CN103210041B - 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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- CN103210041B CN103210041B CN201180054196.7A CN201180054196A CN103210041B CN 103210041 B CN103210041 B CN 103210041B CN 201180054196 A CN201180054196 A CN 201180054196A CN 103210041 B CN103210041 B CN 103210041B
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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 138
- 229910000077 silane Inorganic materials 0.000 claims abstract description 73
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 53
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 52
- 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 87
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 125000003545 alkoxy group Chemical group 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 39
- 238000007789 sealing Methods 0.000 claims description 32
- 239000003566 sealing material Substances 0.000 claims description 21
- 150000002363 hafnium compounds Chemical class 0.000 claims description 19
- 150000003755 zirconium compounds Chemical class 0.000 claims description 19
- 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 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 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 150000003752 zinc compounds Chemical class 0.000 abstract 3
- 239000000203 mixture Substances 0.000 description 73
- 239000002253 acid Substances 0.000 description 46
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 40
- 239000002585 base Substances 0.000 description 34
- 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 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 28
- 238000000034 method Methods 0.000 description 24
- 238000004519 manufacturing process Methods 0.000 description 23
- 229910052726 zirconium Inorganic materials 0.000 description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 17
- 150000002148 esters Chemical group 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 15
- 229910052735 hafnium Inorganic materials 0.000 description 15
- 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
- 125000000524 functional group Chemical group 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
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-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
- 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
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 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
- 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
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical compound OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 7
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- 125000002252 acyl group Chemical group 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 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
- 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
- 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
- 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000008034 disappearance Effects 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
- 239000005639 Lauric acid Substances 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
- 229910052799 carbon Inorganic materials 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
- 230000000630 rising effect Effects 0.000 description 3
- 150000004756 silanes Chemical class 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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004925 Acrylic resin Substances 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
- 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
- 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
- STRNXEROJYKNEG-UHFFFAOYSA-N [Hf].C1(CC1)C(=O)O Chemical compound [Hf].C1(CC1)C(=O)O STRNXEROJYKNEG-UHFFFAOYSA-N 0.000 description 2
- GZJIEVDLAYJNLJ-UHFFFAOYSA-N [Hf].C1(CCCC1)C(=O)O Chemical compound [Hf].C1(CCCC1)C(=O)O GZJIEVDLAYJNLJ-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
- RTLJAQFPDHXRCQ-UHFFFAOYSA-N [Zr].C1(CC1)C(=O)O Chemical compound [Zr].C1(CC1)C(=O)O RTLJAQFPDHXRCQ-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
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 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
- WPOHPTXDRLKQKR-UHFFFAOYSA-N cyclopentanecarboxylic acid zirconium Chemical compound [Zr].C1(CCCC1)C(=O)O WPOHPTXDRLKQKR-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 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
- 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
- 238000002156 mixing Methods 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
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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
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- H—ELECTRICITY
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- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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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 component sealing member that contains silicone resin that the present invention relates to thermohardening type organosilicon resin composition and use said composition and obtain.
Background technology
In the past, have silanol group organopolysiloxane condensation system solidify in, as catalyzer, the compound (for example,, with reference to patent documentation 1,2) of aluminium system, zirconium system, titanium system, tin system etc. has been proposed.
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 room temperature, and Thermocurable is also poor.
Therefore, the object of this invention is to provide stability under room temperature and the thermohardening type organosilicon resin composition that contains tin compound of Thermocurable excellence.
For solving the method for problem
The inventor conducts in-depth research in order to solve above-mentioned problem, found that, the organosilicon resin composition fitting in the organopolysiloxane of regulation and with the zn cpds of specified quantitative and tin compound, the stability under room temperature and Thermocurable excellence, thus complete the present invention.
, the invention provides following (1)～(7).
(1) a kind of thermohardening type organosilicon resin composition, it contains: the organopolysiloxane (A) with silanol group, there is the silane compound (B) of 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) is less than 1 with respect to the value of the mass ratio (C/D) of above-mentioned zn cpds (D).
(2), according to the thermohardening type organosilicon resin composition above-mentioned (1) Suo Shu, above-mentioned zn cpds (D) is the zn cpds shown in following formula (d1) or following formula (d2).
Zn(O－CO－R
1)
2 (d1)
Zn(R
2COCHCOR
3)
2 (d2)
(in formula (d1), R
1represent the alkyl or aryl of carbonatoms 1～18.
In formula (d2), R
2, R
3identical or different, 1 valency alkyl or alkoxyl group of expression carbonatoms 1～18.)
(3) according to the thermohardening type organosilicon resin composition above-mentioned (1) or (2) Suo Shu, above-mentioned organopolysiloxane (A) comprises silicone resin, described silicone resin: by R
3siO
1/2unit (in formula, R represents 1 valency alkyl of the carbonatoms 1～6 that does not replace or replace independently of one another) and SiO
4/2unit 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 unit (in various, R represents 1 valency alkyl of the carbonatoms 1～6 that does 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
3/2adding up to below 1.0 moles of below each unit of unit is respectively 1.0 moles and each unit, and, the silanol group that is less than 6.0 quality % there is.
(4), according to the thermohardening type organosilicon resin composition described in any one of above-mentioned (1)～(3), it also contains zirconium compounds (E) and/or hafnium compound (F).
(5), according to the thermohardening type organosilicon resin composition described in any one of above-mentioned (1)～(4), it also contains two (alkoxyl group) alkane and/or isocyanurate derivative.
(6) structure that contains silicone resin, it possesses: comprise silver-colored member; And cover that thermohardening type organosilicon resin composition described in any one above-mentioned member, that make above-mentioned (1)～(5) solidifies and the silicone resin layer that obtains.
(7) an 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 above-mentioned recess medial surface comprise silver-colored member; And be filled in above-mentioned recess and the thermohardening type organosilicon resin composition described in sealing, that make above-mentioned (1)～(5) to above-mentioned optical semiconductor and above-mentioned member any one solidified and the sealing material that obtains.
The effect of invention
According to the present invention, can provide stability under room temperature and the thermohardening type organosilicon resin composition that contains tin compound of Thermocurable excellence.
Accompanying drawing explanation
Fig. 1 is the sectional view schematically showing 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 schematically showing 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 is the schematic diagram that represents an example of the light-emitting diode display that has used composition of the present invention and/or optical semiconductor sealing member of the present invention.
Embodiment
< thermohardening type organosilicon resin composition >
Thermohardening type organosilicon resin composition of the present invention (following, also referred to as " composition of the present invention ".) be following thermohardening type organosilicon resin composition, it contains: the organopolysiloxane (A) with silanol group, there is the silane compound (B) of 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) is less than 1 with respect to the value of the mass ratio (C/D) of above-mentioned zn cpds (D).
Below, the contained each composition of composition of the present invention is described in detail.
< organopolysiloxane (A) >
The contained organopolysiloxane (A) of composition of the present invention is in 1 molecule, to have 1 above, to be preferably 2 above silanol groups organopolysiloxane.
The alkyl having as organopolysiloxane (A), is not particularly limited, and for example can enumerate the aromatic series bases such as phenyl; Alkyl; Alkenyl; Deng.
The main chain of organopolysiloxane (A) can be straight chain shape, chain or netted any.In addition in a part, can there is, the alkoxysilyl of carbonatoms 1～6.
As organopolysiloxane (A), for example can enumerate, more than 2 silanol group is incorporated into organic polydialkysiloxane of end.
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 following formula (a1).
In formula (a1), R
4identical or different, the alkyl or aryl of expression carbonatoms 1～18, n represents more than 1 integer.
As R
4the alkyl of shown carbonatoms 1～18, for example can enumerate, the alkyl of the straight chain shapes such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl or a chain; The cycloalkyl such as cyclopentyl, cyclohexyl; Deng, as R
4the aryl of shown carbonatoms 1～18, for example can enumerate, and phenyl, naphthyl etc., wherein, be preferably methyl, phenyl, more preferably methyl.
In formula (a1), n can be the numerical value corresponding with the weight-average molecular weight of organopolysiloxane (A), is 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, by R
3siO
1/2unit (in formula, R represents 1 valency alkyl of the carbonatoms 1～6 that does not replace or replace independently of one another) and SiO
4/2unit is as the silicone resin A 1 of repeating unit.
In silicone resin A 1, as R
3siO
1/2r in unit, for example can enumerate, the alkyl such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl; The cycloalkyl such as cyclopentyl, cyclohexyl; The alkenyls such as vinyl, allyl group, pseudoallyl, butenyl, pentenyl, hexenyl; The aryl such as phenyl; Chloromethyl, 3-chloropropyl, 1-chloro-2-methyl propyl group, 3,3, the haloalkyls such as 3-trifluoro propyl; Deng, wherein, be preferably methyl, vinyl, phenyl, more preferably methyl.
In 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 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 unit (in various, R represents 1 valency alkyl of the carbonatoms 1～6 that does 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
3/2adding up to below 1.0 moles of below each unit of unit is respectively 1.0 moles and 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.Such mixing ratio if, the transparency excellence of composition of the present invention.As the concrete example of such mixing 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 unit is 0.7 mole.
In addition, silicone resin A 1 has the silanol group that is less than 6.0 quality %.More than the content of silanol group is preferably 0.1 % by weight, more preferably 0.2～3.0 % by weight.If the content of silanol group is this scope, 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 manufacture by known method in the past, for example, can make the silane compound that contain alkoxyl group corresponding with each unit carry out cohydrolysis and condensation in organic solvent, as not obtaining containing the silicone resin of volatile component in fact.
Particularly, for example, as long as by R
3siOMe and Si (OMe)
4as required with R
2si (OMe)
2and/or RSi (OMe)
3in organic solvent, cohydrolysis and condensation can (in various, R represent 1 valency alkyl of the carbonatoms 1～6 that does not replace or replace independently of one another, and Me represents methyl) together.
As organic solvent, be preferably the organic solvent that can dissolve the organopolysiloxane generating 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.
About the manufacture method of organopolysiloxane (A), be not particularly limited, 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 weight-average molecular weight of the polystyrene conversion that the gel permeation chromatography (GPC) that the molecular weight of organopolysiloxane (A) is served as reasons chloroform as solvent obtains.
Organopolysiloxane (A) can a kind of use separately 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 contained silane compound (B) of composition of the present invention has more than 1 in 1 molecule, be preferably more than 2 alkoxysilyls.Here, so-called alkoxysilyl, refers to the alkoxyl group with the direct combination of Siliciumatom.
As silane compound (B) composition, for example can enumerate, in 1 molecule, there is 1 Siliciumatom, on Siliciumatom, be combined with the compound (following, also referred to as " silane compound B1 ") of more than 2 alkoxyl group; In 1 molecule, have more than 2 Siliciumatom, skeleton is polysiloxane skeleton, has the organopolysiloxane (following, also referred to as " silane compound B2 ") of 2 above alkoxyl groups of being combined with Siliciumatom; Deng.
Silane compound (B) can have more than 1 organic group in 1 molecule, for example can enumerate, can comprise at least one the heteroatomic alkyl being selected from Sauerstoffatom, nitrogen-atoms and 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-1-propylene base, 2-methacrylic etc.As aryl, for example can enumerate phenyl, naphthyl etc.Wherein, be preferably that methyl, (methyl) are acrylate-based, (methyl) acryloxyalkyl.
(silane compound B1)
As silane compound B1, for example can enumerate the silane compound shown in following formula (b1).
Si(OR
5)
nR
6 4-n (b1)
In formula (b1), n represents 2,3 or 4, R
5represent alkyl, R
6represent organic group.R
6the organic group implication that shown organic group is recorded with the organic group that can have as silane compound (B) is identical.
As silane compound B1, for example can enumerate the dialkoxy silicanes such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, diethyl diethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane; The trialkoxy silanes such as methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane; The tetraalkoxysilanes such as tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan; (methyl) acryloxyalkyl trialkoxy silanes such as γ-(methyl) acryloxy propyl trimethoxy silicane, γ-(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 following formula (b2-1).
R
7 mSi(OR
8)
nO
(4-m-n)/2 (b2－1)
In formula (b2-1), R
7for organic group, R
8for 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 recorded with the organic group that can have as silane compound (B) is identical, R
8the alkyl implication that shown alkyl is recorded with the alkyl of the organic group that can have as silane compound (B) is identical.
As silane compound B2, for example can enumerate the organosilicon alcoxyl base oligopolymer such as methyl methoxy base oligopolymer.Organosilicon alcoxyl base oligopolymer is that main chain is organopolysiloxane, the silicone resin that molecular end alkoxy is silyl-capped.Methyl methoxy base oligopolymer is equivalent to the compound shown in formula (b2-1), as its concrete example, can enumerate the compound shown in following formula (b2-2).
In formula (b2-2), R
9represent methyl, a represents 1～100 integer, and 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, at least single end has alkoxysilyl, in 1 molecule, there is the compound (following, also referred to as " silane compound B3 ") of more than 3 alkoxyl group (deriving from the alkoxyl group of alkoxysilyl).
Silane compound B3 for example can be used as with respect to 1 mole of the polysiloxane with two end silanol groups, 1 mole of the silane compound with alkoxysilyl is carried out to the reactant that dealcoholysis condensation forms above and obtain.
As the silane compound with alkoxyl group using in order to manufacture silane compound B3, for example can enumerate the compound shown in the compound shown in above-mentioned formula (b1), formula (b2-1) etc.
As silane compound B3, for example can enumerate the silane compound shown in following formula (b3).
In formula (b3), n can be the numerical value corresponding with the molecular weight of silane compound B3.
Compound shown in formula (b3), for example, can by two ends are had silanol group tetramethoxy-silicane for polysiloxane (with the Compound Phase shown in formula (b1) when) carry out modification and manufacture.
As silane compound (B), be preferably the silane compound shown in the silane compound shown in formula (b1), formula ((b2-1)), more preferably the tetraalkoxysilane such as tetraethoxysilane; (methyl) acryloxyalkyl trialkoxy silanes such as γ-(methyl) acryloxy propyl trimethoxy silicane; Methyl methoxy base oligopolymer.
In addition, in the situation that above-mentioned organopolysiloxane (A) uses 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, in the situation that silane compound (B) is silane compound B2, the weight-average molecular weight of the polystyrene conversion that the gel permeation chromatography (GPC) that its molecular weight is served as reasons chloroform as solvent obtains.
As the manufacture method of silane compound (B), be not particularly limited, for example can enumerate, in the past known manufacture method.
Silane compound (B) can a kind of use separately also can be two or more and use.
The amount of silane compound (B), with respect to organopolysiloxane (A) 100 mass parts, is preferably 0.5～2000 mass parts, more preferably 10～2000 mass parts.
< tin compound (C) >
Composition of the present invention contains tin compound (C).In addition, so-called " tin compound ", refers to the compound that contains 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, from suppressing the thickening the room temperature of composition of the present invention, the more excellent such reason of stability under 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), as long as " tin compound ", be just not particularly limited, for example can enumerate, the tin compound of divalent, the tin compound of 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 the 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 formula (c1); Dimorphism, the polymer-type of the tin compound shown in formula (c1); Deng.
R
10 a－Sn－［O－CO－R
11］
4-a (c1)
In formula (c1), R
10represent alkyl, R
11represent alkyl, a represents 1～3 integer.
As R
10shown alkyl, for example can enumerate, and more than 1 alkyl of carbonatoms, 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 be that straight chain shape can be also side chain shape, can have unsaturated link(age), can have the heteroatomss such as Sauerstoffatom, nitrogen-atoms, sulphur atom, for example can enumerate the aliphatic alkyls such as methyl, ethyl; Ester ring type alkyl; Aromatic hydrocarbyl; Their combination; Deng.
As the dimorphism of the tin compound shown in formula (c1), for example can enumerate the tin compound shown in following formula (c2).
In formula (c2), R
10, R
11with the R in 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 oxalic acid tin methide, two (methyl ethyl diketone) tin methide, dibutyl tin laurate, toxilic acid dibutyl tin, 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, dimethanol dibutyl tin, two (nonylphenol) dibutyl tin, dibutyltin oxide, two (methyl ethyl diketone) dibutyl tin, two (ethylacetoacetone(EAA,HEAA)) dibutyl tin, two dioctyltin laurate, oxalic acid dioctyl tin, the dialkyl tin compounds such as two (methyl ethyl diketone) dioctyl tin, 2 aggressiveness of dialkyl tin compound, the polymkeric substance of the dialkyl tins such as dibutyltin maleate polymer, dioctyl tin maleate polymkeric substance, the reactants such as the reactant of dioctyl pink salt and ethyl orthosilicate, the single-alkyl tin compounds such as three (2 ethyl hexanoic acid) Monobutyltin, Deng.
In addition, from the viewpoint of the impact on 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 ofly use separately, also can two or more and use.
About the manufacture method of tin compound (C), be not particularly limited, for example, can manufacture by known method in the past.
< zn cpds (D) >
In composition of the present invention, in order also to use with tin compound (C) and the moisture curing being caused by this tin compound (C) to be postponed, and contain zn cpds (D).
In the present invention, the content of zn cpds (D) is more than the content of tin compound (C)., in the present invention, tin compound (C) is less than 1 with respect to the value of the mass ratio (C/D) of zn cpds (D).Thus, composition of the present invention, the thickening under room temperature is suppressed, the excellent in stability under room temperature.
The more excellent such reason of stability from the room temperature of composition of the present invention, tin compound (C) is preferably less than 1 and be more than 0.01 with respect to the value of the mass ratio (C/D) of zn cpds (D), 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, with respect to total 100 mass parts of organopolysiloxane (A) and silane compound (B), be 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 obtaining 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) being brought by corrosive gases.But such mechanism is what infer, even if having other mechanism also within the scope of the invention.
As the contained zn cpds of composition of the present invention (D), as long as comprising the compound of zinc, be just not particularly limited, for example can enumerate the zinc salts such as zinc phosphate; Zine coordination compound; Zinc alkoxide; The 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, as long as (comprising mineral acid, organic acid by zinc and acid.) form salt, be just not particularly limited.In addition, as zine coordination compound, as long as the inner complex being formed by zinc and part, be just not particularly limited.
In addition, in the present invention, zn cpds (D), from the viewpoint of heat-resisting tint permanence, preferably in fact not containing benzoglioxaline salt.
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.
First, formula (d1) is as follows.
Zn(O－CO－R
1)
2 (d1)
In formula (d1), R
1represent the alkyl or aryl of carbonatoms 1～18.In addition, the CO in formula (d1) is carbonyl (C=O).
As R
1the alkyl of shown carbonatoms 1～18, for example can enumerate, 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 enumerate, phenyl, naphthyl etc.
Be salt at the zn cpds (D) shown in formula (d1), as zinc salt, for example can enumerate, the zinc salt shown in following formula (d1 ').
Formula (d1 ') in, R
1with the R in formula (d1)
1implication is identical.
As the zn cpds (D) shown in 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 formula (d2), R
2, R
3identical or different, 1 valency alkyl or alkoxyl group of expression carbonatoms 1～18.(R in formula (d2)
2cOCHCOR
3) be respectively any of following formula, be combined with zinc with " C-O-".
Be coordination compound at the zn cpds (D) shown in formula (d2), as zine coordination compound, for example can enumerate, the zine coordination compound shown in following formula (d2 ').
Formula (d2 ') in, R
2, R
3with the R in formula (d2)
2, R
3implication is identical, is positioned at same (R
2cOCHCOR
3) interior R
2, R
3can exchange.
As the R in formula (d2)
2, R
31 valency alkyl of shown carbonatoms 1～18, for example can enumerate, and the alkyl or aryl of carbonatoms 1～18 is (with the R in formula (d1)
1the alkyl or aryl implication of shown carbonatoms 1～18 is identical).
As the R in formula (d2)
2, R
3shown alkoxyl group, for example can enumerate, methoxyl group, oxyethyl group, propoxy-etc.
As the zn cpds (D) shown in formula (d2), for example can enumerate, two (methyl ethyl diketone roots) close zine coordination compound, 2,2,6,6,6 tetramethyl--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 formula (d2), or also with 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--3,5-heptadione zine coordination compound.
Zn cpds (D) can a kind ofly use separately, also can two or more and use.
As the manufacture method of zn cpds (D), for example, can use at least one by being selected from zinc oxide, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate and zinc nitrate with respect to 1 mole, make 1.5 moles above and be less than that the acid of 3 moles is reacted and the zn cpds that obtains.
As the acid that now used, be not particularly limited, for example can enumerate the mineral acids such as phosphoric acid; The 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).Their long-term reliabilities under the high temperature for making composition of the present invention in condensation catalyst are good.
Can think the heating in the time of the initial cure of composition of the present invention or after initial cure of zirconium compounds (E) and/or hafnium compound (F) time, 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 silanol group (for example, reacting with alkoxysilyl by silanol group reaction, silanol group each other) carry out condensation.Thus, composition of the present invention is overall by heating is evenly solidified.
The more excellent such reason of long-term reliability from the high temperature of composition of the present invention, the content of zirconium compounds (E) and/or hafnium compound (F) is, with respect to total 100 mass parts of 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) ］
First, zirconium compounds (E) is described.Zirconium compounds (E), as long as having the zirconium compounds of zirconium atom and organic group, is just not particularly limited.
Here, the organic group having as zirconium, for example can enumerate, organic carboxylate (O-CO-R); The group (O-R) that the alkyl of alkoxyl group, phenoxy group etc. is combined with oxygen base; Part; Their combination; Deng.
More specifically, as zirconium compounds (E), for example can enumerate, compound (compd E 1 '), the compound (compd E 2) shown in following formula (e2) etc. shown in compound shown in following formula (e1) (compd E 1), following formula (e1 '), can be applicable to using them.
In formula (e1), R
12represent the alkyl of carbonatoms 1～18.
In formula (e1 '), R ' represents 1 valency alkyl of carbonatoms 1～18, R " represent 1 valency alkyl or acyl group of carbonatoms 1～18, n represents 0～2 integer.
In 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 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.
The acid using as the zirconium metal-salt in order to manufacture compd E 1, be not particularly limited, for example can enumerate carboxylic acid, as the concrete example of carboxylic acid, can enumerate the aliphatic carboxylic acids such as acetic acid, propionic acid, sad (2 ethyl hexanoic acid), n-nonanoic acid, stearic acid, lauric acid; The ester ring type such as naphthenic acid, naphthenic acid carboxylic acid; The aromatic carboxylic acids such as phenylformic acid; Deng.
As aliphatic carboxylate, for example can enumerate two zirconyl octoates, two neodecanoic acid oxygen zirconiums etc.As ester ring type carboxylate salt, for example can enumerate naphthenic acid oxygen zirconium, cyclohexylenedinitrilotetraacetic acid oxygen zirconium etc.As 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 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 R in 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 above-mentioned formula (d1)
1the alkyl or aryl implication of shown carbonatoms 1～18 is identical).
As the oxygen zirconium coordination compound shown in above-mentioned formula (e1 '), for example can enumerate, R represents methyl, R ' represents acyl group, n represent 1 acetylacetone based-2-ethyl hexanoyl-oxygen zirconium; R represents methyl, and n represents 0 bis-acetylacetonate oxygen zirconium; Deng.
(compd E 2)
Compd E 2, as shown in above-mentioned formula (e2), has 1～3 acyl group (R
13-CO-).In compd E 2 shown in formula (e2), acyl group is contained in formula (e2) as carboxylicesters.In formula (e2), m is 2 above in the situation that, multiple R
13can be the same or different.In addition, in the situation that m is 1～2, multiple R
13can be the same or different.
R in formula (e2)
13the carbonatoms of shown alkyl is preferably 3～16, and more preferably 4～16.
R
13shown alkyl can be that straight chain shape can be also side 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 enumerate, aliphatic alkyl, ester ring type alkyl, aromatic hydrocarbyl, their combination etc.
As ester ring type alkyl, for example can enumerate the cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group; Naphthenic ring (deriving from the naphthenic hydrocarbon ring of naphthenic acid); The 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 the 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 (naphthenic acid esters); The carbonyl oxygen base of the 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-, there is 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 formula (e2)
14the carbonatoms of shown alkyl is preferably 3～8.
As R
14shown alkyl, can be that straight chain shape can be also side 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 enumerate, 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 the alkoxyl group cyclopropane-carboxylic acid zirconiums such as tri-alkoxy list cyclopropane-carboxylic acid zirconium, dialkoxy two cyclopropane-carboxylic acid zirconiums, monoalkoxy three cyclopropane-carboxylic acid zirconiums; The alkoxyl group cyclopentane-carboxylic acid zirconiums such as tri-alkoxy list cyclopentane-carboxylic acid zirconium, dialkoxy two cyclopentane-carboxylic acid zirconiums, monoalkoxy three cyclopentane-carboxylic acid zirconiums; The alkoxyl group naphthenic acid zirconiums such as three butoxy list naphthenic acid zirconiums, dibutoxy bicyclohexane formic acid zirconium, single butoxy three naphthenic acid zirconiums, three isopropoxy list naphthenic acid zirconiums, diisopropoxy bicyclohexane formic acid zirconium, single isopropoxy three naphthenic acid zirconiums; The alkoxyl group adamantanecarboxylic acid zirconiums such as tri-alkoxy list adamantanecarboxylic acid zirconium, dialkoxy two adamantanecarboxylic acid zirconiums, monoalkoxy three adamantanecarboxylic acid zirconiums; The 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 the 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 the 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; The alkoxyl group 2 thylhexoic acid zirconiums such as three butoxy list 2 thylhexoic acid zirconiums, dibutoxy 22 thylhexoic acid zirconiums, single butoxy 32 thylhexoic acid zirconiums, three isopropoxy list 2 thylhexoic acid zirconiums, diisopropoxy 22 thylhexoic acid zirconiums, single isopropoxy 32 thylhexoic acid zirconiums; The 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, there is the compd E 2 of aromatic hydrocarbyl, more preferably tri-alkoxy monocycle alkanoic acid zirconium, tri-alkoxy list isopropylformic acid zirconium, tri-alkoxy list 2 thylhexoic acid zirconiums, tri-alkoxy list cyclopropane-carboxylic acid zirconium, tri-alkoxy cyclobutane formate zirconium, tri-alkoxy list cyclopentane-carboxylic acid zirconium, tri-alkoxy list naphthenic 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 list 2 thylhexoic acid zirconiums, three butoxy list cyclopropane-carboxylic acid zirconiums, three butoxy list cyclopentane-carboxylic acid zirconiums, three butoxy list naphthenic 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 list 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 one in three butoxy list isopropylformic acid zirconiums and three butoxy list 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 formula (e2)
14implication is identical) 1 mole, use 1 mole above and be less than the R of 4 moles
13carboxylic acid (R shown in-COOH
13with the R in formula (e2)
13implication is identical), under nitrogen atmosphere, under the condition of 20～80 ℃, stir, thereby manufacture.
About reacting 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 manufacture 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 manufacture compd E 2, for example can enumerate the aliphatic carboxylic acid such as acetic acid, propionic acid, isopropylformic acid, sad, 2 ethyl hexanoic acid, n-nonanoic acid, lauric acid; The ester ring type carboxylic acids such as naphthenic acid, cyclopropane-carboxylic acid, cyclopentane-carboxylic acid, hexahydrobenzoic acid (naphthenic acid), adamantanecarboxylic acid, norbornane formic acid; The 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 the long-term reliability from the high temperature of composition of the present invention, is preferably the compound shown in the compound shown in following formula (f1) and/or following formula (f2).
In formula (f1), n represents 1～4 integer, R
15represent alkyl, R
16represent the alkyl of carbonatoms 1～18.
In formula (f2), m represents 1～4 integer, R
16represent the alkyl of carbonatoms 1～18, R
17and R
18identical or different, alkyl or the alkoxyl group of expression carbonatoms 1～18.
First, the hafnium compound (F) shown in above-mentioned formula (f1) is described.
R in formula (f1)
15shown alkyl can be that straight chain shape can be also side 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 enumerate, and the aliphatic alkyl of carbonatoms 1～18 (comprises alkyl; The 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 ester ring type alkyl, for example can enumerate the cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group; Naphthenic ring (deriving from the naphthenic hydrocarbon ring of naphthenic acid); The 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 one in cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, naphthenic ring, adamantyl, norborneol alkyl, phenyl, naphthyl and Azulene, more preferably cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, naphthenic ring are (as R
15the naphthenic acid ester group of COO-), phenyl, be particularly preferably cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, naphthenic ring.
R in formula (f1)
16the carbonatoms of shown alkyl is 1～18, 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 enumerate, and methyl, ethyl, propyl group (n-propyl, sec.-propyl), butyl, amyl group, hexyl, octyl group etc., wherein, be preferably methyl, ethyl, propyl group (n-propyl, sec.-propyl), butyl, amyl group.
As thering is ester ring type alkyl as R
15hafnium compound (F) shown in the formula (f1) of shown alkyl, for example can enumerate alkoxyl group (single～tri-) cyclopropane-carboxylic acid hafnium, four cyclopropane-carboxylic acid hafniums, alkoxyl group (single～tri-) cyclopentane-carboxylic acid hafnium, pyramidane formic acid hafnium, alkoxyl group (single～tri-) naphthenic acid hafnium, prismane formic acid hafnium, alkoxyl group (single～tri-) adamantanecarboxylic acid hafnium, four adamantanecarboxylic acid hafniums, alkoxyl group (single～tri-) naphthenic acid hafnium, Fourth Ring alkanoic acid hafnium etc.
As thering is aromatic hydrocarbyl as R
15hafnium compound (F) shown in the formula (f1) of shown alkyl, for example can enumerate, alkoxyl group (single～tri-) phenylformic acid hafnium, four phenylformic acid hafniums etc.
As thering is aliphatic alkyl as R
15hafnium compound (F) shown in the formula (f1) of shown alkyl, for example can enumerate alkoxyl group (single～tri-) butyric acid hafnium, four butyric acid hafniums, alkoxyl group (single～tri-) 2 thylhexoic acid hafniums, 42 thylhexoic acid hafniums, alkoxyl group (single～tri-) neodecanoic acid hafnium, "four news" (new ideas capric acid hafnium etc.
In addition, in this specification sheets, " (single～tri-) " refer to any in 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 list cyclopropane-carboxylic acid hafnium, tri-alkoxy cyclobutane formate hafnium, tri-alkoxy list cyclopentane-carboxylic acid hafnium, tri-alkoxy list naphthenic 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 list 2 thylhexoic acid hafniums, three butoxy list cyclopropane-carboxylic acid hafniums, three butoxy list cyclopentane-carboxylic acid hafniums, three butoxy list naphthenic 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 above-mentioned formula (f2) is described.
R in formula (f2)
16with the R in formula (f1)
16implication is identical.
R in formula (f2)
17, R
18r in the alkyl of shown carbonatoms 1～18 and formula (f1)
15carbonatoms in shown alkyl is that 1～18 alkyl is same.
As the R in formula (f2)
17, R
18shown alkoxyl group, for example can enumerate, the alkoxyl group of the carbonatomss 1～18 such as methoxyl group, oxyethyl group, propoxy-.
R in formula (f2)
17, R
18can there is the halogens such as chlorine atom, bromine atoms, fluorine atom.
In addition, in formula (f2), so-called R
17with R
18can exchange.
As the hafnium compound (F) shown in formula (f2), for example can enumerate, hafnium alkoxide (single～tri-) 2,4-diacetylmethane salt, hafnium-2,4-diacetylmethane salt, hafnium alkyl diacetylmethane salt, hafnium fluorine diacetylmethane salt etc., wherein, be preferably hafnium two-propyl carbinol salt (two-2,4-diacetylmethane salt), hafnium-2,4-diacetylmethane salt, hafnium tetramethyl-diacetylmethane salt, hafnium Aluminum Alkyls salt.
Other composition of < >
Composition of the present invention, not damaging in the scope of object of the present invention, effect, can also contain additive as required.
As additive, for example can enumerate, the weighting agents such as mineral filler, antioxidant, lubricant, UV light absorber, thermo-optical stablizer, dispersion agent, static inhibitor, stopper, defoamer, curing catalyst, solvent, fluorescent substance (inorganics, organism), age resister, free radical inhibitors, cementability modifying agent, fire retardant, tensio-active agent, storage stability modifying agent, ozone ageing preventing agent, thickening material, softening agent, radioactive rays blocker, nucleator, coupling agent, electroconductibility imparting agent, phosphorus is peroxide decomposer, pigment, metal passivator, physical property 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, the 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 1, two (triethoxysilyl) ethane, 1 of 2-, two (trimethoxysilyl) hexanes, 1 of 6-, two (trimethoxysilyl) heptane, 1 of 7-, two (trimethoxysilyl) octanes, 1 of 8-, two (trimethoxysilyl) nonanes and 1 of 9-, at least one in two (trimethoxysilyl) decane of 10-, more preferably 1, two (trimethoxysilyl) hexanes of 6-.
As isocyanurate derivative, be preferably the isocyanurate derivative shown in following formula.
In above-mentioned formula, R represents organic group or has the monovalence alkyl of aliphatics unsaturated link(age) to have the substituting groups such as epoxy group(ing), glycidoxy, alkoxysilyl, (methyl) acryl independently of one another.
As the organic group shown in the R in above-mentioned formula, be not particularly limited, for example can enumerate the alkyl such as methyl, ethyl, propyl group, butyl; The aryl such as phenyl, tolyl, xylyl, naphthyl; The aralkyl such as benzyl, styroyl; The cycloalkyl such as cyclopentyl, cyclohexyl; Haloalkyl; Deng.
In addition, as the monovalence alkyl with aliphatics unsaturated link(age) shown in the R in above-mentioned formula, be not particularly limited, for example can enumerate the unsaturated alkyl of the carbonatomss 2～8 such as vinyl, allyl group, butenyl, pentenyl, hexenyl, heptenyl.
As the isocyanurate derivative shown in 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, in the situation that 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,, in the situation that using 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 composition of the present invention is below 0.1 quality %.
In addition,, from the excellent such reason of operating environment, composition of the present invention is preferably in fact not containing solvent.So-called " in fact not containing solvent " in the present invention, the amount that refers to the solvent in composition of the present invention is below 1 quality %.
The manufacture method of composition of the present invention is not particularly limited, for example can enumerate, by the method that above-mentioned organopolysiloxane (A), silane compound (B), tin compound (C), zn cpds (D), zirconium compounds (E) as required and/or hafnium compound (F) and additive are as required mixed to manufacture.Composition of the present invention can be manufactured 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 the optical semiconductor that composition of the present invention can be used as sealing material, for example can enumerate photodiode (LED), organic electroluminescent device (organic EL), laser diode, LED array etc.As LED, for example can enumerate high-capacity LED, high-brightness LED, general brightness LED etc.
In addition, composition of the present invention can be for for example, the 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 the 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 at least one being selected from copper, silver and gold.
Composition of the present invention from the transparency, the more excellent such reason of sulfidation-resistance, preferably uses under the existence that comprises silver-colored member.The silicone resin layer being obtained by composition of the present invention can be bonding with adherend.
< using method >
As the using method of composition of the present invention, for example can enumerate, possess the using method that makes the curing curing process of composition of the present invention under the existence that comprises silver-colored member.Below, the using method using this using method as composition of the present invention is (below, also referred to as " using method of the present invention ".) describe.
As the silver-colored member that comprises using in using method of the present invention, for example can enumerate, silver, silvering etc., as concrete example, can enumerate reverberator (reflector) etc.
Above-mentioned curing process can, for by heating and/or rayed, make the curing operation of composition of the present invention.As the temperature that composition of the present invention is heated, be preferably near 80 ℃～150 ℃, more preferably near 150 ℃.In addition, the light of use, for example can enumerate ultraviolet ray, electron rays etc. when composition of the present invention is carried out to rayed.
The structure > that < contains silicone resin
The structure that contains silicone resin of the present invention possesses: comprise silver-colored member; 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 for example, cover across other layer (, 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 can using composition of the present invention as sealing material use optical semiconductor and illustrative optical semiconductor.
There is 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 (, 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, between 2 above-mentioned members that can configure side by side vacating interval, configuration optical semiconductor.
Next, the multilayer body (multilayer body 100, multilayer body 200) as the structure that contains silicone resin of the present invention is described based on Fig. 1 and Fig. 2.
Fig. 1 is the sectional view schematically showing 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 and comprises silver-colored member 120.On member 120, directly dispose silicone resin layer 102.
Fig. 2 is another the routine sectional view schematically showing as the multilayer body of the structure that contains silicone resin of the present invention.As shown in Figure 2, multilayer body 200 possesses and comprises silver-colored member 220.On member 220, directly configure optical semiconductor 203, on optical semiconductor 203, directly dispose silicone resin layer 202.In addition, can be between silicone resin layer 202 and optical semiconductor 203, configure 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 above-mentioned recess medial surface comprise silver-colored member; And be filled in above-mentioned recess and by the sealing of above-mentioned optical semiconductor and above-mentioned member, composition of the present invention is solidified and the sealing material that obtains.
As comprising silver-colored member, be not particularly limited, for example can enumerate, comprise silver-colored member and illustratively comprise silver-colored member as what use in using method of the present invention.In addition, as optical semiconductor, be not particularly limited, for example can enumerate, as can using composition of the present invention as sealing material use optical semiconductor and illustrative optical semiconductor.Every 1 of optical semiconductor sealing member of the present invention can have 1 or 2 above above-mentioned optical semiconductors.
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) to surround the mode of this opening.Dispose the substrate 310 with outer electrode 309 at the lower position of framework 304.Substrate 310 has formed the bottom of recess 302.Dispose optical semiconductor 303 in the bottom of recess 302.The direction that optical semiconductor 303 becomes luminescent layer (not shown) with upper surface is disposed at recess 302.The lower surface of optical semiconductor 303 is fixed by installation component 301.Installation component 301 is such as silver-colored thickener, resin etc.Each electrode (not shown) of optical semiconductor 303 carrys out wire-bonded with outer electrode 309 by electroconductibility line 307.
At the medial surface of recess 302, dispose as the reverberator 320 that comprises silver-colored member.In recess 302, be filled with sealing material 308, sealing material 308 encapsulating optical semiconductor elements 303 and reverberator 320.Here, sealing material 308 is for making composition of the present invention solidify the sealing material obtaining.
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.The in the situation that of which, reverberator 320 is not only 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, because making composition of the present invention, use solidifies the sealing material 308 obtaining, therefore can suppress the corrosion (for example, variable color) as the reverberator 320 that comprises silver-colored member.
In addition, owing to being filled in, sealing material 308 hardness of recess 302 are low and cure shrinkage is little, therefore can suppress to peel off from recess 302 due to cure shrinkage, or suppress electroconductibility line 307 and break.
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 Fig. 4 disposes lens 401 on the optical semiconductor sealing member 300 shown in Fig. 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 the optical semiconductor sealing member 500 shown in Fig. 5, in the inside of 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, has the sealing material 502 that composition of the present invention is solidified and obtain in this recess arrangement.
Next,, to the situation for light-emitting diode display by composition of the present invention and/or optical semiconductor sealing member of the present invention, describe based on Fig. 6.
Fig. 6 is the schematic diagram that represents an example of the light-emitting diode display that has used composition of the present invention and/or optical semiconductor sealing member of the present invention.
Light-emitting diode display 600 shown in Fig. 6 has had at one partial configuration the housing 604 of shading member 605.In the inside of housing 604, dispose multiple 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 of the structure that contains silicone resin of the present invention and optical semiconductor sealing member 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, lighting fixtures, indicating meter, signal, projector etc. for stage.
Embodiment
Below, enumerate embodiment and specifically describe the present invention, but the present invention is not limited to this.
The manufacture > of < thermohardening type organosilicon resin composition
To use with the amount (unit: mass parts) shown in table, use vacuum mixer that they are mixed equably the composition shown in following the 1st table, produce thermohardening type organosilicon resin composition.
In addition, in following the 1st table, the scale of composition (C) is shown in the total amount of composition (A) and composition (B) is made as to the amount with respect to this total amount (100 mass parts) in the situation of 100 mass parts.This amount for composition (D)～(F) too.
< evaluates >
Adopt method shown below, evaluate.Show the result in following the 1st table.
< stability/Thermocurable >
First, will mix the composition shown in following the 1st table and the thermohardening type organosilicon resin composition manufactured, under 55%RH, the condition of 23 ℃, place, through 24 hours.
Next, to 24 hours compositions with interior not gelation, further under the condition of 150 ℃, be cured, measure the JIS-A hardness after 8 hours, the JIS-A hardness after 168 hours (being called " saturated hardness "), obtain after 168 hours with respect to the hardness rising (point) after 8 hours.
In not gelation, hardness rises and exceedes in 65% situation with respect to saturated hardness, as the situation of the stability under room temperature and Thermocurable excellence and be evaluated as "○", in the situation that hardness rising is 50～65% with respect to saturated hardness, be evaluated as the slightly poor situation of Thermocurable " △ ", in the situation that hardness rising is less than 50% with respect to saturated hardness, or be gel at thermohardening type organosilicon resin composition, can not carry out in the situation of JIS-A measurement of hardness, as the situation of the poor stability under Thermocurable or room temperature and be evaluated as "×".
< transparency >
For making the thermohardening type organosilicon resin composition of gained at 150 ℃ of cured articles (thickness: 2mm) that solidify 12 hours and obtain, according to JIS K0115:2004, use ultraviolet-visible absorption spectroscopy determinator (society of Shimadzu Seisakusho Ltd. system), the transmissivity (%) while measuring wavelength 400nm.
If transmissivity (%) is more than 80%, can be evaluated as the transparency excellent.
< sulfidation-resistance >
［ solidified sample making ］
On silvering, be coated with the thermohardening type organosilicon resin composition of manufacturing, making thickness is 1mm left and right, under the condition of 150 ℃, 3 hours, be cured, thus the solidified sample of acquisition sulfidation-resistance evaluation use.
［ sulfidation-resistance test ］
In the bottom of the moisture eliminator of 10L, placement is ground into the iron sulphide 10g left and right (significantly superfluous with respect to hydrochloric acid 0.5mmol) of powdery.Next, the top position of the iron sulphide in moisture eliminator, installs porous plate (having communicating pores) not contact the mode of iron sulphide, on this porous plate, places solidified sample.Next, by dripping hydrochloric acid 0.5mmol to iron sulphide, 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 the beginning (generation of hydrogen sulfide) of above-mentioned sulfidation-resistance test 24 hours, by the silver-colored variable color in Visual Confirmation solidified sample.In the situation that variable color can not be confirmed, as the situation of sulfidation-resistance excellence and be evaluated as "○", in the situation that confirming variable color, be evaluated as "×" as the poor situation of sulfidation-resistance.
[table 1]
[table 2]
Each composition in above-mentioned the 1st table uses following composition.
Organopolysiloxane 1: the polydimethylsiloxane-α shown in 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 end 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: the hydrolytic condensate (weight-average molecular weight: 870, reactive functional groups: silanol group) with the dichloromethyl phenylsilane of silanol group and phenyl
Silane compound 1: the two end trimethoxysilyl siloxanes manufactured as following (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, add the polysiloxane (ss10 that two ends have silanol group, chemical industry society of SHIN-ETSU HANTOTAI system) 100 mass parts, tetramethoxy-silicane 10 mass parts and acetic acid 0.1 mass parts, under nitrogen atmosphere, 100 ℃ of reactions 6 hours, pass through
1h-NMR analyzes to confirm the disappearance of the silanol group that ss10 has, and the reactant of gained is made as to silane compound 1.The primary structure of silane compound 1 is as shown in following formula.
Silane compound 2: the end polymethoxy silyl siloxanes manufactured as following (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, 140 ℃ of reactions 15 hours, pass through
1h-NMR analyzes to confirm the disappearance of the silanol group that ss10 has, and the reactant of gained is made as to silane compound 2.The primary structure of silane compound 2 is as 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 silicone oligomer (XR31-B2733 of the alkoxyl group resinous type of the methyl system of containing methoxyl group 14 quality %, 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: there is alkoxysilyl and phenyl, do not there is the organosilicon alcoxyl base oligopolymer (KR480, chemical industry society of SHIN-ETSU HANTOTAI system, 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 manufacturing as following
With respect to 1 mole, zinc oxide (Northeast chemistry society system), add 2 moles of neodecanoic acids, at room temperature stir, thereby obtain transparent uniform liquid (two (neodecanoic acid) zinc).The liquid of gained is made as to 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 manufacturing as following
By 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 there-necked flask, under nitrogen atmosphere, at room temperature stirs about 2 hours, makes 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, is used fourier-transform infrared spectrophotometer (FT-IR) to carry out this analysis.Consequently, belong to the 1700cm of the COOH that derives from carboxylic acid
-1rear disappearance is reacted near being absorbed in, and has confirmed 1450～1560cm
-1near the peak that derives from COOZr.
The synthetics of gained is made as to 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 manufacturing as following
By four butanols hafniums of 45 quality % concentration (Gelest society system) 4.7g (0.01mol) 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 there-necked flask, under nitrogen atmosphere, at room temperature stirs about 2 hours, makes target synthetics.
Synthetics qualitative, is used fourier-transform infrared spectrophotometer (FT-IR) to carry out this analysis.Consequently, belong to the 1700cm of the COOH that derives from carboxylic acid
-1rear disappearance is reacted near being absorbed in, and has confirmed Isosorbide-5-Nitrae 50～1,560cm
-1near the peak that derives from COOHf.
The synthetics of gained is made as to 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 ツモトJiao company 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 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)
From the result shown in above-mentioned the 1st table clearly, in embodiment 1～12, be all stability and both excellences of Thermocurable at room temperature, in addition, the transparency, sulfidation-resistance are also excellent.
See in more detail, only contain any one of tin compound or zn cpds even known, stability under room temperature and Thermocurable be unexcellent (comparative example 1～5,9～13) also, but passes through and use both, thus Thermocurable excellence (embodiment 1～12).
In addition, tin compound is in more than 1 comparative example 6～8 with respect to the value of the mass ratio (C/D) of zn cpds, gelation, the poor stability under 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 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 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. a 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) is less than 1 with respect to the value of the mass ratio C/D of described zn cpds (D),
Described tin compound (C) is the dimorphism of the compound shown in the compound shown in the tin metal carboxylate of divalent, following formula (c1), formula (c1) or the reactant of polymer-type or dioctyl pink salt and ethyl orthosilicate,
Described zn cpds (D) is the zn cpds shown in following formula (d1) or following formula (d2),
R
10 a－Sn－［O－CO－R
11］
4-a (c1)
Zn(O－CO－R
1)
2 (d1)
Zn(R
2COCHCOR
3)
2 (d2)
In formula (c1), R
10represent more than 1 alkyl of carbonatoms, R
11expression can be also side chain shape, can have unsaturated link(age), can have heteroatomic alkyl for straight chain shape, and a represents 1～3 integer,
In formula (d1), R
1represent the alkyl or aryl of carbonatoms 1～18,
In formula (d2), R
2, R
3identical or different, 1 valency alkyl or alkoxyl group of expression carbonatoms 1～18.
2. thermohardening type organosilicon resin composition according to claim 1, described organopolysiloxane (A) comprises silicone resin,
Described silicone resin:
By R
3siO
1/2unit and SiO
4/2unit 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, R
3siO
1/2in, R represents 1 valency alkyl of the carbonatoms 1～6 that does not replace or replace independently of one another,
In addition, also can there is R
2siO
2/2unit and RSiO
3/2in unit at least a kind, and make with respect to SiO
4/21 mole of unit, R
2siO
2/2unit and RSiO
3/2adding up to below 1.0 moles of below each unit of unit is respectively 1.0 moles and each unit, R
2siO
2/2and RSiO
3/2in, R represents 1 valency alkyl of the carbonatoms 1～6 that does not replace or replace independently of one another,
And, there is the silanol group that is less than 6.0 quality %.
3. thermohardening type organosilicon resin composition according to claim 1, it also contains zirconium compounds (E) and/or hafnium compound (F).
4. thermohardening type organosilicon resin composition according to claim 2, it also contains zirconium compounds (E) and/or hafnium compound (F).
5. according to the thermohardening type organosilicon resin composition described in any one of claim 1～4, it also contains two (alkoxyl group) alkane and/or isocyanurate derivative.
6. a structure that contains silicone resin, it possesses:
Comprise silver-colored member; And
Cover that thermohardening type organosilicon resin composition described in any one described member, that make claim 1～5 solidifies and the silicone resin layer that obtains.
7. an optical semiconductor sealing member, it possesses:
There is the framework of recess;
Be disposed at the optical semiconductor of the bottom of described recess;
Be disposed at described recess medial surface comprise silver-colored member; And
Be filled in described recess and the thermohardening type organosilicon resin composition described in sealing, that make claim 1～5 to described optical semiconductor and described member any one solidified and the sealing material that obtains.
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 CN103210041A (en) | 2013-07-17 |
| CN103210041B true 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) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014119907A1 (en) * | 2013-01-31 | 2014-08-07 | Kolon Industries, Inc. | Silicone resin and method of preparing the same |
| KR101545471B1 (en) * | 2013-08-01 | 2015-08-18 | 주식회사 다이셀 | Curable resin composition and semiconductor device using same |
| WO2015016001A1 (en) * | 2013-08-02 | 2015-02-05 | 株式会社ダイセル | Curable resin composition and semiconductor device using same |
| JP5830201B2 (en) * | 2013-08-06 | 2015-12-09 | 株式会社ダイセル | Curable resin composition and semiconductor device using the 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 |
| KR20220117895A (en) * | 2019-12-17 | 2022-08-24 | 다우 실리콘즈 코포레이션 | sealant composition |
| 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 |
| 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 |
| 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 |
Family Cites Families (5)
| 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 |
| CA2499782A1 (en) * | 2005-03-07 | 2006-09-07 | Queen's University At Kingston | Sol gel functionalized silicate catalyst and scavenger |
| US8084535B2 (en) * | 2005-04-06 | 2011-12-27 | Dow Corning Corporation | Organosiloxane compositions |
| JP5444631B2 (en) * | 2007-04-06 | 2014-03-19 | 横浜ゴム株式会社 | Composition for sealing optical semiconductor element, cured product thereof and sealed optical semiconductor element |
| JP4877381B2 (en) | 2008-12-16 | 2012-02-15 | 横浜ゴム株式会社 | Silanol condensation catalyst, heat-curable silicone resin composition for encapsulating optical semiconductor, and optical semiconductor encapsulant using the same |
-
2011
- 2011-11-08 KR KR1020137006541A patent/KR101332171B1/en active IP Right Grant
- 2011-11-08 JP JP2012505525A patent/JP5045861B2/en not_active Expired - Fee Related
- 2011-11-08 WO PCT/JP2011/075727 patent/WO2012063822A1/en active Application Filing
- 2011-11-08 CN CN201180054196.7A patent/CN103210041B/en not_active Expired - Fee Related
- 2011-11-10 TW TW100141042A patent/TWI540183B/en not_active IP Right Cessation
Non-Patent Citations (3)
| Title |
|---|
| JP特开2000-38451A 2000.02.08 |
| JP特开2008-274272A 2008.11.13 |
| JP特开2010-163602A 2010.07.29 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103210041A (en) | 2013-07-17 |
| TWI540183B (en) | 2016-07-01 |
| WO2012063822A1 (en) | 2012-05-18 |
| JP5045861B2 (en) | 2012-10-10 |
| KR101332171B1 (en) | 2013-11-25 |
| TW201237105A (en) | 2012-09-16 |
| KR20130034666A (en) | 2013-04-05 |
| JPWO2012063822A1 (en) | 2014-05-12 |
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