-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BOZRCGLDOHDZBP-UHFFFAOYSA-N 2-ethylhexanoic acid;tin Chemical compound [Sn].CCCCC(CC)C(O)=O BOZRCGLDOHDZBP-UHFFFAOYSA-N 0.000 description 2
- GXBPIJOAHZFSJY-UHFFFAOYSA-N 7,7-dimethyloctanoic acid zinc Chemical compound [Zn].CC(C)(C)CCCCCC(O)=O GXBPIJOAHZFSJY-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- GDRJBDPMKHTBJQ-UHFFFAOYSA-N C(=O)O.CCCCC Chemical compound C(=O)O.CCCCC GDRJBDPMKHTBJQ-UHFFFAOYSA-N 0.000 description 2
- FNDLPWWLTIWOAL-UHFFFAOYSA-M C(C=C)(=O)[O-].C[Zn+] Chemical compound C(C=C)(=O)[O-].C[Zn+] FNDLPWWLTIWOAL-UHFFFAOYSA-M 0.000 description 2
- AVCOEQTZBWHZAJ-UHFFFAOYSA-N CCC.OC=O Chemical compound CCC.OC=O AVCOEQTZBWHZAJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- WPRCGBSKPTUOBH-UHFFFAOYSA-N [Hf].C12(CC3CC(CC(C1)C3)C2)C(=O)O Chemical compound [Hf].C12(CC3CC(CC(C1)C3)C2)C(=O)O WPRCGBSKPTUOBH-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- SUWYTDUHVCILRX-UHFFFAOYSA-N adamantane-1-carboxylic acid zirconium Chemical compound [Zr].C1C(C2)CC3CC2CC1(C(=O)O)C3 SUWYTDUHVCILRX-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000007973 cyanuric acids Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 2
- AXCUOSJGDDJDRU-UHFFFAOYSA-N formic acid propane zirconium Chemical compound [Zr].C(=O)O.CCC AXCUOSJGDDJDRU-UHFFFAOYSA-N 0.000 description 2
- NVARWQKCEFWQBV-UHFFFAOYSA-N formic acid;hafnium Chemical compound [Hf].OC=O NVARWQKCEFWQBV-UHFFFAOYSA-N 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 125000005474 octanoate group Chemical group 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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Images
Classifications
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- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- H—ELECTRICITY
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- 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
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- C—CHEMISTRY; METALLURGY
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Abstract
The purpose of the present invention is to provide a thermosetting silicone resin composition containing a tin compound and having excellent thermosetting properties and stability at room temperature. This thermosetting silicone resin composition contains an organopolysiloxane (A) having a silanol group, a silane compound (B) having an alkoxysilyl group, a tin compound (C), and a zinc compound (D). The tin compound (C) content is 0.001-1 parts by mass relative to 100 parts by mass of the total of the organopolysiloxane (A) and the silane compound (B). The zinc compound (D) content is 0.01-5 parts by mass relative to 100 parts by mass of the total of the organopolysiloxane (A) and the silane compound (B). The mass ratio (C/D) value of the tin compound (C) relative to the zinc compound (D) is less than 1.
Description
Technical field
The structure photoreactive semiconductor element sealing member that contains silicone resin that the present invention relates to thermohardening type organosilicon resin composition and use said composition and get.
Background technology
In the past, in the condensation system of the organopolysiloxane with silanol group is solidified, as catalyzer, the compound (for example, with reference to patent documentation 1,2) of aluminium system, zirconium system, titanium system, tin system etc. had been proposed.
The prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Application Publication 2008-534768 communique
Patent documentation 2: Japanese Unexamined Patent Application Publication 2008-535645 communique
Summary of the invention
Invent problem to be solved
Tin compound is widely used as the catalyzer of wet-cured type, but the organosilicon resin composition that contains tin compound at room temperature can gelation etc. and poor stability under the room temperature, and Thermocurable is also poor.
Therefore, the purpose of this invention is to provide stability under the room temperature and the thermohardening type organosilicon resin composition that contains tin compound of Thermocurable excellence.
Be used for solving the method for problem
The inventor furthers investigate in order to solve above-mentioned problem, found that, in the organopolysiloxane of regulation and the organosilicon resin composition that fits in the zn cpds of specified quantitative and tin compound, the stability under the room temperature and Thermocurable excellence, thus finish the present invention.
That is, the invention provides following (1)～(7).
(1) a kind of thermohardening type organosilicon resin composition, it contains: the organopolysiloxane (A) with silanol group, silane compound (B) with alkoxysilyl, tin compound (C) and zn cpds (D), the content of above-mentioned tin compound (C) is, total 100 mass parts with respect to above-mentioned organopolysiloxane (A) and above-mentioned silane compound (B) are 0.001～1 mass parts, the content of above-mentioned zn cpds (D) is, total 100 mass parts with respect to above-mentioned organopolysiloxane (A) and above-mentioned silane compound (B) are 0.01～5 mass parts, above-mentioned tin compound (C) with respect to the value of the mass ratio (C/D) of above-mentioned zn cpds (D) less than 1.
(2) according to above-mentioned (1) described thermohardening type organosilicon resin composition, above-mentioned zn cpds (D) is the zn cpds shown in following formula (d1) or the following formula (d2).
Zn(O－CO－R
1)
2 (d1)
Zn(R
2COCHCOR
3)
2 (d2)
(in the formula (d1), R
1The alkyl or aryl of expression carbonatoms 1～18.
In the formula (d2), R
2, R
3Identical or different, 1 valency alkyl or alkoxyl group of expression carbonatoms 1～18.)
(3) according to above-mentioned (1) or (2) described thermohardening type organosilicon resin composition, above-mentioned organopolysiloxane (A) comprises silicone resin, described silicone resin: with R
3SiO
1/2Unit (in the formula, R represents 1 valency alkyl of the carbonatoms 1～6 that do not replace or replace independently of one another) and SiO
4/2The unit is as repeating unit, with respect to SiO
4/21 mole of unit, R
3SiO
1/2The ratio of unit is 0.5～1.2 mole, in addition, also can have R
2SiO
2/2Unit and RSiO
3/2In the unit (in various, R represents 1 valency alkyl of the carbonatoms 1～6 that do not replace or replace independently of one another) at least a kind, and make with respect to SiO
4/21 mole of unit, R
2SiO
2/2Unit and RSiO
3/2Each unit of unit is respectively below 1.0 moles and the adding up to below 1.0 moles of each unit, and, have the silanol group less than 6.0 quality %.
(4) according to each described thermohardening type organosilicon resin composition of above-mentioned (1)～(3), it also contains zirconium compounds (E) and/or hafnium compound (F).
(5) according to each described thermohardening type organosilicon resin composition of above-mentioned (1)～(4), it also contains two (alkoxyl group) alkane and/or isocyanurate derivative.
(6) a kind of structure that contains silicone resin, it possesses: the member that comprises silver; And cover that each described thermohardening type organosilicon resin composition above-mentioned member, that make above-mentioned (1)～(5) solidifies and the silicone resin layer that obtains.
(7) a kind of optical semiconductor sealing member, it possesses: the framework with recess; Be disposed at the optical semiconductor of the bottom of above-mentioned recess; Be disposed at the member that comprises silver of the medial surface of above-mentioned recess; And be filled in above-mentioned recess and above-mentioned optical semiconductor and above-mentioned member each described thermohardening type organosilicon resin composition sealing, that make above-mentioned (1)～(5) solidified and the sealing material that obtains.
The effect of invention
According to the present invention, can provide stability under the room temperature and the thermohardening type organosilicon resin composition that contains tin compound of Thermocurable excellence.
Description of drawings
Fig. 1 is the sectional view that schematically shows as an example of the multilayer body of the structure that contains silicone resin of the present invention.
Fig. 2 is another the routine sectional view that schematically shows as the multilayer body of the structure that contains silicone resin of the present invention.
Fig. 3 is the sectional view that schematically shows an example of optical semiconductor sealing member of the present invention.
Fig. 4 is another the routine sectional view that schematically shows optical semiconductor sealing member of the present invention.
Fig. 5 is another the routine sectional view again that schematically shows optical semiconductor sealing member of the present invention.
Fig. 6 has used the synoptic diagram of an example of the light-emitting diode display of composition of the present invention and/or optical semiconductor sealing member of the present invention for expression.
Embodiment
＜thermohardening type organosilicon resin composition＞
Thermohardening type organosilicon resin composition of the present invention (below, be also referred to as " composition of the present invention ".) be following thermohardening type organosilicon resin composition, it contains: the organopolysiloxane (A) with silanol group, silane compound (B) with alkoxysilyl, tin compound (C) and zn cpds (D), the content of above-mentioned tin compound (C) is, total 100 mass parts with respect to above-mentioned organopolysiloxane (A) and above-mentioned silane compound (B) are 0.001～1 mass parts, the content of above-mentioned zn cpds (D) is, total 100 mass parts with respect to above-mentioned organopolysiloxane (A) and above-mentioned silane compound (B) are 0.01～5 mass parts, above-mentioned tin compound (C) with respect to the value of the mass ratio (C/D) of above-mentioned zn cpds (D) less than 1.
Below, each composition that composition of the present invention is contained is described in detail.
＜organopolysiloxane (A)＞
The organopolysiloxane that composition of the present invention contains (A) is the organopolysiloxane that has more than 1 in 1 molecule, is preferably the silanol group more than 2.
Alkyl as organopolysiloxane (A) has is not particularly limited, and for example can enumerate aromatic series bases such as phenyl; Alkyl; Alkenyl; Deng.
The main chain of organopolysiloxane (A) can be straight chain shape, chain or netted any.The alkoxysilyl that can have in addition, carbonatoms 1～6 in the part.
As organopolysiloxane (A), for example can enumerate, 2 above silanol groups are incorporated into terminal organic polydialkysiloxane.
As such organopolysiloxane (A), be preferably organic polydimethylsiloxane that 2 silanol groups are incorporated into two ends, more preferably 2 silanol groups are incorporated into organic polydimethylsiloxane (organic polydimethylsiloxane-α of straight chain shape of the straight chain shape of two ends, omega-diol), as concrete example, can enumerate the organopolysiloxane shown in the following formula (a1).
In the formula (a1), R
4Identical or different, the alkyl or aryl of expression carbonatoms 1～18, n represents the integer more than 1.
As R
4The alkyl of shown carbonatoms 1～18 for example can be enumerated, the alkyl of straight chain shape such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl or a chain; Cycloalkyl such as cyclopentyl, cyclohexyl; Deng, as R
4The aryl of shown carbonatoms 1～18 for example can be enumerated, and phenyl, naphthyl etc. wherein, are preferably methyl, phenyl, more preferably methyl.
In the formula (a1), n can for the weight-average molecular weight value corresponding of organopolysiloxane (A), be preferably 10～15,000 integer.
In addition, as organopolysiloxane (A), can enumerate main chain is netted silicone resin.As such silicone resin, for example can enumerate, with R
3SiO
1/2Unit (in the formula, R represents 1 valency alkyl of the carbonatoms 1～6 that do not replace or replace independently of one another) and SiO
4/2The unit is as the silicone resin A 1 of repeating unit.
In the silicone resin A 1, as R
3SiO
1/2R in the unit for example can enumerate, alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl; Cycloalkyl such as cyclopentyl, cyclohexyl; Alkenyls such as vinyl, allyl group, pseudoallyl, butenyl, pentenyl, hexenyl; Aryl such as phenyl; Chloromethyl, 3-chloropropyl, 1-chloro-2-methyl-propyl, 3,3, haloalkyls such as 3-trifluoro propyl; Deng, wherein, be preferably methyl, vinyl, phenyl, more preferably methyl.
In the silicone resin A 1, with respect to SiO
4/21 mole of unit, R
3SiO
1/2The ratio of unit is 0.5～1.2 mole, is preferably 0.65～1.15 mole.If R
3SiO
1/2The ratio of unit is this scope, and then the intensity of the cured article of composition of the present invention becomes suitably, and in addition, the transparency is also excellent.
In addition, silicone resin A 1 can have R
2SiO
2/2Unit and RSiO
3/2In the unit (in various, R represents 1 valency alkyl of the carbonatoms 1～6 that do not replace or replace independently of one another) at least a kind, and make with respect to SiO
4/21 mole of unit, R
2SiO
2/2Unit and RSiO
3/2Each unit of unit is respectively below 1.0 moles and the adding up to below 1.0 moles of each unit, more preferably R
2SiO
2/2Unit and RSiO
3/2Each unit of unit is adding up to below 1.0 moles of 0.2～0.8 mole and each unit.If be such cooperation ratio, then the transparency of composition of the present invention is excellent.As the concrete example of such cooperation ratio, can enumerate with respect to SiO
4/21 mole of unit, R
2SiO
2/20.2 mole of unit and RSiO
3/2The combination that the unit is 0.7 mole.
In addition, silicone resin A 1 has the silanol group less than 6.0 quality %.The content of silanol group is preferably more than the 0.1 weight %, more preferably 0.2～3.0 weight %.If the content of silanol group is this scope, then the hardness of the cured article of composition of the present invention becomes suitably and cementability becomes good, and in addition, it is suitable that intensity also becomes.
In addition, silicone resin A 1 can have alkoxysilyl.As the resin with silanol group and alkoxyl group, for example can enumerate MK resin (ワ ッ カ ー シ リ コ ー Application society of Asahi Chemical Industry system) etc.
The manufacture method of silicone resin A 1 is not particularly limited, can make by known method in the past, for example, can make the silane compound that contain alkoxyl group corresponding with each unit in organic solvent, carry out cohydrolysis and condensation obtains as the silicone resin that does not contain volatile component in fact.
Particularly, for example, as long as with R
3SiOMe and Si (OMe)
4As required with R
2Si (OMe)
2And/or RSi (OMe)
3Cohydrolysis and condensation get final product (in various, R represents 1 valency alkyl of the carbonatoms 1～6 that do not replace or replace independently of one another, and Me represents methyl) in organic solvent together.
As organic solvent, be preferably the organic solvent that can dissolve the organopolysiloxane that generates by cohydrolysis-condensation reaction, as concrete example, can enumerate toluene, dimethylbenzene, methylene dichloride, petroleum naphtha mineral spirits etc.
As such silicone resin A 1, can use commercially available product, for example can enumerate " SR1000 " of モ メ Application テ ィ Block パ フ ォ ー マ Application ス マ テ リ ア Le ズ ジ ャ パ Application contract commercial firm system.
Manufacture method about organopolysiloxane (A) is not particularly limited, and can use known manufacture method in the past.
The molecular weight of organopolysiloxane (A) is preferably 1,000～1, and 000,000, more preferably 6,000～100,000.
In addition, in the present invention, the serve as reasons weight-average molecular weight of polystyrene conversion that chloroform is obtained as the gel permeation chromatography (GPC) of solvent of the molecular weight of organopolysiloxane (A).
Organopolysiloxane (A) can a kind of independent use also can be two or more and use.
＜silane compound (B)＞
From the viewpoint of Thermocurable, composition of the present invention contains silane compound (B).The silane compound that composition of the present invention contains (B) has more than 1 in 1 molecule, be preferably the alkoxysilyl more than 2.Here, so-called alkoxysilyl refers to the alkoxyl group with the direct combination of Siliciumatom.
As silane compound (B) composition, for example can enumerate, have 1 Siliciumatom in 1 molecule, be combined with the compound (below, be also referred to as " silane compound B1 ") of 2 above alkoxyl groups on the Siliciumatom; Have 2 above Siliciumatoms in 1 molecule, skeleton is the polysiloxane skeleton, has the organopolysiloxane (below, be also referred to as " silane compound B2 ") of the alkoxyl group of being combined with Siliciumatom more than 2; Deng.
Silane compound (B) can have 1 above organic group in 1 molecule, for example can enumerate, can comprise at least a heteroatomic alkyl that is selected from Sauerstoffatom, nitrogen-atoms and the sulphur atom, as concrete example, can enumerate alkyl and (be preferably the alkyl of carbonatoms 1～6.), (methyl) acrylate-based, alkenyl, aryl, their combination etc.As alkyl, for example can enumerate methyl, ethyl, propyl group, sec.-propyl etc.As alkenyl, for example can enumerate vinyl, allyl group, propenyl, pseudoallyl, 2-methyl isophthalic acid-propenyl, 2-methacrylic etc.As aryl, for example can enumerate phenyl, naphthyl etc.Wherein, be preferably methyl, (methyl) acrylate-based, (methyl) acryloxyalkyl.
(silane compound B1)
As silane compound B1, for example can enumerate the silane compound shown in the following formula (b1).
Si(OR
5)
nR
6 4-n (b1)
In the formula (b1), n represents 2,3 or 4, R
5The expression alkyl, R
6The expression organic group.R
6The organic group implication that shown organic group is put down in writing with the organic group that can have as silane compound (B) is identical.
As silane compound B1, for example can enumerate dialkoxy silicanes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, diethyl diethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane; Trialkoxy silanes such as methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane; Tetraalkoxysilanes such as tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan; γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(methyl) acryloxyalkyl trialkoxy silanes such as (methyl) acryloxy propyl-triethoxysilicane; Deng.
In addition, (methyl) acryloxy trialkoxy silane refers to acryloxy trialkoxy silane or methacryloxy trialkoxy silane., (methyl) acryloxyalkyl acrylate-based about (methyl) too.
(silane compound B2)
As silane compound B2, for example can enumerate the compound shown in the following formula (b2-1).
R
7 mSi(OR
8)
nO
(4-m-n)/2 (b2－1)
In the formula (b2-1), R
7Be organic group, R
8Be hydrogen and/or alkyl, m is 0＜m＜2, and n is 0＜n＜2, and m+n is 0＜m+n≤3.Here, R
7The organic group implication that shown organic group is put down in writing with the organic group that can have as silane compound (B) is identical, R
8The alkyl implication that shown alkyl is put down in writing with the alkyl of the organic group that can have as silane compound (B) is identical.
As silane compound B2, for example can enumerate organosilicon alcoxyl base oligopolymer such as methyl methoxy base oligopolymer.Organosilicon alcoxyl base oligopolymer is that main chain is organopolysiloxane, the silicone resin that the molecular end alkoxy is silyl-capped.Methyl methoxy base oligopolymer is equivalent to the compound shown in the formula (b2-1), as its concrete example, can enumerate the compound shown in the following formula (b2-2).
In the formula (b2-2), R
9The expression methyl, a represents 1～100 integer, b represents 0～100 integer.
Methyl methoxy base oligopolymer can use commercially available product, for example can enumerate, x-40-9246 (weight-average molecular weight: 6000, chemical industry society of SHIN-ETSU HANTOTAI system).
In addition, as silane compound B2, for example can enumerate, single at least end has alkoxysilyl, has the compound (below, be also referred to as " silane compound B3 ") of 3 above alkoxyl groups (deriving from the alkoxyl group of alkoxysilyl) in 1 molecule.
Silane compound B3 for example can be used as with respect to 1 mole of the polysiloxane with two terminal silanol groups, and the silane compound that will have an alkoxysilyl carries out the reactant that the dealcoholysis condensation forms and obtains more than 1 mole.
As the silane compound with alkoxyl group that uses in order to make silane compound B3, for example can enumerate the compound shown in the compound shown in the above-mentioned formula (b1), the formula (b2-1) etc.
As silane compound B3, for example can enumerate the silane compound shown in the following formula (b3).
In the formula (b3), n can for the molecular weight value corresponding of silane compound B3.
Compound shown in the formula (b3) for example, can carry out modification with tetramethoxy-silicane (suitable with the compound shown in the formula (b1)) by the polysiloxane that two ends is had silanol group and make.
As silane compound (B), be preferably the silane compound shown in the silane compound shown in the formula (b1), the formula ((b2-1)), more preferably tetraalkoxysilane such as tetraethoxysilane; γ-(methyl) acryloxyalkyl trialkoxy silanes such as (methyl) acryloxy propyl trimethoxy silicane; Methyl methoxy base oligopolymer.
In addition, use at above-mentioned organopolysiloxane (A) under the situation of silicone resin A 1, as silane compound (B), be preferably (methyl) acryloxyalkyl trialkoxy silane of (methyl) acrylic acid series functionality.
The molecular weight of silane compound (B) is preferably 100～1, and 000,000, more preferably 1000～100,000.
In addition, be under the situation of silane compound B2 at silane compound (B), the serve as reasons weight-average molecular weight of polystyrene conversion that chloroform is obtained as the gel permeation chromatography (GPC) of solvent of its molecular weight.
Manufacture method as silane compound (B) is not particularly limited, and for example can enumerate, in the past known manufacture method.
Silane compound (B) can a kind of independent use also can be two or more and use.
The amount of silane compound (B) is preferably 0.5～2000 mass parts, more preferably 10～2000 mass parts with respect to organopolysiloxane (A) 100 mass parts.
＜tin compound (C)＞
Composition of the present invention contains tin compound (C).In addition, so-called " tin compound " refers to contain the compound of tin (Sn).
The content of tin compound (C) is, total 100 mass parts with respect to organopolysiloxane (A) and silane compound (B) are 0.001～1 mass parts, thickening under the room temperature that suppresses composition of the present invention, the more excellent such reason of stability under the room temperature is set out, be preferably 0.001～0.5 mass parts, more preferably 0.01～0.1 mass parts.
As tin compound (C), so long as " tin compound " just is not particularly limited, for example can enumerate, the tin compound of the tin compound of divalent, 4 valencys etc., but from the viewpoint of serviceable time, be preferably the tin compound of 4 valencys.
As the tin compound of divalent, for example can enumerate the tin metal carboxylate of divalents such as two (2 ethyl hexanoic acid) tin, two (n-caprylic acid) tin, two naphthenic acid tin, distearyl acid tin.
As the tin compound of 4 valencys, for example can enumerate the tin compound shown in the formula (c1); Dimorphism, the polymer-type of the tin compound shown in the formula (c1); Deng.
R
10 a－Sn－［O－CO－R
11］
4-a (c1)
In the formula (c1), R
10The expression alkyl, R
11The expression alkyl, a represents 1～3 integer.
As R
10Shown alkyl for example can be enumerated, and the alkyl of carbonatoms more than 1 as concrete example, can be enumerated methyl, ethyl, propyl group, butyl, amyl group, octyl group etc.
As R
11Shown alkyl is not particularly limited, and can also can be the side chain shape for the straight chain shape, can have unsaturated link(age), can have heteroatomss such as Sauerstoffatom, nitrogen-atoms, sulphur atom, for example can enumerate aliphatic alkyls such as methyl, ethyl; The ester ring type alkyl; Aromatic hydrocarbyl; Their combination; Deng.
As the dimorphism of the tin compound shown in the formula (c1), for example can enumerate the tin compound shown in the following formula (c2).
In the formula (c2), R
10, R
11With the R in the formula (c1)
10, R
11Implication is identical, and a represents 1 or 2.
As the concrete example of the tin compound of 4 valencys, can enumerate the oxalic acid tin methide, two (methyl ethyl diketone) tin methide, dibutyl tin laurate, the toxilic acid dibutyl tin, the phthalic acid dibutyl tin, two sad dibutyl tins, two (2 ethyl hexanoic acid) dibutyl tin, two (methyl-maleic acid) dibutyl tin, two (ethyl toxilic acid) dibutyl tin, two (butyl toxilic acid) dibutyl tin, two (octyl group toxilic acid) dibutyl tin, two (tridecyl toxilic acid) dibutyl tin, two (benzyl toxilic acid) dibutyl tin, dibutyltin diacetate, two (ethyl toxilic acid) dioctyl tin, two (octyl group toxilic acid) dioctyl tin, the dimethanol dibutyl tin, two (nonylphenol) dibutyl tin, dibutyltin oxide, two (methyl ethyl diketone) dibutyl tin, two (ethylacetoacetone(EAA,HEAA)) dibutyl tin, two lauric acid dioctyl tins, the oxalic acid dioctyl tin, dialkyl tin compounds such as two (methyl ethyl diketone) dioctyl tin; 2 aggressiveness of dialkyl tin compound; The polymkeric substance of dialkyl tins such as dibutyltin maleate polymer, dioctyl tin maleate polymkeric substance; The reactants such as reactant of dioctyl pink salt and ethyl orthosilicate; Single-alkyl tin compounds such as three (2 ethyl hexanoic acid) Monobutyltin; Deng.
In addition, from the viewpoint to the influence of human body, be preferably the tin compound of dioctyl tin system, for example, the reactant of two (methyl ethyl diketone) dioctyl tin, dioctyl pink salt and ethyl orthosilicate etc. can be in industrial acquisition.
Tin compound (C) can a kind of independent use, also can be two or more and use.
Manufacture method about tin compound (C) is not particularly limited, and for example, can make by known method in the past.
＜zn cpds (D)＞
In composition of the present invention, for tin compound (C) and with and make the moisture curing delay that is caused by this tin compound (C), and contain zn cpds (D).
In the present invention, the content of zn cpds (D) is more than the content of tin compound (C).That is, in the present invention, tin compound (C) with respect to the value of the mass ratio (C/D) of zn cpds (D) less than 1.Thus, composition of the present invention, the thickening under the room temperature is suppressed, the excellent in stability under the room temperature.
The more excellent such reason of stability under the room temperature of composition of the present invention, tin compound (C) with respect to the value of the mass ratio (C/D) of zn cpds (D) preferably less than 1 and be more than 0.01, more preferably below 0.1 more than 0.01.
In addition, in the present invention, the content of zn cpds (D) is, is 0.01～5 mass parts with respect to total 100 mass parts of above-mentioned organopolysiloxane (A) and silane compound (B).Thus, the Thermocurable of composition of the present invention is also excellent.
From the more excellent such reason of Thermocurable, the content of zn cpds (D) is that total 100 mass parts with respect to organopolysiloxane (A) and silane compound (B) are preferably 0.01～5 mass parts, more preferably 0.1～1 mass parts.
In addition, composition of the present invention is by containing zn cpds (D), thereby sulfidation-resistance is also excellent.This thinks, in the sealing material that obtains in that composition of the present invention is solidified, zn cpds (D) (for example catches airborne corrosive gases, hydrogen sulfide, amine etc. have the gas of unshared electron pair), therefore can prevent the corrosion of metal (for example, variable color) that brought by corrosive gases.But such mechanism is what infer, even other mechanism is arranged also within the scope of the invention.
Zn cpds (D) as composition of the present invention contains so long as comprise the compound of zinc, just is not particularly limited, and for example can enumerate zinc salts such as zinc phosphate; Zine coordination compound; The zinc alkoxide; Zinc oxide such as zinc oxide, zinc; Deng.
Wherein, from sulfidation-resistance, the more excellent such viewpoint of the transparency, be preferably zinc salt and/or zine coordination compound.
Here, as zinc salt, so long as (comprise mineral acid, organic acid by zinc and acid.) salt that forms, just be not particularly limited.In addition, as zine coordination compound, so long as the inner complex that is formed by zinc and part just is not particularly limited.
In addition, in the present invention, zn cpds (D) from the viewpoint of heat-resisting tint permanence, does not preferably contain benzoglioxaline salt in fact.
As the concrete example of zn cpds (D), can enumerate following formula (d1) or (d2) shown in zn cpds; The zine coordination compound of salicylic acid compound; The zine coordination compound of diamine compound; Deng compound.
At first, formula (d1) is as follows.
Zn(O－CO－R
1)
2 (d1)
In the formula (d1), R
1The alkyl or aryl of expression carbonatoms 1～18.In addition, the CO in the formula (d1) is carbonyl (C=O).
As R
1The alkyl of shown carbonatoms 1～18 for example can be enumerated, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, 1-ethyl pentyl group, new nonyl, new decyl etc.
As R
1The aryl of shown carbonatoms 1～18 for example can be enumerated, phenyl, naphthyl etc.
Be under the situation of salt at the zn cpds (D) shown in the formula (d1), as zinc salt, for example can enumerate, the zinc salt shown in the following formula (d1 ').
Formula (d1 ') in, R
1With the R in the formula (d1)
1Implication is identical.
As the zn cpds (D) shown in the formula (d1), for example can enumerate zinc acetate, 2 ethyl hexanoic acid zinc, zinc octoate, zinc neodecanoate, etheric acid zinc, (methyl) zinc acrylate resin, zinc salicylate etc.
Next, formula (d2) is as follows.
Zn(R
2COCHCOR
3)
2 (d2)
In the formula (d2), R
2, R
3Identical or different, 1 valency alkyl or alkoxyl group of expression carbonatoms 1～18.(R in the formula (d2)
2COCHCOR
3) be respectively any of following formula, be combined with zinc with " C-O-".
Be under the situation of coordination compound at the zn cpds (D) shown in the formula (d2), as zine coordination compound, for example can enumerate, the zine coordination compound shown in the following formula (d2 ').
Formula (d2 ') in, R
2, R
3With the R in the formula (d2)
2, R
3Implication is identical, is positioned at same (R
2COCHCOR
3) interior R
2, R
3Can exchange.
As the R in the formula (d2)
2, R
31 valency alkyl of shown carbonatoms 1～18 for example can be enumerated, and the alkyl or aryl of carbonatoms 1～18 is (with the R in the formula (d1)
1The alkyl or aryl implication of shown carbonatoms 1～18 is identical).
As the R in the formula (d2)
2, R
3Shown alkoxyl group for example can be enumerated, methoxyl group, oxyethyl group, propoxy-etc.
As the zn cpds (D) shown in the formula (d2), for example can enumerate, two (methyl ethyl diketone roots) close zine coordination compound, 2,2,6,6,6 tetramethyl-s-3,5-heptadione zine coordination compound etc.
More excellent from Thermocurable, sulfidation-resistance also more excellent such reason sets out, zn cpds (D) is preferably the zn cpds shown in formula (d1) or the formula (d2), or also use them, more preferably zinc acetate, 2 ethyl hexanoic acid zinc, zinc octoate, zinc neodecanoate, etheric acid zinc, (methyl) zinc acrylate resin, zinc salicylate, two (methyl ethyl diketone roots) close zine coordination compound, 2,2,6,6,6 tetramethyl-s-3,5-heptadione zine coordination compound.
Zn cpds (D) can a kind of independent use, also can be two or more and use.
Manufacture method as zn cpds (D), for example, can use by being selected from least a in zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and the zinc nitrate with respect to 1 mole, make more than 1.5 moles and react and the zn cpds that obtains less than 3 moles acid.
As employed acid this moment, be not particularly limited, for example can enumerate mineral acids such as phosphoric acid; Organic acids such as stearic acid, palmitinic acid, lauric acid, 2 ethyl hexanoic acid, (methyl) vinylformic acid, neodecanoic acid; Their ester; Deng.
＜zirconium compounds (E) and/or hafnium compound (F)＞
Composition of the present invention can also contain zirconium compounds (E) and/or hafnium compound (F).They for the long-term reliability under the high temperature that makes composition of the present invention in the condensation catalyst good.
Can think zirconium compounds (E) and/or hafnium compound (F) when the initial cure of composition of the present invention or during the heating after the initial cure, work as Lewis acid, promote the crosslinking reaction of organopolysiloxane (A) and silane compound (B).
More specifically, zirconium compounds (E) and/or hafnium compound (F) can be activated by heating, make the silanol group reaction of silanol group reaction, silanol group and alkoxysilyl each other (for example, by) carry out condensation.Thus, composition of the present invention is whole by heating is evenly solidified.
The more excellent such reason of long-term reliability under the high temperature of composition of the present invention, the content of zirconium compounds (E) and/or hafnium compound (F) is, total 100 mass parts with respect to organopolysiloxane (A) and silane compound (B), be preferably 0.001～1 mass parts, more preferably 0.01～0.5 mass parts, more preferably 0.001～0.05 mass parts.
Below, zirconium compounds (E) and hafnium compound (F) are described respectively.
［ zirconium compounds (E) ］
At first, zirconium compounds (E) is described.Zirconium compounds (E) just is not particularly limited so long as have zirconium atom and the zirconium compounds of organic group.
Here, as the organic group that zirconium has, for example can enumerate, organic carboxylate (O-CO-R); The group that the alkyl of alkoxyl group, phenoxy group etc. is combined with the oxygen base (O-R); Part; Their combination; Deng.
More specifically, as zirconium compounds (E), for example can enumerate, the compound (compd E 1 ') shown in the compound shown in the following formula (e1) (compd E 1), following formula (e1 '), the compound (compd E 2) shown in the following formula (e2) etc. can be fit to use them.
In the formula (e1), R
12The alkyl of expression carbonatoms 1～18.
In the formula (e1 '), 1 valency alkyl of R ' expression carbonatoms 1～18, R " 1 valency alkyl or acyl group of expression carbonatoms 1～18, n represents 0～2 integer.
In the formula (e2), R
13Identical or different, the alkyl of expression carbonatoms 1～16, R
14Identical or different, the alkyl of expression carbonatoms 1～18, m represents 1～3 integer.
(compd E 1)
Compd E 1 is for comprising the oxygen zirconium ［ (Zr=O)
2+As the zirconium metal-salt of integrant.Composition of the present invention is by inclusion compound E1, thereby Thermocurable is more excellent.
Acid as using for the zirconium metal-salt of making compd E 1 is not particularly limited, and for example can enumerate, and carboxylic acid as the concrete example of carboxylic acid, can be enumerated aliphatic carboxylic acids such as acetic acid, propionic acid, sad (2 ethyl hexanoic acid), n-nonanoic acid, stearic acid, lauric acid; Ester ring type such as naphthenic acid, naphthenic acid carboxylic acid; Aromatic carboxylic acids such as phenylformic acid; Deng.
As the aliphatic carboxylate, for example can enumerate two zirconyl octoates, two neodecanoic acid oxygen zirconiums etc.As the ester ring type carboxylate salt, for example can enumerate naphthenic acid oxygen zirconium, cyclohexylenedinitrilotetraacetic acid oxygen zirconium etc.As the aromatic carboxylic acid salt, for example can enumerate phenylformic acid oxygen zirconium.
Wherein, from the more excellent such reason of Thermocurable, be preferably any one or both of two zirconyl octoates and naphthenic acid oxygen zirconium.
(compd E 1 ')
Compd E 1 ' is similarly for comprising the oxygen zirconium ［ (Zr=O)
2+As the oxygen zirconium coordination compound of integrant, composition of the present invention is by inclusion compound E1 ', thereby Thermocurable is more excellent.
As R ' and the R in the above-mentioned formula (e1 ') " shown in 1 valency alkyl of carbonatoms 1～18, for example can enumerate, the alkyl or aryl of carbonatoms 1～18 is (with the R in the above-mentioned formula (d1)
1The alkyl or aryl implication of shown carbonatoms 1～18 is identical).
As the oxygen zirconium coordination compound shown in the above-mentioned formula (e1 '), for example can enumerate, R represents methyl, and R ' represents acyl group, and n represents acetylacetone based-2-ethyl hexanoyl-oxygen zirconium of 1; R represents methyl, and n represents 0 bis-acetylacetonate oxygen zirconium; Deng.
(compd E 2)
Compd E 2 like that, has 1～3 acyl group (R shown in above-mentioned formula (e2)
13-CO-).In the compd E 2 shown in the formula (e2), acyl group is contained in the formula (e2) as carboxylicesters.M is under the situation more than 2 in formula (e2), a plurality of R
13Can be the same or different.In addition, be under 1～2 the situation at m, a plurality of R
13Can be the same or different.
R in the formula (e2)
13The carbonatoms of shown alkyl is preferably 3～16, and more preferably 4～16.
R
13Shown alkyl can also can be the side chain shape for the straight chain shape, can have unsaturated link(age), can have heteroatoms (for example, Sauerstoffatom, nitrogen-atoms, sulphur atom etc.).
As R
13Shown alkyl for example can be enumerated, aliphatic alkyl, ester ring type alkyl, aromatic hydrocarbyl, their combination etc.
As the ester ring type alkyl, for example can enumerate cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group; Naphthenic ring (deriving from the naphthenic hydrocarbon ring of naphthenic acid); Condensed ring system alkyl such as adamantyl, norborneol alkyl; Deng.
As aromatic hydrocarbyl, for example can enumerate phenyl, naphthyl, Azulene etc.
As aliphatic alkyl, for example can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl, octyl group, 2-ethylhexyl, nonyl, decyl, undecyl etc.
Wherein, be preferably ester ring type alkyl, aromatic hydrocarbyl, more preferably cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, naphthenic ring are (as R
13The naphthenic acid ester group of COO-), phenyl, more preferably cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, naphthenic ring.
As the R with ester ring type alkyl
13COO-for example can enumerate, cycloalkyl carbonyl oxygen bases such as cyclopropyl carbonyl oxygen base, cyclobutyl carbonyl oxygen base, cyclopentyl carbonyl oxygen base, cyclohexyl carbonyl oxygen base (hexahydrobenzoic acid ester group), suberyl carbonyl oxygen base (suberyl formic acid ester group), ring octyl group carbonyl oxygen base; Naphthenic acid ester group (cycloalkanes acid esters); The carbonyl oxygen base of condensed ring system alkyl such as adamantyl carbonyl oxygen base, norborneol alkyl carbonyl oxygen base; Deng.
As the R with aromatic hydrocarbyl
13COO-for example can enumerate, phenyl carbonyl oxygen base, naphthyl carbonyl oxygen base, Azulene base carboxyl etc.
As the R with aliphatic alkyl
13COO-for example can enumerate, acetic ester, propionic ester, butyric ester, isobutyrate, octanoate, 2-ethylhexanoate, pelargonate, laurate etc.
Wherein, be preferably the R with ester ring type alkyl
13COO-, has the R of aromatic hydrocarbyl
13COO-, 2 ethylhexoates, more preferably cyclopropyl carbonyl oxygen base, cyclopentyl carbonyl oxygen base, cyclohexyl carbonyl oxygen base, adamantyl carbonyl oxygen base, naphthenic acid ester group, phenyl carbonyl oxygen base, more preferably cyclopropyl carbonyl oxygen base, cyclopentyl carbonyl oxygen base, cyclohexyl carbonyl oxygen base, adamantyl carbonyl oxygen base, naphthenic acid ester group.
R in the formula (e2)
14The carbonatoms of shown alkyl is preferably 3～8.
As R
14Shown alkyl can also can be the side chain shape for the straight chain shape, can have unsaturated link(age), can have heteroatoms (for example, Sauerstoffatom, nitrogen-atoms, sulphur atom etc.).
As R
14Shown alkyl for example can be enumerated, aliphatic alkyl, ester ring type alkyl, aromatic hydrocarbyl, their combination etc.
As the R with aliphatic alkyl
14O-(alkoxyl group) for example can enumerate, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, pentyloxy, hexyloxy, octyloxy etc., wherein, as the R with aliphatic alkyl
14O-(alkoxyl group) is preferably methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, isopropoxy.
As the compd E 2 with ester ring type alkyl, for example can enumerate alkoxyl group cyclopropane-carboxylic acid zirconiums such as tri-alkoxy monocycle propane formic acid zirconium, dialkoxy two cyclopropane-carboxylic acid zirconiums, monoalkoxy three cyclopropane-carboxylic acid zirconiums; Alkoxyl group cyclopentane-carboxylic acid zirconiums such as tri-alkoxy monocycle pentane formic acid zirconium, dialkoxy two cyclopentane-carboxylic acid zirconiums, monoalkoxy three cyclopentane-carboxylic acid zirconiums; Alkoxyl group naphthenic acid zirconiums such as three butoxy monocycle hexane formic acid zirconiums, dibutoxy bicyclohexane formic acid zirconium, single butoxy three naphthenic acid zirconiums, three isopropoxy monocycle hexane formic acid zirconiums, diisopropoxy bicyclohexane formic acid zirconium, single isopropoxy three naphthenic acid zirconiums; Alkoxyl group adamantanecarboxylic acid zirconiums such as tri-alkoxy list adamantanecarboxylic acid zirconium, dialkoxy two adamantanecarboxylic acid zirconiums, monoalkoxy three adamantanecarboxylic acid zirconiums; Alkoxyl group zirconium naphthenates such as three butoxy monocycle alkanoic acid zirconiums, dibutoxy two zirconium naphthenates, single butoxy three zirconium naphthenates, three isopropoxy monocycle alkanoic acid zirconiums, diisopropoxy two zirconium naphthenates, single isopropoxy three zirconium naphthenates; Deng.
As the compd E 2 with aromatic hydrocarbyl, for example can enumerate alkoxybenzoic acid zirconiums such as three butoxy list phenylformic acid zirconiums, dibutoxy dibenzoic acid zirconium, single butoxy three phenylformic acid zirconiums, three isopropoxy list phenylformic acid zirconiums, diisopropoxy dibenzoic acid zirconium, single isopropoxy three phenylformic acid zirconiums.
As the compd E 2 with aliphatic alkyl, for example can enumerate alkoxyl group butyric acid zirconiums such as three butoxy list isopropylformic acid zirconiums, dibutoxy two isopropylformic acid zirconiums, single butoxy three isopropylformic acid zirconiums, three isopropoxy list isopropylformic acid zirconiums, diisopropoxy two isopropylformic acid zirconiums, single isopropoxy three isopropylformic acid zirconiums; Alkoxyl group 2 thylhexoic acid zirconiums such as three butoxy lists, 2 thylhexoic acid zirconiums, dibutoxy 22 thylhexoic acid zirconiums, single butoxy 32 thylhexoic acid zirconiums, three isopropoxy lists, 2 thylhexoic acid zirconiums, diisopropoxy 22 thylhexoic acid zirconiums, single isopropoxy 32 thylhexoic acid zirconiums; Alkoxyl group neodecanoic acid zirconiums such as three butoxy list neodecanoic acid zirconiums, dibutoxy two neodecanoic acid zirconiums, single butoxy three neodecanoic acid zirconiums, three isopropoxy list neodecanoic acid zirconiums, diisopropoxy two neodecanoic acid zirconiums, single isopropoxy three neodecanoic acid zirconiums; Deng.
Wherein, be preferably the compd E 2 with ester ring type alkyl, compd E 2 with aromatic hydrocarbyl, tri-alkoxy monocycle alkanoic acid zirconium more preferably, tri-alkoxy list isopropylformic acid zirconium, tri-alkoxy list 2 thylhexoic acid zirconiums, tri-alkoxy monocycle propane formic acid zirconium, tri-alkoxy cyclobutane formate zirconium, tri-alkoxy monocycle pentane formic acid zirconium, tri-alkoxy monocycle hexane formic acid zirconium, tri-alkoxy list adamantanecarboxylic acid zirconium, tri-alkoxy monocycle alkanoic acid zirconium, more preferably three butoxy monocycle alkanoic acid zirconiums, three butoxy list isopropylformic acid zirconiums, three butoxy lists, 2 thylhexoic acid zirconiums, three butoxy monocycle propane formic acid zirconiums, three butoxy monocycle pentane formic acid zirconiums, three butoxy monocycle hexane formic acid zirconiums, three butoxy list adamantanecarboxylic acid zirconiums, three butoxy monocycle alkanoic acid zirconiums.
In addition, compd E 2 is preferably the zirconium metal-salt that contains alkoxyl group with 1～3 acyl group (ester bond).
As the zirconium metal-salt that contains alkoxyl group with 1～3 acyl group; for example can enumerate; three butoxy monocycle alkanoic acid zirconiums; three butoxy list isopropylformic acid zirconiums; three butoxy lists, 2 thylhexoic acid zirconiums; three butoxy list neodecanoic acid zirconiums; dibutoxy two zirconium naphthenates; dibutoxy two isopropylformic acid zirconiums; dibutoxy 22 thylhexoic acid zirconiums; dibutoxy two neodecanoic acid zirconiums; single butoxy three zirconium naphthenates; single butoxy three isopropylformic acid zirconiums; single butoxy 32 thylhexoic acid zirconiums; single butoxy three neodecanoic acid zirconiums; wherein, be preferably and be selected from three butoxy monocycle alkanoic acid zirconiums; at least a in three butoxy list isopropylformic acid zirconiums and three butoxy lists, the 2 thylhexoic acid zirconiums.
As the manufacture method of compd E 2, for example, can pass through with respect to Zr (OR
14)
4Shown tetrol zirconium (R
14With the R in the formula (e2)
14Implication is identical) 1 mole, use more than 1 mole and less than 4 moles R
13Carboxylic acid (R shown in the-COOH
13With the R in the formula (e2)
13Implication is identical), under nitrogen atmosphere, under 20～80 ℃ condition, stir, thereby make.
About the reaction of Zr alkoxide and carboxylic acid, can be with reference to D.C.Bradley work " Metal alkoxide " Academic Press (1978).
As the Zr (OR that can use in order to make compd E 2
14)
4, for example can enumerate tetramethyl alcohol zirconium, tetraethoxide zirconium, four zirconium-n-propylates, four zirconium iso-propoxides, four zirconium-n-butylates etc.
As the carboxylic acid that can use in order to make compd E 2, for example can enumerate aliphatic carboxylic acid such as acetic acid, propionic acid, isopropylformic acid, sad, 2 ethyl hexanoic acid, n-nonanoic acid, lauric acid; Ester ring type carboxylic acids such as naphthenic acid, cyclopropane-carboxylic acid, cyclopentane-carboxylic acid, hexahydrobenzoic acid (naphthenic acid), adamantanecarboxylic acid, norbornane formic acid; Aromatic carboxylic acids such as phenylformic acid; Deng.
［ hafnium compound (F) ］
Next, hafnium compound (F) is described.Hafnium compound (F) is as long as for having the compound of hafnium atom and organic group, just be not particularly limited, but the more excellent such reason of long-term reliability under the high temperature of composition of the present invention is preferably the compound shown in the compound shown in the following formula (f1) and/or the following formula (f2).
In the formula (f1), n represents 1～4 integer, R
15The expression alkyl, R
16The alkyl of expression carbonatoms 1～18.
In the formula (f2), m represents 1～4 integer, R
16The alkyl of expression carbonatoms 1～18, R
17And R
18Identical or different, alkyl or the alkoxyl group of expression carbonatoms 1～18.
At first, the hafnium compound (F) shown in the above-mentioned formula (f1) is described.
R in the formula (f1)
15Shown alkyl can also can be the side chain shape for the straight chain shape, can have unsaturated link(age), can have heteroatoms (for example, Sauerstoffatom, nitrogen-atoms, sulphur atom etc.).
As R
15Shown alkyl for example can be enumerated, and the aliphatic alkyl of carbonatoms 1～18 (comprises alkyl; Unsaturated fatty hydrocarbons bases such as allyl group; Deng), ester ring type alkyl, aryl (aromatic hydrocarbyl), their combination etc.
As aliphatic alkyl, for example can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, hexyl, octyl group, 2-ethylhexyl, nonyl, decyl, undecyl etc.
As the ester ring type alkyl, for example can enumerate cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group; Naphthenic ring (deriving from the naphthenic hydrocarbon ring of naphthenic acid); Condensed ring system alkyl such as adamantyl, norborneol alkyl; Deng.
As aromatic hydrocarbyl, for example can enumerate phenyl, naphthyl, Azulene etc.
Wherein, more excellent from Thermocurable, the excellent such viewpoint of sulfidation-resistance is set out, be preferably ester ring type alkyl, aromatic hydrocarbyl, their combination, more preferably be selected from least a in cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, naphthenic ring, adamantyl, norborneol alkyl, phenyl, naphthyl and the Azulene, more preferably cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, naphthenic ring are (as R
15The naphthenic acid ester group of COO-), phenyl, be preferably cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, naphthenic ring especially.
R in the formula (f1)
16The carbonatoms of shown alkyl is 1～18, and is more excellent from Thermocurable, and the excellent such reason of sulfidation-resistance is set out, and is preferably 3～8.
As R
16Shown alkyl for example can be enumerated, and methyl, ethyl, propyl group (n-propyl, sec.-propyl), butyl, amyl group, hexyl, octyl group etc. wherein, are preferably methyl, ethyl, propyl group (n-propyl, sec.-propyl), butyl, amyl group.
As having the ester ring type alkyl as R
15Hafnium compound (F) shown in the formula of shown alkyl (f1), for example can enumerate alkoxyl group (single～three) cyclopropane-carboxylic acid hafnium, Fourth Ring propane formic acid hafnium, alkoxyl group (single～three) cyclopentane-carboxylic acid hafnium, pyramidane formic acid hafnium, alkoxyl group (single～three) naphthenic acid hafnium, prismane formic acid hafnium, alkoxyl group (single～three) adamantanecarboxylic acid hafnium, four adamantanecarboxylic acid hafniums, alkoxyl group (single～three) naphthenic acid hafnium, Fourth Ring alkanoic acid hafnium etc.
As having aromatic hydrocarbyl as R
15Hafnium compound (F) shown in the formula of shown alkyl (f1) for example can be enumerated, alkoxyl group (single～three) phenylformic acid hafnium, four phenylformic acid hafniums etc.
As having aliphatic alkyl as R
15Hafnium compound (F) shown in the formula of shown alkyl (f1), for example can enumerate alkoxyl group (single～three) butyric acid hafnium, four butyric acid hafniums, alkoxyl group (single～three) 2 thylhexoic acid hafniums, 42 thylhexoic acid hafniums, alkoxyl group (single～three) neodecanoic acid hafnium, "four news" (new ideas capric acid hafnium etc.
In addition, in this specification sheets, " (single～three) " refer to any in the list, two and three.
Wherein, more excellent from Thermocurable, the excellent such reason of sulfidation-resistance is set out, be preferably tri-alkoxy monocycle alkanoic acid hafnium, tri-alkoxy list isopropylformic acid hafnium, tri-alkoxy list 2 thylhexoic acid hafniums, tri-alkoxy monocycle propane formic acid hafnium, tri-alkoxy cyclobutane formate hafnium, tri-alkoxy monocycle pentane formic acid hafnium, tri-alkoxy monocycle hexane formic acid hafnium, tri-alkoxy list adamantanecarboxylic acid hafnium, tri-alkoxy list phenylformic acid hafnium, dialkoxy two naphthenic acid hafniums, more preferably three butoxy monocycle alkanoic acid hafniums, three butoxy list isopropylformic acid hafniums, three butoxy lists, 2 thylhexoic acid hafniums, three butoxy monocycle propane formic acid hafniums, three butoxy monocycle pentane formic acid hafniums, three butoxy monocycle hexane formic acid hafniums, tri-alkoxy list phenylformic acid hafnium, three butoxy list adamantanecarboxylic acid hafniums, dibutoxy two naphthenic acid hafniums, tripropoxy monocycle alkanoic acid hafnium.
Next, the hafnium compound (F) shown in the above-mentioned formula (f2) is described.
R in the formula (f2)
16With the R in the formula (f1)
16Implication is identical.
R in the formula (f2)
17, R
18R in the alkyl of shown carbonatoms 1～18 and the formula (f1)
15Carbonatoms in the shown alkyl is that 1～18 alkyl is same.
As the R in the formula (f2)
17, R
18Shown alkoxyl group for example can be enumerated, the alkoxyl group of carbonatomss 1～18 such as methoxyl group, oxyethyl group, propoxy-.
R in the formula (f2)
17, R
18Can have halogens such as chlorine atom, bromine atoms, fluorine atom.
In addition, in the formula (f2), so-called R
17With R
18Can exchange.
As the hafnium compound (F) shown in the formula (f2), for example can enumerate, hafnium alkoxide (single～three) 2,4-diacetylmethane salt, hafnium-2,4-diacetylmethane salt, hafnium alkyl diacetylmethane salt, hafnium fluorine diacetylmethane salt etc. wherein, are preferably hafnium two-propyl carbinol salt (two-2,4-diacetylmethane salt), hafnium-2,4-diacetylmethane salt, hafnium tetramethyl-diacetylmethane salt, hafnium trifluoro diacetylmethane salt.
＜other composition＞
Composition of the present invention in the scope of not damaging purpose of the present invention, effect, can also contain additive as required.
As additive, for example can enumerate weighting agents such as mineral filler, antioxidant, lubricant, UV light absorber, hot photostabilizer, dispersion agent, static inhibitor, stopper, defoamer, curing catalyst, solvent, fluorescent substance (inorganics, organism), age resister, free radical inhibitors, the cementability modifying agent, fire retardant, tensio-active agent, the storage stability modifying agent, ozone ageing prevents agent, thickening material, softening agent, the radioactive rays blocker, nucleator, coupling agent, the electroconductibility imparting agent, phosphorus is peroxide decomposer, pigment, metal passivator, the rerum natura conditioning agent, tackifier, bonding auxiliary agent etc.
As fluorescent substance (inorganics), for example can enumerate, YAG is that fluor, ZnS are fluor, Y
2O
2S is fluor, red light-emitting phosphor, blue-light-emitting fluorescent material, green emitting fluor etc.
As tackifier or bonding auxiliary agent, for example can enumerate, known epoxies such as epoxy silane, epoxy silane oligomer are silane coupling agent; Two (alkoxyl group) alkane; Isocyanurate derivative; Deng, wherein, be preferably two (alkoxyl group) alkane and/or isocyanurate derivative.
As two (alkoxyl group) alkane, for example be preferably, be selected from two (triethoxysilyl) ethane, 1 of 1,2-, two (trimethoxysilyl) hexanes, 1 of 6-, two (trimethoxysilyl) heptane, 1 of 7-, two (trimethoxysilyl) octanes, 1 of 8-, at least a in two (trimethoxysilyl) nonanes of 9-and two (trimethoxysilyl) decane of 1,10-, more preferably 1, two (trimethoxysilyl) hexanes of 6-.
As isocyanurate derivative, be preferably the isocyanurate derivative shown in the following formula.
In the above-mentioned formula, R represents organic group or has the monovalence alkyl of aliphatics unsaturated link(age) to have substituting groups such as epoxy group(ing), glycidoxy, alkoxysilyl, (methyl) acryl independently of one another.
Organic group as shown in the R in the above-mentioned formula is not particularly limited, and for example can enumerate alkyl such as methyl, ethyl, propyl group, butyl; Aryl such as phenyl, tolyl, xylyl, naphthyl; Aralkyl such as benzyl, styroyl; Cycloalkyl such as cyclopentyl, cyclohexyl; Haloalkyl; Deng.
In addition, the monovalence alkyl with aliphatics unsaturated link(age) as shown in the R in the above-mentioned formula is not particularly limited, and for example can enumerate the unsaturated alkyl of carbonatomss 2～8 such as vinyl, allyl group, butenyl, pentenyl, hexenyl, heptenyl.
As the isocyanurate derivative shown in the above-mentioned formula, for example can enumerate three-(3-trimethoxy-silylpropyl) isocyanuric acid esters.
These tackifier or bonding auxiliary agent may be used singly or in combination of two or more.
As the content of these tackifier or bonding auxiliary agent, under the situation of using two (alkoxyl group) alkane, be preferably 0.1～5 mass parts with respect to total 100 mass parts of above-mentioned organopolysiloxane (A) and silane compound (B).In addition, using under the situation of isocyanurate derivative, be preferably 0.1～10 mass parts with respect to total 100 mass parts of above-mentioned organopolysiloxane (A) and silane compound (B), more preferably 0.1～5 mass parts.
Composition of the present invention, from the excellent such reason of stability in storage, preferably not moisture in fact.In the present invention, so-called " not moisture in fact ", the amount that refers to the water in the composition of the present invention is below the 0.1 quality %.
In addition, from the excellent such reason of operating environment, composition of the present invention is preferably and does not contain solvent in fact.In the present invention so-called " not containing solvent in fact ", the amount that refers to the solvent in the composition of the present invention is below the 1 quality %.
The manufacture method of composition of the present invention is not particularly limited, for example can enumerate, by with above-mentioned organopolysiloxane (A), silane compound (B), tin compound (C), zn cpds (D), as required zirconium compounds (E) and/or hafnium compound (F) and the additive as required method of mixing to make.Composition of the present invention can be made as one-pack type or two-component-type.
Composition of the present invention can be used as and for example seals material (for example, optical semiconductor is used) use.As can for example enumerating photodiode (LED), organic electroluminescent device (organic EL), laser diode, led array etc. with composition of the present invention as the optical semiconductor that the sealing material uses.As LED, for example can enumerate high-capacity LED, high-brightness LED, general brightness LED etc.
In addition, composition of the present invention can for example be used for purposes such as display material, optical recording medium material, optical device material, light component materials, fiber optic materials, light/electric function organic materials, semiconductor integrated circuit periphery material.
As the adherend of composition of the present invention, for example can enumerate resins such as metal (for example, the metal of the 11st family), glass, rubber, semi-conductor (for example, optical semiconductor), polyphthalamide etc.In addition, as the metal of the 11st family, be preferably and be selected from least a in copper, silver and the gold.
Composition of the present invention from the transparency, the more excellent such reason of sulfidation-resistance, preferably uses in the presence of the member that comprises silver.Can be bonding with adherend by the silicone resin layer that composition of the present invention obtains.
＜using method＞
As the using method of composition of the present invention, for example can enumerate, possess the using method of the curing process that in the presence of the member that comprises silver, makes composition curing of the present invention.Below, with this using method as the using method of composition of the present invention (below, be also referred to as " using method of the present invention ".) describe.
As the member that comprises silver that uses in the using method of the present invention, for example can enumerate, silver, silvering etc. as concrete example, can be enumerated reverberator (reflector) etc.
Above-mentioned curing process can make the operation of composition curing of the present invention for by heating and/or rayed.As the temperature that composition of the present invention is heated, be preferably near 80 ℃～150 ℃, more preferably near 150 ℃.In addition, the light that uses when composition of the present invention is carried out rayed for example can be enumerated ultraviolet ray, electron rays etc.
＜contain the structure of silicone resin＞
The structure that contains silicone resin of the present invention possesses: the member that comprises silver; Cover above-mentioned member, composition of the present invention is solidified and the silicone resin layer that obtains.Above-mentioned silicone resin layer can directly cover above-mentioned member, can cover across other layer (for example, resin layer, glass coating, gas cloud).
The structure that contains silicone resin of the present invention preferably has optical semiconductor.As optical semiconductor, be not particularly limited, for example can enumerate, as the optical semiconductor that composition of the present invention can be used as the sealing material and illustrative optical semiconductor.
Has the mode of optical semiconductor as the structure that contains silicone resin of the present invention, for example can enumerate, above-mentioned silicone resin layer covers the mode (that is the mode of optical semiconductor between above-mentioned silicone resin layer and above-mentioned member) of above-mentioned member across optical semiconductor; Above-mentioned silicone resin layer directly covers the optical semiconductor of configuration side by side and the mode of above-mentioned member; Deng.In addition, in the latter's mode, can be between 2 above-mentioned members vacating configuration at interval and side by side, the configuration optical semiconductor.
Next, will describe based on Fig. 1 and Fig. 2 as the multilayer body (multilayer body 100, multilayer body 200) that contains the structure of silicone resin of the present invention.
Fig. 1 is the sectional view that schematically shows as an example of the multilayer body of the structure that contains silicone resin of the present invention.As shown in Figure 1, multilayer body 100 possesses the member 120 that comprises silver.On member 120, directly dispose silicone resin layer 102.
Fig. 2 is another the routine sectional view that schematically shows as the multilayer body of the structure that contains silicone resin of the present invention.As shown in Figure 2, multilayer body 200 possesses the member 220 that comprises silver.On member 220, directly dispose optical semiconductor 203, on optical semiconductor 203, directly dispose silicone resin layer 202.In addition, can between silicone resin layer 202 and optical semiconductor 203, dispose not shown transparent layer (for example, resin layer, glass coating, gas cloud etc.).
＜optical semiconductor sealing member＞
Optical semiconductor sealing member of the present invention possesses: the framework with recess; Be disposed at the optical semiconductor of the bottom of above-mentioned recess; Be disposed at the member that comprises silver of the medial surface of above-mentioned recess; And be filled in above-mentioned recess and with the sealing of above-mentioned optical semiconductor and above-mentioned member, composition of the present invention is solidified and the sealing material that obtains.
Member as comprising silver is not particularly limited, and for example can enumerate, and comprises silver-colored member and the illustrative member that comprises silver as what use in the using method of the present invention.In addition, as optical semiconductor, be not particularly limited, for example can enumerate, as the optical semiconductor that composition of the present invention can be used as the sealing material and illustrative optical semiconductor.Per 1 of optical semiconductor sealing member of the present invention can have above-mentioned optical semiconductor more than 1 or 2.
Next, to optical semiconductor sealing member of the present invention, describe based on Fig. 3～Fig. 5.
Fig. 3 is the sectional view that schematically shows an example of optical semiconductor sealing member of the present invention.As shown in Figure 3, optical semiconductor sealing member 300 possesses the framework 304 with recess 302.The bottom surface opening of recess 302.Therefore, in framework 304, be formed with end (end 312, end 314) in the mode of surrounding this opening.Lower position in framework 304 disposes the substrate 310 with outer electrode 309.Substrate 310 has formed the bottom of recess 302.Dispose optical semiconductor 303 in the bottom of recess 302.Optical semiconductor 303 is disposed at recess 302 with the direction that upper surface becomes luminescent layer (not shown).The lower surface of optical semiconductor 303 is fixed by installation component 301.Installation component 301 is for example silver-colored thickener, resin etc.Each electrode (not shown) of optical semiconductor 303 comes wire-bonded with outer electrode 309 by electroconductibility line 307.
At the medial surface of recess 302, dispose the reverberator 320 as the member that comprises silver.In recess 302, be filled with sealing material 308, sealing material 308 sealing optical semiconductor 303 and reverberators 320.Here, sealing material 308 solidifies the sealing material that obtains for making composition of the present invention.
In addition, as optical semiconductor sealing member 300, can be end (end 312, the end 314) combination integratedly of framework 304, form the mode of the bottom of recess 302.Under the situation of this mode, reverberator 320 not only is disposed at the medial surface of recess 302, and is disposed at the bottom of recess 302.And optical semiconductor 303 is configured on the reverberator 320 of the bottom that is disposed at recess 302.
In such optical semiconductor sealing member 300, owing to making composition of the present invention solidify the sealing material 308 that obtains, therefore can suppress the corrosion (for example, variable color) as the reverberator 320 of the member that comprises silver.
In addition, because it is low and cure shrinkage is little to be filled in sealing material 308 hardness of recess 302, therefore can suppresses because cure shrinkage and peeling off from recess 302, or suppress electroconductibility line 307 broken strings.
Fig. 4 is another the routine sectional view that schematically shows optical semiconductor sealing member of the present invention.Optical semiconductor sealing member 400 shown in Figure 4 disposes lens 401 at optical semiconductor sealing member 300 shown in Figure 3.As lens 401, can adopt the lens that use composition of the present invention and form.
Fig. 5 is another the routine sectional view again that schematically shows optical semiconductor sealing member of the present invention.In optical semiconductor sealing member 500 shown in Figure 5, in the inside of the resin 506 with lamp function, dispose substrate 510 and inner lead 505.Substrate 510 possesses the framework with recess, disposes optical semiconductor 503 in the bottom of this recess, disposes reverberator 520 at the medial surface of this recess, and the sealing material 502 that composition of the present invention is solidified and obtain is arranged in this recess arrangement.
Next, to composition of the present invention and/or optical semiconductor sealing member of the present invention being used for the situation of light-emitting diode display, describe based on Fig. 6.
Fig. 6 has used the synoptic diagram of an example of the light-emitting diode display of composition of the present invention and/or optical semiconductor sealing member of the present invention for expression.
Light-emitting diode display 600 shown in Figure 6 has the housing 604 that has disposed shading member 605 in its part.In the inside of housing 604, dispose a plurality of optical semiconductor sealing members 601 with rectangular.Optical semiconductor sealing member 601 is sealed by sealing material 606.
Here, as sealing material 606, can use composition of the present invention to solidify and the sealing material that obtains.In addition, as optical semiconductor sealing member 601, can use optical semiconductor sealing member of the present invention.
As the purposes that contains structure and the optical semiconductor sealing member of the present invention of silicone resin of the present invention, for example can enumerate, lamps for vehicle (for example, head lamp, taillight, indicator etc.), home-use lighting fixtures, industrial lighting fixtures, stage lighting fixtures, indicating meter, signal, projector etc.
Embodiment
Below, enumerate embodiment and specifically describe the present invention, but the present invention is not limited to this.
The manufacturing of＜thermohardening type organosilicon resin composition＞
With the composition shown in following the 1st table with (the unit: mass parts) use, use vacuum mixer that they are mixed equably, produce the thermohardening type organosilicon resin composition of the amount shown in the table.
In addition, in following the 1st table, the scale of composition (C) is shown in the amount with respect to this total amount (100 mass parts) under the situation that total amount with composition (A) and composition (B) is made as 100 mass parts.This for the amount of composition (D)～(F) too.
＜estimate＞
Adopt method shown below, estimate.Show the result in following the 1st table.
＜stability/Thermocurable＞
At first, with the thermohardening type organosilicon resin composition that mixes the composition shown in following the 1st table and make, under 55%RH, 23 ℃ condition, place, through 24 hours.
Next, to 24 hours compositions with interior not gelation, further under 150 ℃ condition, be cured, mensuration is through the JIS-A hardness after 8 hours, through the JIS-A hardness (being called " saturated hardness ") after 168 hours, obtain through after 168 hours with respect to rise through the hardness after 8 hours (point).
In not gelation, hardness rises and surpasses under 65% the situation with respect to saturated hardness, as the situation of the stability under the room temperature and Thermocurable excellence and be evaluated as " zero ", rising with respect to saturated hardness in hardness is under 50～65% the situation, be evaluated as the poor slightly situation of Thermocurable " △ ", hardness rise with respect to saturated hardness less than 50% situation under, or be gel at the thermohardening type organosilicon resin composition, can not carry out under the situation of JIS-A measurement of hardness, as the situation of the poor stability under Thermocurable or the room temperature and be evaluated as " * ".
＜the transparency＞
For the thermohardening type organosilicon resin composition that makes gained at 150 ℃ of cured article (thickness: 2mm) that solidified 12 hours and obtained, according to JIS K0115:2004, use ultraviolet-visible absorption spectroscopy determinator (society of Shimadzu Seisakusho Ltd. system), the transmissivity (%) when measuring wavelength 400nm.
If transmissivity (%) is more than 80%, it is excellent then can be evaluated as the transparency.
＜sulfidation-resistance＞
［ solidified sample making ］
Thermohardening type organosilicon resin composition in silvering coating manufacturing makes that thickness is about 1mm, under 150 ℃, 3 hours condition, is cured, thus the solidified sample of acquisition sulfidation-resistance evaluation usefulness.
［ sulfidation-resistance test ］
In the bottom of the moisture eliminator of 10L, place (significantly superfluous with respect to hydrochloric acid 0.5mmol) about the iron sulphide 10g that is ground into powdery.Next, porous plate (having communicating pores) is installed in the mode that does not contact iron sulphide in the top position of the iron sulphide in moisture eliminator, places solidified sample at this porous plate.Next, by to iron sulphide dripping hydrochloric acid 0.5mmol, thereby make hydrogen sulfide 0.25mmol (concentration: be 560ppm as theoretical value) produce (reaction formula: FeS+2HCl → FeCl
2+ H
2S).
［ metewand of sulfidation-resistance ］
From (generation of hydrogen sulfide) of above-mentioned sulfidation-resistance test after 24 hours, by the variable color of the silver in the Visual Confirmation solidified sample.Under the situation that can not confirm variable color, as the situation of sulfidation-resistance excellence and be evaluated as " zero ", confirming under the situation of variable color, as the situation of sulfidation-resistance difference and be evaluated as " * ".
[table 1]
[table 2]
Each composition in above-mentioned the 1st table uses following composition.
Organopolysiloxane 1: the polydimethylsiloxane-α shown in the following formula, omega-diol (ss10, SHIN-ETSU HANTOTAI's chemical industry, weight-average molecular weight: 49000, reactive functional groups: silanol group, average functional group number: 2)
2: two terminal silanol dimethyl organic silicone oils of organopolysiloxane (PRX-413, eastern レ ダ ウ コ ー ニ Application グ society system, weight-average molecular weight: 4000, reactive functional groups: silanol group, average functional group number: 2)
Organopolysiloxane 3: silicone resin (SR1000, モ メ Application テ ィ Block パ フ ォ ー マ Application ス マ テ リ ア Le ズ ジ ャ パ Application contract commercial firm system, weight-average molecular weight: 4000, reactive functional groups: silanol group)
Organopolysiloxane 4: have the dichloromethyl phenylsilane of silanol group and phenyl hydrolytic condensate (weight-average molecular weight: 870, reactive functional groups: silanol group)
Silane compound 1: the two terminal trimethoxysilyl siloxanes of as following, making (weight-average molecular weight: 55000, reactive functional groups: methoxy methyl silylation, average functional group number: 6)
In 3 mouthfuls of flasks of 500mL, stirrer and reflux exchanger are installed, are added polysiloxane (ss10, chemical industry society of SHIN-ETSU HANTOTAI system) 100 mass parts, tetramethoxy-silicane 10 mass parts and acetic acid 0.1 mass parts that two ends have silanol group, under nitrogen atmosphere, reacted 6 hours at 100 ℃, by
1The disappearance of the silanol group that H-NMR analyzes to confirm that ss10 has is made as silane compound 1 with the reactant of gained.The primary structure of silane compound 1 is shown in following formula.
Silane compound 2: the terminal polymethoxy silyl siloxanes of as following, making (weight-average molecular weight: 60000, reactive functional groups: methoxy methyl silylation, average functional group number: 14)
In 3 mouthfuls of flasks of 500mL, stirrer and reflux exchanger are installed, add the polysiloxane (ss10 that two ends have silanol group, chemical industry society of SHIN-ETSU HANTOTAI system) partial hydrolystate (KC-89 of 100 mass parts, methyltrimethoxy silane, chemical industry society of SHIN-ETSU HANTOTAI system) 10 mass parts and acetic acid 0.1 mass parts, under nitrogen atmosphere, reacted 15 hours at 140 ℃, by
1The disappearance of the silanol group that H-NMR analyzes to confirm that ss10 has is made as silane compound 2 with the reactant of gained.The primary structure of silane compound 2 is shown in following formula.
Silane compound 3: organosilicon alcoxyl base oligopolymer (x-40-9246, chemical industry society of SHIN-ETSU HANTOTAI system, weight-average molecular weight: 6000, reactive functional groups: alkoxysilyl, average functional group number: 0＜n＜2)
Silane compound 4: the organosilicon oligopolymer (XR31-B2733 of the alkoxyl group resinous type that the methyl that contains methoxyl group 14 quality % is, モ メ Application テ ィ Block パ フ ォ ー マ Application ス マ テ リ ア Le ズ ジ ャ パ Application contract commercial firm system, weight-average molecular weight: 20000, reactive functional groups: alkoxysilyl)
Silane compound 5: have alkoxysilyl and phenyl, do not have organosilicon alcoxyl base oligopolymer (KR480, chemical industry society of SHIN-ETSU HANTOTAI system, the reactive functional groups: alkoxysilyl) of silanol group
Tin compound 1: dibutyltin diacetate (U-200, day east changes into society's system)
Tin compound 2: dioctyl pink salt and ethyl orthosilicate (Si (OC
2H
5)
4) reactant (s-1, day east change into society's system)
Tin compound 3: two (2 ethyl hexanoic acid) tin (ネ オ ス タ Application U-28, day east changes into society's system)
Zn cpds 1: two (2 ethyl hexanoic acid) zinc (オ ク ト ー プ Zn ， ホ ー プ pharmacy society system)
Zn cpds 2: two (neodecanoic acid) zinc of as following, making
With respect to 1 mole in zinc oxide (Northeast chemistry society system), add 2 moles of neodecanoic acids, at room temperature stir, thereby obtain transparent and uniform liquid (two (neodecanoic acid) zinc).The liquid of gained is made as zn cpds 2.
Zn cpds 3: two (methyl ethyl diketone roots) close zine coordination compound (Northeast chemistry society system)
Zirconium compounds 1: naphthenic acid oxygen zirconium (Japanese chemical industry society system)
Zirconium compounds 2: the three butoxy monocycle alkanoic acid zirconiums of as following, making
With four butanols zirconiums of 87.5 quality % concentration (Northeast chemistry society system) 11.4g (0.026mol) and naphthenic acid (Tokyo changes into society's system, the carbonatoms of the alkyl of being combined with carboxyl average: 15, neutralization value 220mg, below equally.) 6.6g (0.026mol) is fed in the there-necked flask, at room temperature stirs about 2 hours under nitrogen atmosphere, makes the target synthetics.
In addition, the neutralization value of naphthenic acid be in and the amount of the required KOH of naphthenic acid 1g.
Synthetics qualitative uses fourier-transform infrared spectrophotometer (FT-IR) to carry out this analysis.Consequently, belong to the 1700cm of the COOH that derives from carboxylic acid
-1Near the reaction back that is absorbed in disappears, and has confirmed 1450～1560cm
-1Near the peak that derives from COOZr.
The synthetics of gained is made as zirconium compounds 2.The average carbon atom number of R in the naphthenic acid alkali (RCOO-) that zirconium compounds 2 has is 15.
Hafnium compound 1: the three butoxy monocycle alkanoic acid hafniums of as following, making
With four butanols hafniums (the Gelest society system) 4.7g (0.01mol) of 45 quality % concentration and naphthenic acid (Tokyo changes into society's system, the carbonatoms of the alkyl of being combined with carboxyl average: 15, neutralization value 220mg.In addition, the neutralization value of naphthenic acid be in and the amount of the required KOH of naphthenic acid 1g.) 2.55g (0.01mol) is fed in the there-necked flask, at room temperature stirs about 2 hours under nitrogen atmosphere, makes the target synthetics.
Synthetics qualitative uses fourier-transform infrared spectrophotometer (FT-IR) to carry out this analysis.Consequently, belong to the 1700cm of the COOH that derives from carboxylic acid
-1Near the reaction back that is absorbed in disappears, and has confirmed 1,450～1,560cm
-1Near the peak that derives from COOHf.
The synthetics of gained is made as hafnium compound 1.The average carbon atom number of R in the naphthenic acid alkali (RCOO-) that hafnium compound 1 has is 15.
Titanium compound: two (methyl ethyl diketone) titanium isopropoxide (trade(brand)name: TC-100, マ Star モ ト hands over company's system)
Aluminum compound: ethyl acetoacetic acid diisopropoxy aluminium (trade(brand)name: ALCH, Off ァ イ Application ケ ミ カ Le society system is ground in the river)
(tackifier)
Epoxy compounds: epoxy silane oligomer (trade(brand)name: x-41-1053, chemical industry society of SHIN-ETSU HANTOTAI system)
Bis-alkoxy alkane: two trimethoxysilyl hexanes (trade(brand)name: Z6830, eastern レ ダ ウ コ ー ニ Application グ society system)
Isocyanurate derivative: three-(3-trimethoxy-silylpropyl) isocyanuric acid esters (trade(brand)name: x-12-965, chemical industry society of SHIN-ETSU HANTOTAI system)
As can be known clear and definite by the result shown in above-mentioned the 1st table, among the embodiment 1～12, all be stability and Thermocurable both excellences at room temperature, in addition, the transparency, sulfidation-resistance are also excellent.
See that in more detail even only contain tin compound or zn cpds any one as can be known, the stability under the room temperature and Thermocurable be unexcellent (comparative example 1～5,9～13) also, but by and use both, thereby Thermocurable excellence (embodiment 1～12).
In addition, tin compound is in the comparative example 6～8 more than 1 with respect to the value of the mass ratio (C/D) of zn cpds, gelation, the poor stability under the room temperature.
In addition, in tin compound and used the comparative example 9 of titanium compound and in tin compound and used in the comparative example 10 of aluminum compound gelation, the poor stability under the room temperature.
Composition of the present invention excellent in stability at room temperature can be with the sufficient length setting serviceable time, the balance excellence of the stability under the room temperature and Thermocurable.
The explanation of symbol
100,200 multilayer body (structure that contains silicone resin)
102,202 silicone resin layers
120,220 members
203,303,503 optical semiconductors
300,400,500,601 optical semiconductor sealing members
301,501 installation components
302 recesses
304 frameworks
306 oblique line portions
307,507 electroconductibility lines
308,502,606 sealing materials (other transparent layer)
309 outer electrodes
312,314 ends
310,510 substrates
320,520 reverberators
401 lens
506 resins
600 light-emitting diode displays
604 housings
605 shading members.
Claims (7)
1. thermohardening type organosilicon resin composition, it contains: have the organopolysiloxane (A) of silanol group, the silane compound (B) with alkoxysilyl, tin compound (C) and zn cpds (D),
The content of described tin compound (C) is, is 0.001～1 mass parts with respect to total 100 mass parts of described organopolysiloxane (A) and described silane compound (B),
The content of described zn cpds (D) is, is 0.01～5 mass parts with respect to total 100 mass parts of described organopolysiloxane (A) and described silane compound (B),
Described tin compound (C) with respect to the value of the mass ratio C/D of described zn cpds (D) less than 1.
2. thermohardening type organosilicon resin composition according to claim 1, described zn cpds (D) is the zn cpds shown in following formula (d1) or the following formula (d2),
Zn(O－CO－R
1)
2(d1)
Zn(R
2COCHCOR
3)
2(d2)
In the formula (d1), R
1The alkyl or aryl of expression carbonatoms 1～18,
In the formula (d2), R
2, R
3Identical or different, 1 valency alkyl or alkoxyl group of expression carbonatoms 1～18.
3. thermohardening type organosilicon resin composition according to claim 1 and 2, described organopolysiloxane (A) comprises silicone resin,
Described silicone resin:
With R
3SiO
1/2Unit (in the formula, R represents 1 valency alkyl of the carbonatoms 1～6 that do not replace or replace independently of one another) and SiO
4/2The unit is as repeating unit, with respect to SiO
4/21 mole of unit, R
3SiO
1/2The ratio of unit is 0.5～1.2 mole,
In addition, also can have R
2SiO
2/2Unit and RSiO
3/2In the unit (in various, R represents 1 valency alkyl of the carbonatoms 1～6 that do not replace or replace independently of one another) at least a kind, and make with respect to SiO
4/21 mole of unit, R
2SiO
2/2Unit and RSiO
3/2Each unit of unit is respectively below 1.0 moles and the adding up to below 1.0 moles of each unit,
And, have the silanol group less than 6.0 quality %.
4. according to each described thermohardening type organosilicon resin composition of claim 1～3, it also contains zirconium compounds (E) and/or hafnium compound (F).
5. according to each described thermohardening type organosilicon resin composition of claim 1～4, it also contains two (alkoxyl group) alkane and/or isocyanurate derivative.
6. structure that contains silicone resin, it possesses:
The member that comprises silver; And
The silicone resin layer that covers each described thermohardening type organosilicon resin composition curing described member, that make claim 1～5 and obtain.
7. optical semiconductor sealing member, it possesses:
Framework with recess;
Be disposed at the optical semiconductor of the bottom of described recess;
Be disposed at the member that comprises silver of the medial surface of described recess; And
The sealing material that is filled in described recess and each described thermohardening type organosilicon resin composition curing sealing, that make claim 1～5 of described optical semiconductor and described member is obtained.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010251966 | 2010-11-10 | ||
| JP2010-251966 | 2010-11-10 | ||
| PCT/JP2011/075727 WO2012063822A1 (en) | 2010-11-10 | 2011-11-08 | Thermosetting silicone resin composition, and silicone resin-containing structure and optical semiconductor element encapsulant obtained using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103210041A true CN103210041A (en) | 2013-07-17 |
| CN103210041B CN103210041B (en) | 2014-06-11 |
Family
ID=46050964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180054196.7A Expired - Fee Related CN103210041B (en) | 2010-11-10 | 2011-11-08 | Thermosetting silicone resin composition, and silicone resin-containing structure and optical semiconductor element encapsulant obtained using same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5045861B2 (en) |
| KR (1) | KR101332171B1 (en) |
| CN (1) | CN103210041B (en) |
| TW (1) | TWI540183B (en) |
| WO (1) | WO2012063822A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI564321B (en) * | 2013-01-31 | 2017-01-01 | 可隆股份有限公司 | Silicone resin and method of preparing the same |
| CN111072712A (en) * | 2019-12-23 | 2020-04-28 | 东莞市贝特利新材料有限公司 | Organic silicon tackifier, preparation method thereof and high-transparency self-adhesive addition type organic silicon rubber composition |
| CN113337245A (en) * | 2021-07-26 | 2021-09-03 | 深圳市希顺有机硅科技有限公司 | Dealcoholized photovoltaic module sealant and preparation method thereof |
| CN115627120A (en) * | 2022-10-26 | 2023-01-20 | 深圳市华思电子科技有限公司 | Single-component solvent-free addition type organic silicon three-proofing coating |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY170153A (en) * | 2013-08-01 | 2019-07-09 | Daicel Corp | Curable resin composition and semiconductor device using same |
| JP5736525B1 (en) * | 2013-08-02 | 2015-06-17 | 株式会社ダイセル | Curable resin composition and semiconductor device using the same |
| WO2015019767A1 (en) * | 2013-08-06 | 2015-02-12 | 株式会社ダイセル | Curing resin composition and semiconductor device employing same |
| JP6803539B2 (en) * | 2016-08-23 | 2020-12-23 | パナソニックＩｐマネジメント株式会社 | Light emitting device and lighting device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000038451A (en) * | 1998-07-23 | 2000-02-08 | Ge Toshiba Silicones Co Ltd | Production of alkoxy-terminated polydiogranosiloxane |
| JP2008274272A (en) * | 2007-04-06 | 2008-11-13 | Yokohama Rubber Co Ltd:The | Composition for sealing optical semiconductor device, its cured product and sealed body of optical semiconductor device |
| JP2010163602A (en) * | 2008-12-16 | 2010-07-29 | Yokohama Rubber Co Ltd:The | Silanol condensation catalyst, heat-curable silicone resin composition for sealing photosemiconductor and sealed photosemiconductor using the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2499782A1 (en) * | 2005-03-07 | 2006-09-07 | Queen's University At Kingston | Sol gel functionalized silicate catalyst and scavenger |
| JP5096311B2 (en) * | 2005-04-06 | 2012-12-12 | ダウ コーニング コーポレーション | Organosiloxane composition |
-
2011
- 2011-11-08 CN CN201180054196.7A patent/CN103210041B/en not_active Expired - Fee Related
- 2011-11-08 JP JP2012505525A patent/JP5045861B2/en not_active Expired - Fee Related
- 2011-11-08 KR KR1020137006541A patent/KR101332171B1/en active IP Right Grant
- 2011-11-08 WO PCT/JP2011/075727 patent/WO2012063822A1/en active Application Filing
- 2011-11-10 TW TW100141042A patent/TWI540183B/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000038451A (en) * | 1998-07-23 | 2000-02-08 | Ge Toshiba Silicones Co Ltd | Production of alkoxy-terminated polydiogranosiloxane |
| JP2008274272A (en) * | 2007-04-06 | 2008-11-13 | Yokohama Rubber Co Ltd:The | Composition for sealing optical semiconductor device, its cured product and sealed body of optical semiconductor device |
| JP2010163602A (en) * | 2008-12-16 | 2010-07-29 | Yokohama Rubber Co Ltd:The | Silanol condensation catalyst, heat-curable silicone resin composition for sealing photosemiconductor and sealed photosemiconductor using the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI564321B (en) * | 2013-01-31 | 2017-01-01 | 可隆股份有限公司 | Silicone resin and method of preparing the same |
| CN111072712A (en) * | 2019-12-23 | 2020-04-28 | 东莞市贝特利新材料有限公司 | Organic silicon tackifier, preparation method thereof and high-transparency self-adhesive addition type organic silicon rubber composition |
| CN113337245A (en) * | 2021-07-26 | 2021-09-03 | 深圳市希顺有机硅科技有限公司 | Dealcoholized photovoltaic module sealant and preparation method thereof |
| CN113337245B (en) * | 2021-07-26 | 2022-03-25 | 深圳市希顺有机硅科技有限公司 | Dealcoholized photovoltaic module sealant and preparation method thereof |
| CN115627120A (en) * | 2022-10-26 | 2023-01-20 | 深圳市华思电子科技有限公司 | Single-component solvent-free addition type organic silicon three-proofing coating |
| CN115627120B (en) * | 2022-10-26 | 2023-06-16 | 深圳市华思电子科技有限公司 | Single-component solvent-free addition type organosilicon three-proofing coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2012063822A1 (en) | 2014-05-12 |
| JP5045861B2 (en) | 2012-10-10 |
| CN103210041B (en) | 2014-06-11 |
| TWI540183B (en) | 2016-07-01 |
| KR101332171B1 (en) | 2013-11-25 |
| TW201237105A (en) | 2012-09-16 |
| WO2012063822A1 (en) | 2012-05-18 |
| KR20130034666A (en) | 2013-04-05 |
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