CN106459584A - Curable resin composition, cured product, sealing material, and semiconductor device - Google Patents
Curable resin composition, cured product, sealing material, and semiconductor device Download PDFInfo
- Publication number
- CN106459584A CN106459584A CN201580029165.4A CN201580029165A CN106459584A CN 106459584 A CN106459584 A CN 106459584A CN 201580029165 A CN201580029165 A CN 201580029165A CN 106459584 A CN106459584 A CN 106459584A
- Authority
- CN
- China
- Prior art keywords
- mentioned
- resin composition
- hardening resin
- silsesquioxane
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 114
- 239000004065 semiconductor Substances 0.000 title claims abstract description 32
- 239000000047 product Substances 0.000 title description 10
- 239000003566 sealing material Substances 0.000 title description 3
- -1 isocyanurate compound Chemical class 0.000 claims abstract description 279
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 59
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 53
- 125000003118 aryl group Chemical group 0.000 claims abstract description 41
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 39
- 229920001296 polysiloxane Polymers 0.000 claims description 87
- 229910052799 carbon Inorganic materials 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 55
- 229910052710 silicon Inorganic materials 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 125000001931 aliphatic group Chemical group 0.000 claims description 41
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 32
- 229910000077 silane Inorganic materials 0.000 claims description 31
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 28
- 239000008393 encapsulating agent Substances 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 229910052684 Cerium Inorganic materials 0.000 claims description 18
- 238000007711 solidification Methods 0.000 claims description 13
- 230000008023 solidification Effects 0.000 claims description 13
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 12
- 229910052779 Neodymium Inorganic materials 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims 5
- 239000007789 gas Substances 0.000 abstract description 39
- 238000005260 corrosion Methods 0.000 abstract description 26
- 230000007797 corrosion Effects 0.000 abstract description 25
- 230000003287 optical effect Effects 0.000 abstract description 15
- 238000007789 sealing Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 40
- 239000010703 silicon Substances 0.000 description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 28
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 27
- 230000032683 aging Effects 0.000 description 26
- 229920002554 vinyl polymer Polymers 0.000 description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 230000004888 barrier function Effects 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 20
- 150000002148 esters Chemical group 0.000 description 20
- 125000001424 substituent group Chemical group 0.000 description 19
- 239000007788 liquid Substances 0.000 description 18
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical class CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 15
- 125000005843 halogen group Chemical group 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 13
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 13
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 13
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 125000002769 thiazolinyl group Chemical group 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 125000004414 alkyl thio group Chemical group 0.000 description 9
- 238000006459 hydrosilylation reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 125000005108 alkenylthio group Chemical group 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 150000004678 hydrides Chemical class 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 125000000962 organic group Chemical group 0.000 description 8
- 229910002808 Si–O–Si Inorganic materials 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 125000003302 alkenyloxy group Chemical group 0.000 description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004423 acyloxy group Chemical group 0.000 description 6
- 230000006978 adaptation Effects 0.000 description 6
- 125000001118 alkylidene group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 125000004442 acylamino group Chemical group 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 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 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 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 5
- 125000001544 thienyl group Chemical group 0.000 description 5
- 125000006023 1-pentenyl group Chemical group 0.000 description 4
- DWQHHFSPGQRLMB-UHFFFAOYSA-N 2-ethylhexanoic acid;yttrium Chemical compound [Y].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O DWQHHFSPGQRLMB-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 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 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 229920001558 organosilicon polymer Polymers 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- QYCGBAJADAGLLK-UHFFFAOYSA-N 1-(cyclohepten-1-yl)cycloheptene Chemical compound C1CCCCC=C1C1=CCCCCC1 QYCGBAJADAGLLK-UHFFFAOYSA-N 0.000 description 3
- 125000006024 2-pentenyl group Chemical group 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000005110 aryl thio group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 description 3
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 3
- 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 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 2
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 2
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- OPSIPADNUJORFA-UHFFFAOYSA-N 2-ethylhexanoic acid lanthanum Chemical compound [La].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O OPSIPADNUJORFA-UHFFFAOYSA-N 0.000 description 2
- IVIABZGPROAOAR-UHFFFAOYSA-N 2-ethylhexanoic acid neodymium Chemical compound [Nd].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O IVIABZGPROAOAR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical compound C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 125000005394 methallyl group Chemical group 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- QVTVDJWJGGEOGX-UHFFFAOYSA-N urea;cyanide Chemical compound N#[C-].NC(N)=O QVTVDJWJGGEOGX-UHFFFAOYSA-N 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- 125000005837 1,2-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([*:2])C1([H])[H] 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- 125000005838 1,3-cyclopentylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:2])C([H])([H])C1([H])[*:1] 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- VFCHHMABGOYOQI-UHFFFAOYSA-N 2,4-dimethylhex-3-ene Chemical compound CCC(C)=CC(C)C VFCHHMABGOYOQI-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- WKRJCCZAZDZNJL-UHFFFAOYSA-N 2-methoxyethoxysilicon Chemical compound COCCO[Si] WKRJCCZAZDZNJL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZMWJQGOYIBHQJG-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-ol Chemical compound CCO[Si](C)(OCC)CCCO ZMWJQGOYIBHQJG-UHFFFAOYSA-N 0.000 description 1
- MQSZOZMNAJHVML-UHFFFAOYSA-N 3-phenylbut-1-yn-1-ol Chemical compound OC#CC(C)C1=CC=CC=C1 MQSZOZMNAJHVML-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical class C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- JUPXMUGTWUWGCT-UHFFFAOYSA-N 4-triethoxysilylbutan-2-yl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCC(C)OC(=O)C=C JUPXMUGTWUWGCT-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CFYWWVKFAUAATB-UHFFFAOYSA-N C(=O)=C=C.[Pt] Chemical group C(=O)=C=C.[Pt] CFYWWVKFAUAATB-UHFFFAOYSA-N 0.000 description 1
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 description 1
- XQIDGXXNEIMJLG-UHFFFAOYSA-N CO[SiH](CCC(C)OC(=O)C=C)OC Chemical compound CO[SiH](CCC(C)OC(=O)C=C)OC XQIDGXXNEIMJLG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 206010018612 Gonorrhoea Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UIEXFJVOIMVETD-UHFFFAOYSA-N P([O-])([O-])[O-].[Pt+3] Chemical compound P([O-])([O-])[O-].[Pt+3] UIEXFJVOIMVETD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910020381 SiO1.5 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- HHWWIVLPIGGYDR-UHFFFAOYSA-N but-1-enoxy(dimethoxy)silane Chemical compound C(CC)=CO[SiH](OC)OC HHWWIVLPIGGYDR-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical compound [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- PWAPCRSSMCLZHG-UHFFFAOYSA-N cyclopentylidene Chemical group [C]1CCCC1 PWAPCRSSMCLZHG-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- DFNRUVXBGPHQIX-UHFFFAOYSA-N diethoxy(pent-2-en-2-yloxy)silane Chemical compound CCC=C(C)O[SiH](OCC)OCC DFNRUVXBGPHQIX-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- ZKFHZTZYWXIDJJ-UHFFFAOYSA-N methyl(silyloxysilyloxysilyloxy)silane Chemical compound C[SiH2]O[SiH2]O[SiH2]O[SiH3] ZKFHZTZYWXIDJJ-UHFFFAOYSA-N 0.000 description 1
- SWGZAKPJNWCPRY-UHFFFAOYSA-N methyl-bis(trimethylsilyloxy)silicon Chemical compound C[Si](C)(C)O[Si](C)O[Si](C)(C)C SWGZAKPJNWCPRY-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical compound P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000012898 sample dilution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Silicon Polymers (AREA)
- Led Device Packages (AREA)
Abstract
The purpose of the present invention is to provide a curable resin composition useful for sealing semiconductor elements (particularly optical semiconductor elements), said curable resin composition having both heat resistance and corrosion resistance against corrosive gases. This curable resin composition is characterized by including a polyorganosiloxane (A), a silsesquioxane (B), an isocyanurate compound (C), and a carboxylate (E) of a rare-earth metal element, wherein a polyorganosiloxane not containing an aryl group is included as the polyorganosiloxane (A), and a ladder-type silsesquioxane is included as the silsesquioxane (B).
Description
Technical field
The present invention relates to it is hardening resin composition and the solidfied material being obtained using this hardening resin composition, close
Closure material and the semiconductor device being obtained using this encapsulant.The application was filed an application in Japan based on June 6th, 2014
Japanese Patent Application 2014-117841 claim priority, and its content is incorporated herein.
Background technology
In the semiconductor device having high demands heat-resisting/high proof voltage, for the material of cladding semiconductor element, generally
Require 150 DEG C about above heat resistances.Particularly, for the material (sealing material of the optical materials such as cladding optical semiconductor
Material) for, in addition to heat resistance, also require the physical properties excellent such as the transparency, flexibility.At present, as such as liquid crystal display
Backlight unit in encapsulant, the silicone resin material having patent document 1～4 grade of use.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-206721 publication
Patent document 2：Japanese Unexamined Patent Publication 2007-031619 publication
Patent document 3：Japanese Unexamined Patent Publication 2002-314140 publication
Patent document 4：Japanese Unexamined Patent Publication 2011-178983 publication
Content of the invention
Problems to be solved by the invention
In patent document 1, as the material that heat resistance is high, thermal diffusivity is good, disclose a kind of synthetic macromolecular compound, its
The 3rd organosilicon polymer being 20,000～800,000 containing more than a kind of molecular weight, described 3rd organosilicon polymer is based on by having
At least a kind the 1st organosilicon polymer of the cross-linked structure of siloxanes (Si-O-Si bonding body) and have linear based on siloxanes
At least a kind the 2nd organosilicon polymer of connecting structure is linked by siloxanes key.However, the solidfied material of these compounds
Physical property still unsatisfactory.
In addition, in patent document 2, as the optical element sealing resin that the transparency, uv-resistance, heat-resisting coloring are excellent
Composition, discloses and combines as the optical element sealing resin of resinous principle containing following at least one silsesquioxanes
Thing, described silsesquioxane is selected from：The liquid of cagelike structure body containing aliphatic carbon-to-carbon unsaturated bond and without Si -- H bond
Silsesquioxane and containing Si -- H bond and without aliphatic carbon-to-carbon unsaturated bond the liquid of cagelike structure body silsesquioxane
Alkane.And, wherein describe the description below：Transmitance after heating 100 hours at 150 DEG C reduces less.However, its heat resistance
Still unsatisfactory, and, comprise that the solidfied material of the resin combination of the silsesquioxane of cage modle is harder, flexibility not
Foot, therefore there is a problem of being also easy to produce crackle, cracking.
In addition, Patent Document 3 discloses a kind of solidification compound, it contains following compositions as neccessary composition：1 point
In son containing at least 2 have with SiH base the organic compounds such as the reactive triallyl isocyanurate of carbon-to-carbon double bond, 1 point
Containing at least compound such as the chain of 2 SiH bases and/or cyclic polyorganosiloxane, hydrosilylation catalysts in son.However, this
The heat resistance of a little materials, the resistance to physical property such as anti-thread breakage are still unsatisfactory.
On the other hand, there is energising in the metal material such as electrode in optical semiconductor device easily being corroded property gas attack
There is the such problem of deterioration in characteristic (for example, energising characteristic in hot environment).For this reason, for photosemiconductor sealing
Material it is desirable to have high barrier (with respect to the corrosion resistance of corrosive gas) to corrosive gas.However, just employing specially
Barrier for traditional encapsulant of silicone resin material disclosed in sharp document 1～3 grade, to corrosive gas
Still insufficient.
Patent Document 4 discloses a kind of excellent organosilicon resin composition of sulfidation-resistance, said composition contains：(A)
There are at least 2 polysiloxanes with the thiazolinyl of silicon atom bonding, (B) have at least 2 poly- with the hydrogen-based of silicon atom bonding
Siloxane crosslinker, (C) silicon hydrogenation catalyst and (D) zinc compound, and become with respect to above-mentioned (A) composition and above-mentioned (B)
Total amount 100 mass parts divided, the content of above-mentioned (D) composition is 0.1～5 mass parts.Though however, disclosing pin in this patent document
To hydrogen sulfide (H2S corrosion resistance), but for the corrosion resistance for other corrosive gas, be silent on completely.And,
With regard to heat resistance, also fail to satisfactory.
As light source encapsulant of new generation it is desirable to more excellent heat resistance.In addition, the miniaturization of adjoint equipment,
Slimming, it is desirable to more excellent heat resistance for the material of cladding semiconductor element.
Further, can lead to semiconductor device occur corrosion corrosive gas exist multiple, it is therefore desirable to also have concurrently right
The barrier of varied corrosive gas.Wherein, the present inventor etc. finds, for the material of cladding semiconductor element,
At least have concurrently to hydrogen sulfide (H2S) barrier (the resistance to H of gas2S corrosivity) and to oxysulfide (SOx) gas barrier (resistance to
SOxCorrosivity) both is important.
Therefore, it is an object of the invention to provide heat resistance (particularly more than 180 DEG C of heat resistances) and to corrosivity
The corrosion resistance of gas is (particularly to hydrogen sulfide (H2S) barrier (the resistance to H of gas2S corrosivity) and to oxysulfide (SOx) gas
Barrier (the resistance to SO of bodyxCorrosivity)) the consolidating of the seal applications being applied to semiconductor element (particularly optical semiconductor)
The property changed resin combination.Other purposes of the present invention are to be provided with the transparency, flexibility, have heat resistance concurrently, to corruption simultaneously
The curability tree of the seal applications being applied to semiconductor element (particularly optical semiconductor) of the corrosion resistance of corrosion gas
Oil/fat composition.
The method of solve problem
The present inventor etc. finds, in specific organic siliconresin during the carboxylate of interpolation rare earth, can suppress
Hardness after the heating of solidfied material rises, and heat resistance significantly improves, and resistance to H2S corrosivity also improves.Further, by spy
In the carboxylate of fixed organic siliconresin and rare earth, cooperation comprises the silsesquioxane of ladder type silsesquioxane and different
Cyanurate compound, is not result in heat resistance, resistance to H2S corrosivity (H2S barrier properties for gases) reduce, resistance to SOxCorrosivity (SOxGas
Body barrier) also excellent, and then complete the present invention.
That is, the present invention provides hardening resin composition, and it comprises polysiloxane (A), silsesquioxane (B), different
The carboxylate (E) of cyanurate compound (C) and rare earth, as polysiloxane (A), comprises not have aryl
Polysiloxane, as silsesquioxane (B), comprise ladder type silsesquioxane.
As above-mentioned ladder type silsesquioxane, preferably comprise the ladder type sesquialter silicon that intramolecular has aliphatic carbon-to-carbon double bond
Oxygen alkane.
As above-mentioned ladder type silsesquioxane, preferably comprise the ladder type silsesquioxane that intramolecular has Si -- H bond.
As above-mentioned ladder type silsesquioxane, preferably comprise the ladder type silsesquioxane that intramolecular has aryl.
As isocyanurate compound (C), preferably comprise the isocyanurate compound shown in formula (1).
[chemical formula 1]
[in formula (1), Rx、Ry、RzIdentical or different, the group shown in expression (2) or the group shown in formula (3).
[chemical formula 2]
[chemical formula 3]
[in formula (2) and formula (3), R1And R2Identical or different, represent the straight-chain of hydrogen atom or carbon number 1～8 or prop up
The alkyl of chain.]].
Above-claimed cpd shown in formula (1) is preferably Rx、Ry、RzIn any one above be the group shown in formula (3)
Compound.
Carboxylate (E) as rare earth, preferably comprises carboxylic acid yttrium.
The carboxylate (E) of rare earth is preferably cerium carboxylate, the mixture of carboxylic acid lanthanum, carboxylic acid praseodymium and carboxylic acid neodymium.
The sum of the Si-H base being present in contained compound in hardening resin composition is with respect to being present in solidification
The ratio of the sum of the aliphatic carbon-to-carbon double bond with silicon atom bonding in contained compound in property resin combination is preferably smaller than
1.
Preferably further comprise silane coupler (D).
Further, the present invention is provided solidfied material obtained from the solidification of above-mentioned hardening resin composition.
Further, the present invention provides and uses encapsulant obtained from above-mentioned hardening resin composition.
Further, the present invention provides and uses semiconductor device obtained from above-mentioned encapsulant.
That is, the present invention relates to following aspect.
[1] a kind of hardening resin composition, it comprises polysiloxane (A), silsesquioxane (B), isocyanuric acid
The carboxylate (E) of ester compounds (C) and rare earth, as polysiloxane (A), comprising not have the poly- of aryl has
Organic siloxane, as silsesquioxane (B), comprises ladder type silsesquioxane.
[2] hardening resin composition described in above-mentioned [1], wherein, as above-mentioned ladder type silsesquioxane, comprises molecule
Inside there is the ladder type silsesquioxane of aliphatic carbon-to-carbon double bond.
[3] hardening resin composition described in above-mentioned [1] or [2], wherein, as above-mentioned ladder type silsesquioxane, wraps
There is the ladder type silsesquioxane of Si -- H bond containing intramolecular.
[4] hardening resin composition any one of above-mentioned [1]～[3], wherein, as above-mentioned ladder type sesquialter silicon
Oxygen alkane, comprises the ladder type silsesquioxane that intramolecular has aryl.
[5] hardening resin composition any one of above-mentioned [1]～[4], wherein, as isocyanuric acid ester chemical combination
Thing (C), comprises the isocyanurate compound shown in above-mentioned formula (1).
[6] hardening resin composition described in above-mentioned [5], wherein, the above-mentioned isocyanuric acid esterification shown in above-mentioned formula (1)
Compound is Rx、Ry、RzOne of above be the group shown in above-mentioned formula (3) isocyanurate compound.
[7] hardening resin composition any one of above-mentioned [1]～[6], wherein, as rare earth
Carboxylate (E), comprises carboxylic acid yttrium.
[8] hardening resin composition any one of above-mentioned [1]～[6], wherein, the carboxylic acid of rare earth
Salt (E) is cerium carboxylate, the mixture of carboxylic acid lanthanum, carboxylic acid praseodymium and carboxylic acid neodymium.
[9] hardening resin composition any one of above-mentioned [1]～[8], wherein, is present in curable resin group
The sum of the Si-H base in contained compound in compound is with respect to being present in contained compound in hardening resin composition
In the sum of the aliphatic carbon-to-carbon double bond with silicon atom bonding ratio be less than 1.
[10] hardening resin composition any one of above-mentioned [1]～[9], it comprises silane coupler further
(D).
[11] hardening resin composition any one of above-mentioned [1]～[10], wherein, above-mentioned polysiloxane
(A) polysiloxane comprising in is the straight of the group that has hydrosilyl or comprise aliphatic carbon-to-carbon unsaturated bond
Chain or the polysiloxane of branched.
[12] hardening resin composition any one of above-mentioned [1]～[11], wherein, above-mentioned poly-organosilicon epoxide
Silicon alkylidene is the poly-organosilicon epoxide silicon alkylidene with the structure shown in formula (6).
[13] hardening resin composition any one of above-mentioned [1]～[12], wherein, with respect to poly organo
The total amount of alkane (A), the ratio of the above-mentioned polysiloxane without aryl is more than 50 weight %.
[14] hardening resin composition any one of above-mentioned [1]～[13], wherein, with respect to curable resin
The total amount of composition, the content of above-mentioned polysiloxane (A) is 55～95 weight %.
[15] hardening resin composition any one of above-mentioned [1]～[14], wherein, with respect to silsesquioxane
(B) total amount, the content of above-mentioned ladder type silsesquioxane is more than 50 weight %.
[16] hardening resin composition any one of above-mentioned [2]～[15], wherein, with respect to silsesquioxane
(B) total amount, above-mentioned intramolecular have the ladder type silsesquioxane of aliphatic carbon-to-carbon double bond content be 20 weight % with
On.
[17] hardening resin composition any one of above-mentioned [3]～[16], wherein, with respect to silsesquioxane
(B) total amount, the content that above-mentioned intramolecular has the ladder type silsesquioxane of Si -- H bond is more than 10 weight %.
[18] hardening resin composition any one of above-mentioned [1]～[17], wherein, with respect to curable resin
The total amount of composition, the content of above-mentioned silsesquioxane (B) is 5～45 weight %.
[19] hardening resin composition any one of above-mentioned [1]～[18], wherein, with respect to curable resin
The total amount of composition, the content of above-mentioned isocyanurate compound (C) is 0.01～10 weight %.
[20] hardening resin composition any one of above-mentioned [1]～[19], wherein, with respect to curable resin
The total amount of composition, the content of above-mentioned silane coupler (D) is 0.01～15 weight %.
[21] hardening resin composition any one of above-mentioned [1]～[20], wherein, with respect to curable resin
Total composition, the content of the above-mentioned carboxylate (E) of rare earth is 0.008～1.000 weight %.
[22] a kind of solidfied material, it is to obtain the hardening resin composition solidification any one of [1]～[21]
Arrive.
[23] a kind of encapsulant, its be use [1]～[21] any one of hardening resin composition and obtain
Arrive.
[24] a kind of semiconductor device, it is obtained from the encapsulant using described in [23].
The effect of invention
The hardening resin composition of the present invention due to having an above-mentioned composition, therefore heat resistance and for H2S gas,
SOxBarrier (the resistance to H of multiple corrosive gas such as gas2S corrosivity, resistance to SOxCorrosivity etc.) excellent.In addition, it is transparent, soft
Soft, reflux-resisting welded property, adaptation etc. are also excellent.Therefore, the hardening resin composition of the present invention is as semiconductor device
The encapsulant of the optical semiconductors such as encapsulant, particularly LED and useful.In addition, the curable resin group of the present invention
Compound is as the non-existent so far light source of new generation requiring the heat resistance in high temperature (for example, more than 180 DEG C) environment
Useful with encapsulant.Further, the solidfied material by using the hardening resin composition of the present invention is first to photosemiconductor
Part is sealed, it is possible to obtain the excellent optical semiconductor device such as quality, durability.
Specific embodiment
The hardening resin composition of the present invention includes at least polysiloxane (A), silsesquioxane (B), isocyanide urea
The carboxylate (E) of ester compound (C) and rare earth.Polysiloxane (A) includes at least does not have the poly- of aryl
Organosiloxane.Silsesquioxane (B) includes at least ladder type silsesquioxane.
[polysiloxane (A)]
Polysiloxane (A) in the hardening resin composition of the present invention is that have to comprise siloxanes key (Si-O-
The polysiloxane of main chain Si), it includes at least the polysiloxane without aryl.
It should be noted that in this manual, also will have the poly- organic of the main chain comprising siloxanes key (Si-O-Si)
Siloxanes is referred to as " polysiloxane ".
As the polysiloxane comprising in polysiloxane (A), it is not particularly limited, can enumerate for example：Do not have
The polysiloxane having aryl, the polysiloxane with aryl, as main chain except having-Si-O- base (siloxy)
There is-Si-A- base [silicon alkylidene in addition further；A represents bivalent hydrocarbon radical (for example, alkylidene)] the poly- of aryl that do not have have
Organic siloxane (below, this polysiloxane being referred to as " poly-organosilicon epoxide silicon alkylidene ") etc..
In addition, the polysiloxane comprising in polysiloxane (A) can also be with hydrosilyl or tool
There are the straight-chain of the group of aliphatic carbon-to-carbon unsaturated bond or the polysiloxane of branched.As polysiloxane (A)
In the polysiloxane that comprises, can enumerate and there is the known usual silicone such as dimethyl silscone skeleton (dimethyl silicone polymer)
The polysiloxane of skeleton.
It should be noted that the polysiloxane comprising in polysiloxane (A) does not include silsesquioxane (B).
The polysiloxane comprising in above-mentioned polysiloxane (A) can also be have straight chain and/or side chain poly-
Organosiloxane.
As the aryl in the above-mentioned polysiloxane with aryl, it is not particularly limited, can enumerate for example：Phenyl,
The C such as naphthyl6-14Aryl (particularly C6-10Aryl) etc..These aryl can also be that the silicon atom in polysiloxane (A) is had
Some substituents (group with silicon atom Direct Bonding).
The above-mentioned polysiloxane without aryl is preferably the poly organo that intramolecular contains substantially no aryl
Alkane.Specifically, the content of the aryl in the above-mentioned polysiloxane (100 weight %) without aryl is preferably 0.5 weight
Below amount below %, more preferably 0.2 weight %, below more preferably 0.1 weight %, particularly preferably in poly organo
There is not aryl in alkane (A).It is below 0.5 weight % (particularly, by there is not aryl) by the content making aryl, solidification
It is readily available desired physical property (heat resistance, refractive index etc.) in thing.The content of the aryl in polysiloxane can be passed through1H-
NMR and measure.
The substituent having as silicon atom in the polysiloxane comprising in above-mentioned polysiloxane (A), can
Enumerate for example：There is the group of Si -- H bond, substituted or unsubstituted alkyl (preferably alkyl, thiazolinyl, cycloalkyl or cyclenes
Base), hydroxyl, alkoxyl, alkenyloxy group, acyloxy, sulfydryl (mercapto), alkylthio group, alkenylthio group, carboxyl, alkoxy carbonyl, amino
Or substituted-amino (list or dialkyl amido, acyl amino etc.), epoxy radicals, halogen atom etc..
As abovementioned alkyl, preferably C1-10Alkyl, more preferably C1-4Alkyl.As above-mentioned thiazolinyl, preferably C2-10Alkene
Base, more preferably C2-4Thiazolinyl.As above-mentioned cycloalkyl, preferably C3-12Cycloalkyl.As above-mentioned cycloalkenyl group, preferably C3-12Ring
Thiazolinyl.As above-mentioned alkoxyl, preferably C1-6Alkoxyl.As above-mentioned alkenyloxy group, preferably C1-6Alkenyloxy group.As above-mentioned acyl
Epoxide, preferably C1-6Acyloxy.As above-mentioned alkylthio group, preferably C1-6Alkylthio group.As above-mentioned alkenylthio group, preferably C1-6
Alkenylthio group.As above-mentioned alkoxy carbonyl, preferably C1-6Alkoxy carbonyl.As above-mentioned halogen atom, preferably fluorine atom, chlorine
Atom, bromine atoms, atomic iodine etc..
As above-mentioned substituent, it is preferably selected from that there is the group of Si -- H bond, substituted or unsubstituted alkyl (preferably alkane
Base or thiazolinyl) at least more than a kind substituent.
The position of the above-mentioned substituent in polysiloxane is not particularly limited, with respect to comprising siloxanes key (Si-O-
Si main chain), may be located at side chain, can also be located at end.
It should be noted that the polysiloxane with hydrosilyl can also be have simultaneously aliphatic carbon-
The polysiloxane of carbon unsaturated bond.In addition, the polysiloxane with aliphatic carbon-to-carbon unsaturated bond can also be same
When there is the polysiloxane of hydrosilyl.
As the bivalent hydrocarbon radical (above-mentioned A) in the silicon alkylidene of above-mentioned poly-organosilicon epoxide silicon alkylidene, can enumerate for example：
Alkylidene (straight-chain of carbon number 1～18 or the alkylidene of branched etc.), divalence ester ring type alkyl etc., preferably carbon atom
The alkylidene (particularly ethylidene) of the straight-chain of number 2～4 or branched.
As above-mentioned poly-organosilicon epoxide silicon alkylidene, can enumerate and for example there is the poly- of structure shown in following formula (6) have
Machine siloxy silicon alkylidene.
[chemical formula 4]
In formula (6), R21～R26Identical or different, represent hydrogen atom, monovalent hydrocarbon or monovalence hetero ring type group.And,
R21～R26One of above be the univalent perssad comprising aliphatic carbon-to-carbon unsaturated bond.
As above-mentioned monovalent hydrocarbon, can enumerate for example：Univalent aliphatic series alkyl；Monovalence ester ring type alkyl；Aliphatic alkyl
And the univalent perssad of ester ring type alkyl bonding etc..
As above-mentioned monovalence hetero ring type group, can enumerate for example：Pyridine radicals, furyl, thienyl etc..
As above-mentioned univalent aliphatic series alkyl, can enumerate for example：Alkyl, thiazolinyl, alkynyl etc..As abovementioned alkyl, can arrange
Citing is such as：The straight-chain such as methyl, ethyl, propyl group, isopropyl, butyl, hexyl, octyl group, iso-octyl, decyl, dodecyl or
The C of chain1-20Alkyl (preferably C1-10Alkyl, more preferably C1-4Alkyl) etc..As above-mentioned thiazolinyl, can enumerate for example：Ethene
Base, pi-allyl, methacrylic, 1- acrylic, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2-
The C such as pentenyl, 3- pentenyl, 4- pentenyl, 5- hexenyl2-20Thiazolinyl (preferably C2-10Thiazolinyl, more preferably C2-4Alkene
Base) etc..As above-mentioned alkynyl, can enumerate for example：The C such as acetenyl, propinyl2-20Alkynyl (preferably C2-10Alkynyl, excellent further
Elect C as2-4Alkynyl) etc..
As above-mentioned monovalence ester ring type alkyl, can enumerate for example：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, ring 12
The C such as alkyl3-12Cycloalkyl；The C such as cyclohexenyl group3-12Cycloalkenyl group；The C such as bicycloheptane base, bicycloheptene base4-15Endocyclic
Alkyl etc..
In addition, as the univalent perssad of aliphatic alkyl and ester ring type alkyl bonding, can enumerate for example：Cyclohexyl first
Base, methylcyclohexyl etc..
Above-mentioned monovalent hydrocarbon and above-mentioned monovalence hetero ring type group can also have substituent.
That is, above-mentioned monovalent hydrocarbon or above-mentioned monovalence hetero ring type group can also be the above-mentioned monovalent hydrocarbon enumerated or monovalence is miscellaneous
At least one hydrogen atom replacement in ring type group is the monovalent hydrocarbon of substituent or monovalence hetero ring type group.Above-mentioned replacement
The carbon number of base is preferably 0～20, more preferably 0～10.As above-mentioned substituent, specifically can enumerate for example：Halogen atom；Hydroxyl
Base；Alkoxyl；Alkenyloxy group；Acyloxy；Sulfydryl；Alkylthio group；Alkenylthio group；Carboxyl；Alkoxy carbonyl；Amino；List or dialkyl amino
Base；Acyl amino；Group containing epoxy radicals；Group containing oxetanylmethoxy；Acyl group；Oxo base；NCO；These
In group 2 are above according to needs via C1-6Group of alkylene etc..
As above-mentioned halogen atom, chlorine atom, bromine atoms, atomic iodine etc. can be enumerated.As above-mentioned alkoxyl, example can be enumerated
As：The C such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy1-6Alkoxyl (preferably C1-4Alkoxyl)
Deng.As above-mentioned alkenyloxy group, can enumerate for example：The C such as allyloxy2-6Alkenyloxy group (preferably C2-4Alkenyloxy group) etc..As above-mentioned
Acyloxy, can enumerate for example：The C such as acetoxyl group, propionyloxy, (methyl) acryloxy1-12Acyloxy etc..
As above-mentioned alkylthio group, can enumerate for example：The C such as methyl mercapto, ethylmercapto group1-6Alkylthio group (preferably C1-4Alkylthio group)
Deng.As above-mentioned alkenylthio group, can enumerate for example：The C such as allyl sulfenyl2-6Alkenylthio group (preferably C2-4Alkenylthio group) etc..As above-mentioned
Alkoxy carbonyl, can enumerate for example：The C such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl1-6Alkoxyl-
Carbonyl etc..As above-mentioned list or dialkyl amido, can enumerate：Methylamino, ethylamino, dimethylamino, diethylamino
Deng single or two-C1-6Alkyl amino etc..As above-mentioned acyl amino, can enumerate for example：Acetyl-amino, propanoylamino etc.
C1-11Acyl amino etc..As the above-mentioned group containing epoxy radicals, can enumerate for example：Glycidyl, glycidoxypropyl, 3,
4- epoxycyclohexyl etc..As the above-mentioned group containing oxetanylmethoxy, can enumerate for example：Ethyl oxa- cyclobutoxy group etc..Make
For above-mentioned acyl group, can enumerate for example：Acetyl group, propiono, benzoyl etc..
As above-mentioned monovalent hydrocarbon, monovalence hetero ring type group, preferably methyl, ethyl, propyl group, isopropyl, butyl, hexyl,
Octyl group, decyl, pyridine radicals, furyl, thienyl, vinyl, pi-allyl, there are alkyl (for example, 2- (3, the 4- rings of substituent
Oxygen cyclohexyl) ethyl, 3- glycidylpropyl, 3- methacryloxypropyl, 3- acryloxypropyl, N-2- (ammonia
Base ethyl) -3- aminopropyl, 3- aminopropyl, 3- mercaptopropyi, 3- isocyanates propyl group etc.) etc..
R in above-mentioned formula (6)21～R26Each can identical it is also possible to different.
In formula (6), R27Represent bivalent hydrocarbon radical.As above-mentioned bivalent hydrocarbon radical, can enumerate for example：Straight-chain or the Asia of branched
Alkyl, divalence ester ring type alkyl etc..As the alkylidene of straight-chain or branched, can enumerate for example：Methylene, methyl methylene
The carbon numbers such as base, dimethylated methylene base, ethylidene, propylidene, trimethylene are 1～18 straight-chain or the alkylene of branched
Base.As divalence ester ring type alkyl, can enumerate for example：1,2- cyclopentylene, 1,3- cyclopentylene, cyclopentylidene, 1,2- Asia hexamethylene
The divalence cycloalkylidenes such as base, 1,3- cyclohexylidene, 1,4- cyclohexylidene, cyclohexylidene (comprise cycloalkanes fork).Wherein, as R27, excellent
Elect carbon number 1～18 (preferably carbon number 1～8, more preferably carbon number 1～5, further preferred carbon number 2～4) as
Straight-chain or the alkylidene of branched, more preferably ethylidene.
In formula (6), r represents more than 1 integer.In the case that r is more than 2 integer, divide with the structure in the bracket of r
Not can identical it is also possible to different.In the case of the structure in the bracket of r each difference, each structure addition shape each other
State is not particularly limited, and can be random or block type.In addition, in formula (6), s represents more than 1 integer.S is 2
In the case of above integer, with the structure in the bracket of s respectively can identical it is also possible to different.With in the bracket of s
Each in the case of difference, each structure addition form each other is not particularly limited structure, can be random or embedding
Segment type.Additionally, in formula (6), the addition form with the structure in the structure in the bracket of r and the bracket with s does not have spy yet
Different restriction, can be random or block type.It should be noted that r and s can be the same or different.That is, formula
(6) in, r, s are identical or different, represent more than 1 integer respectively.
The end structure of above-mentioned poly-organosilicon epoxide silicon alkylidene is not particularly limited, and can enumerate for example：Comprise aliphatic
The group of carbon-to-carbon double bond, hydrosilyl, silanol group, alkoxysilyl, trialkylsilkl (for example, front three
Base silicyl) etc..
Above-mentioned poly-organosilicon epoxide silicon alkylidene is as set forth above, it is possible to have straight chain, any chain structure in side chain.
Above-mentioned poly-organosilicon epoxide silicon alkylidene for example can be by the side described in Japanese Unexamined Patent Publication 2012-140617 publication
Method is manufacturing.
The polysiloxane comprising in polysiloxane (A) can be used alone a kind or makes two or more combination
With.
Polysiloxane (for example, the poly-organosilicon epoxide silicon alkylene without aryl in polysiloxane (A)
Base) ratio be not particularly limited, but from the viewpoint of flexibility, such as with respect to polysiloxane (A) total amount (100
Weight %), more than preferably 50 weight %, more than more preferably 80 weight %, more than more preferably 95 weight %.Its
In, from the viewpoint of obtaining more excellent flexibility, particularly preferred polysiloxane (A) is only does not have the poly- of aryl
Organosiloxane.It should be noted that in the case of comprising the polysiloxane that two or more does not have aryl, referring to close
The ratio of meter content (weight).
In the case of being applied in combination two or more polysiloxane, preferably at least a kind have hydrosilyl, at least 1
Plant and there is aliphatic carbon-to-carbon unsaturated bond.
The polysiloxane (particularly there is no the polysiloxane of aryl) comprising in polysiloxane (A)
Number-average molecular weight (Mn) is preferably 500～20000, more preferably 1000～10000, more preferably 2000～8000.Separately
Outward, weight average molecular weight (Mw) be preferably 500～50000, more preferably 5000～40000, more preferably 10000～
30000.It is more than 500 by making number-average molecular weight and/or weight average molecular weight, the excellent heat resistance of gained solidfied material.By making
Number-average molecular weight is less than 20000 and/or make weight average molecular weight be less than 50000, polysiloxane (A) and other compositions
Excellent compatibility.
It should be noted that the above-mentioned number-average molecular weight of this specification, weight average molecular weight refer to for example to utilize gel
The form of the molecular weight of the polystyrene conversion of permeation chromatography, Alliance HPLC system 2695 (Waters system),
Refractive Index Detector 2414 (Waters system), chromatographic column:Tskgel GMHHR- M × 2 (eastern Cao's (strain) system),
Guard column:Tskgel guard column HHRL (eastern Cao's (strain) system), column oven:COLUMN HEATER U-620(Sugai
System), solvent:THF, condition determination:The molecular weight measuring under conditions of 40 DEG C.
Therefore, even number-average molecular weight, weight average molecular weight are included in other in the case of using other analytical equipments
The polysiloxane of scope, as long as under the conditions of said determination, number-average molecular weight and/or weight average molecular weight are in above range, then
Belong to comprise in the polysiloxane (A) constituting as one of the composition of hardening resin composition of the present invention poly- organic
Siloxanes.
(particularly, there is no the poly organo of aryl for the polysiloxane comprising in polysiloxane (A)
Alkane) be not particularly limited by the molecular weight dispersity (Mw/Mn) that weight average molecular weight (Mw) and number-average molecular weight (Mn) calculate, but
From heat resistance and with the compatibility of other compositions from the viewpoint of, such as preferably 1.0～7.0, more preferably 2.0～6.5,
More preferably 3.0～6.0, particularly preferably 4.0～5.5.
The polysiloxane (particularly there is no the polysiloxane of aryl) comprising in polysiloxane (A)
The content (vinyl conversion) of intramolecular aliphatic carbon-to-carbon double bond is not particularly limited, but from easily to being present in curability
The number of the aliphatic carbon-to-carbon double bond with silicon atom bonding in contained compound in resin combination is adjusted, easily
From the viewpoint of obtaining flexibility and the solidfied material of excellent strength, (such as 0.5～3.0 weight below preferably such as 3.0 weight %
Amount %).It should be noted that the content of intramolecular aliphatic carbon-to-carbon double bond for example can be passed through1H-NMR is measured.
The content (use level) of the polysiloxane (A) in the hardening resin composition of the present invention does not have special limit
Fixed, but the total amount (100 weight %) preferably with respect to hardening resin composition is 55～95 weight %, is more preferably 60～92
Weight %, more preferably 65～90 weight %.When content is less than 55 weight %, the resistance to anti-thread breakage fall of solidfied material may be led to
Low.On the other hand, when content is more than 90 weight %, possibly the gas barrier property to corrosive gas cannot fully be obtained.
[silsesquioxane (B)]
The hardening resin composition of the present invention includes at least ladder type silsesquioxane as silsesquioxane (B).Above-mentioned
Ladder type silsesquioxane is the polysiloxanes of the three-dimensional structure with crosslinking.
Polysiloxanes is the compound with the main chain being made up of siloxanes key (Si-O-Si), substantially constitutes list as it
Unit, can enumerate：M unit (unit being made up of 1 valency group of silicon atom and 1 oxygen atoms bond), D unit are (former by silicon
The unit of son and the divalent group of 2 oxygen atoms bond composition), T unit is (by silicon atom and 3 oxygen atoms bond
Trivalent group constitute unit), Q unit (unit being made up of 4 valency groups of silicon atom and 4 oxygen atoms bond).Separately
Outward, as the structure of Si-O-Si skeleton, can enumerate：Disordered structure, basket structure, trapezoidal-structure.
In silsesquioxane (B) contained silsesquioxane be with above-mentioned T unit be basic Component units, with empirical formula
(basic structural formula) SiO1.5The polysiloxanes representing, can enumerate for example：Have disordered structure Si-O-Si skeleton structure times
Half siloxanes, have basket structure the silsesquioxane of Si-O-Si skeleton structure, have trapezoidal-structure Si-O-Si skeleton knot
Silsesquioxane (ladder type silsesquioxane) of structure etc..Above-mentioned silsesquioxane (for example, the ladder comprising in silsesquioxane (B)
Type silsesquioxane) can be used alone a kind or two or more is applied in combination.
Empirical formula (basic structural formula) RSiO as above-mentioned ladder type silsesquioxane1.5In above-mentioned R, can enumerate for example：
Hydrogen atom, halogen atom, monovalent organic group, monovalence contain oxygen atom group (do not comprise carbon atom monovalence contain oxygen atom group), one
Valency nitrogen atom group (not comprising the monovalence nitrogen atom group of carbon atom, oxygen atom) or monovalence sulfur atom-containing group (do not wrap
Carbon atoms, the monovalence sulfur atom-containing group of oxygen atom) etc..At least a portion of preferably above-mentioned R is monovalent organic group.Above-mentioned
R can be the same or different respectively.
As the above-mentioned halogen atom in above-mentioned R, can enumerate for example：Fluorine atom, chlorine atom, bromine atoms, atomic iodine etc..
As the above-mentioned monovalent organic group in above-mentioned R, can enumerate for example：Substituted or unsubstituted alkyl (monovalent hydrocarbon
Base), alkoxyl, alkenyloxy group, aryloxy group, aralkoxy, acyloxy, alkylthio group, alkenylthio group, arylthio, aromatic alkylthio, carboxyl,
Alkoxy carbonyl, aryloxycarbonyl, aromatic alkoxy carbonyl, epoxy radicals, cyano group, NCO, carbamoyl, isothiocyanic acid
Ester group etc..
As the above-mentioned alkyl in above-mentioned R, can enumerate for example：Aliphatic alkyl, ester ring type alkyl, aromatic hydrocarbyl, this
More than 2 groups being bonded in a little.
As the above-mentioned aliphatic alkyl in above-mentioned R, can enumerate for example：Alkyl, thiazolinyl, alkynyl.As alkyl, can enumerate
For example：The C such as methyl, ethyl, propyl group, isopropyl, butyl, hexyl, octyl group, iso-octyl, decyl, dodecyl1-20Alkyl is (preferably
For C1-10Alkyl, more preferably C1-4Alkyl) etc..As thiazolinyl, can enumerate for example：Vinyl, pi-allyl, methallyl
Base, 1- acrylic, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 4-
The C such as pentenyl, 5- hexenyl2-20Thiazolinyl (preferably C2-10Thiazolinyl, more preferably C2-4Thiazolinyl) etc..As alkynyl, can arrange
Citing is such as：The C such as acetenyl, propinyl2-20Alkynyl (preferably C2-10Alkynyl, more preferably C2-4Alkynyl) etc..
As the above-mentioned ester ring type alkyl in above-mentioned R, can enumerate for example：Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, ring
The C such as dodecyl3-12Cycloalkyl；The C such as cyclohexenyl group3-12Cycloalkenyl group；The C such as bicycloheptane base, bicycloheptene base4-15Bridge
Ring type alkyl etc..
As the above-mentioned aromatic hydrocarbyl in above-mentioned R, can enumerate for example：The C such as phenyl, naphthyl6-14Aryl (particularly C6-10
Aryl) etc..
In addition, example can be enumerated as in above-mentioned R by the group of above-mentioned aliphatic alkyl and ester ring type alkyl bonding
As：Cyclohexyl methyl, methylcyclohexyl etc..As the group by aliphatic alkyl and aromatic hydrocarbyl bonding, can enumerate
For example：The C such as benzyl, phenethyl7-18Aralkyl (particularly C7-10Aralkyl), the C such as cinnamyl6-10Aryl-C2-6Thiazolinyl, tolyl
Deng C1-4The C such as alkyl substituting aromatic base, styryl2-4Thiazolinyl substituted aryl etc..
Alkyl in above-mentioned R can also have substituent.The carbon number of the substituent in above-mentioned alkyl be preferably 0～
20th, more preferably 0～10.As this substituent, can enumerate for example：The halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine；
Hydroxyl；The C such as methyl, ethyl, propyl group, isopropyl, butyl, hexyl, octyl group, iso-octyl, decyl, dodecyl1-20Alkyl is (preferably
For C1-10Alkyl, more preferably C1-4Alkyl)；Vinyl, pi-allyl, methacrylic, 1- acrylic, isopropenyl, 1-
The C such as cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 4- pentenyl, 5- hexenyl2-20Alkene
Base (preferably C2-10Thiazolinyl, more preferably C2-4Thiazolinyl)；Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy,
The alkoxyls such as isobutoxy (preferably C1-6Alkoxyl, more preferably C1-4Alkoxyl)；The alkenyloxy groups such as allyloxy are (preferably
C2-6Alkenyloxy group, more preferably C2-4Alkenyloxy group)；C is optionally had on the aromatic rings such as phenoxy group, toloxyl, naphthoxy1-4Alkyl,
C2-4Thiazolinyl, halogen atom, C1-4Aryloxy group (the preferably C of the substituents such as alkoxyl6-14Aryloxy group)；Benzyloxy, benzene ethyoxyl etc.
Aralkoxy (preferably C7-18Aralkoxy)；Acetoxyl group, propionyloxy, (methyl) acryloxy, benzoyloxy etc.
Acyloxy (preferably C1-12Acyloxy)；Sulfydryl；The alkylthio groups such as methyl mercapto, ethylmercapto group (preferably C1-6Alkylthio group, more preferably
C1-4Alkylthio group)；The alkenylthio groups such as allyl sulfenyl (preferably C2-6Alkenylthio group, more preferably C2-4Alkenylthio group)；Thiophenyl, toluene sulphur
On the aromatic rings such as base, naphthalene sulfenyl, optionally there is C1-4Alkyl, C2-4Thiazolinyl, halogen atom, C1-4The arylthio of the substituents such as alkoxyl is (excellent
Elect C as6-14Arylthio)；Aromatic alkylthio (the preferably C such as benzylthio, benzene ethylmercapto group7-18Aromatic alkylthio)；Carboxyl；Methoxycarbonyl,
The alkoxy carbonyls such as ethoxy carbonyl, propoxycarbonyl, butoxy carbonyl (preferably C1-6Alkoxy-carbonyl)；Phenoxy group carbonyl
Aryloxycarbonyl (the preferably C such as base, toloxyl carbonyl, naphthoxycarbonyl6-14Aryloxy-carbonyl)；The virtues such as benzyloxycarbonyl
Alkoxy carbonyl (preferably C7-18Aralkoxy-carbonyl)；Amino；Methylamino, ethylamino, dimethylamino, diethyl
The lists such as amino or dialkyl amido (preferably single or two-C1-6Alkyl amino)；Acetyl-amino, propanoylamino, benzoyl
The acyl aminos such as amino (preferably C1-11Acyl amino)；The group containing epoxy radicals such as glycidoxypropyl；Ethyl oxa- ring
The group containing oxetanylmethoxy such as butoxy；The acyl groups such as acetyl group, propiono, benzoyl；Oxo base；In these 2
Above according to needs via C1-6Group of alkylene etc..
As the above-mentioned alkoxyl in above-mentioned R, above-mentioned alkenyloxy group, above-mentioned acyloxy, above-mentioned alkylthio group, above-mentioned alkenylthio group,
Above-mentioned alkoxy carbonyl, can enumerate as the above-mentioned R in formula (6)21～R26And those of example.
As the above-mentioned aryloxy group in above-mentioned R, can enumerate for example：Optionally have on phenoxy group, toloxyl, naphthoxy aromatic ring
There is C1-4Alkyl, C2-4Thiazolinyl, halogen atom, C1-4The C of the substituents such as alkoxyl6-14Aryloxy group etc..As above-mentioned aralkoxy, can
Enumerate for example：The C such as benzyloxy, benzene ethyoxyl7-18Aralkoxy etc..As above-mentioned arylthio, can enumerate for example：Thiophenyl, first
On the aromatic rings such as thiophenyl, naphthalene sulfenyl, optionally there is C1-4Alkyl, C2-4Thiazolinyl, halogen atom, C1-4The C of the substituents such as alkoxyl6-14Virtue
Sulfenyl etc..As above-mentioned aromatic alkylthio, can enumerate for example：The C such as benzylthio, benzene ethylmercapto group7-18Aromatic alkylthio etc..As above-mentioned virtue
Epoxide carbonyl, can enumerate for example：The C such as phenyloxycarbonyl, toloxyl carbonyl, naphthoxycarbonyl6-14Aryloxy-carbonyl etc..Make
For above-mentioned aromatic alkoxy carbonyl, can enumerate for example：The C such as benzyloxycarbonyl7-18Aralkoxy-carbonyl etc..
Contain oxygen atom group as the above-mentioned monovalence in above-mentioned R, can enumerate for example：Hydroxyl, hydroperoxy, sulfo group etc..Make
For above-mentioned monovalence nitrogen atom group, can enumerate for example：Amino or substituted-amino (list or dialkyl amido, acyl amino etc.)
Deng.In addition, as above-mentioned monovalence sulfur atom-containing group, can enumerate for example：Sulfydryl (thiol base) etc..
Further, as above-mentioned empirical formula (basic structural formula) RSiO1.5In above-mentioned R, can enumerate for example：Following formula (4)
Shown group.
[chemical formula 5]
Multiple R ' in above-mentioned formula (4) can be the same or different respectively.As the R ' in formula (4), can enumerate for example：
Hydrogen atom, halogen atom, monovalent organic group, monovalence contain oxygen atom group, monovalence nitrogen atom group or monovalence sulfur atom-containing base
Group etc..As these groups, can enumerate and as above-mentioned empirical formula (basic structural formula) RSiO1.5In R and the identical of example
Group.
In group shown in above-mentioned formula (4), as each R ', it is respectively preferably hydrogen atom, C1-10Alkyl (particularly C1-4Alkane
Base), C2-10Thiazolinyl (particularly C2-4Thiazolinyl), C3-12Cycloalkyl, C3-12C is optionally had on cycloalkenyl group, aromatic ring1-4Alkyl, C2-4Alkene
Base, halogen atom, C1-4The C of the substituents such as alkoxyl6-14Aryl, C7-18Aralkyl, C6-10Aryl-C2-6Thiazolinyl, hydroxyl, C1-6Alcoxyl
Base, halogen atom.
Wherein, as above-mentioned empirical formula (basic structural formula) RSiO1.5In above-mentioned R, preferably hydrogen atom or replace or
Unsubstituted alkyl, more preferably substituted or unsubstituted alkyl, more preferably aliphatic alkyl (particularly alkyl), virtue
Fragrant race alkyl (particularly phenyl).
As above-mentioned ladder type silsesquioxane, it can be the such as ladder type silsesquioxane shown in following formula (5).
[chemical formula 6]
In above-mentioned formula (5), p be more than 1 integer (preferably 1～5000, more preferably 1～2000, more preferably
1～1000).T in above-mentioned formula (5) represents end group.As the R (hereinafter also referred to " side chain ") in above-mentioned formula (5), example can be enumerated
As：Empirically formula RSiO1.5In R and example those.As the T in above-mentioned formula (5), can enumerate for example：Empirically formula
RSiO1.5In R and example those.Wherein, as R or T in above-mentioned formula (5), preferably hydrogen atom or replacement or nothing take
Group shown in the alkyl in generation, formula (4), more preferably hydrogen atom, aliphatic alkyl (particularly, alkyl, thiazolinyl), aromatic hydrocarbon
Base (particularly, phenyl).Particularly, as the T in above-mentioned formula (5), preferably comprise trimethyl, more preferably comprise trimethyl and second
Thiazolinyl or trimethyl and group containing SiH.
Total amount (100 moles of %) with respect to above-mentioned R in formula (5), the ratio shared by substituted or unsubstituted alkyl does not have
Particular determination, but preferably 50 moles more than %, more preferably 80 moles more than %, more preferably 90 moles of more than %.
Particularly, the total amount with respect to above-mentioned R in formula (5) (100 moles of %), substituted or unsubstituted alkyl (preferably carbon number 1
The alkyl of the carbon number such as～10 alkyl, particularly methyl or ethyl 1～4), substituted or unsubstituted aryl (preferably carbon
The aryl of atomicity 6～10, particularly phenyl), (preferably carbon is former for the aralkyl of substituted or unsubstituted carbon number 7～10
The aralkyl of subnumber 7～10, particularly benzyl) total amount be preferably 50 moles of more than %, more preferably 80 moles more than %, enter
One step is preferably 90 moles of more than %.Particularly, from the viewpoint of the barrier to corrosive gas for the solidfied material, preferably above-mentioned
R's is partly or entirely substituted or unsubstituted aryl.
[ladder type silsesquioxane (B1)]
As above-mentioned ladder type silsesquioxane, the ladder type times that such as intramolecular has aliphatic carbon-to-carbon double bond can be comprised
Half siloxanes (B1) (hereinafter also referred to as " ladder type silsesquioxane (B1) ").Above-mentioned ladder type silsesquioxane is preferably ladder type times
Half siloxanes (B1).As ladder type silsesquioxane (B1), as long as above-mentioned side chain or above-mentioned end group have comprise aliphatic carbon-
The compound of the group of carbon double bond is then not particularly limited.
As the above-mentioned group with aliphatic carbon-to-carbon double bond, can enumerate for example：Vinyl, pi-allyl, methallyl
Base, 1- acrylic, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 4-
The C such as pentenyl, 5- hexenyl2-20Thiazolinyl (preferably C2-10Thiazolinyl, more preferably C2-4Thiazolinyl)；The C such as cyclohexenyl group3-12's
Cycloalkenyl group；The C such as bicycloheptene base4-15Endocyclic unsaturated alkyl；The C such as styryl2-4Thiazolinyl substituted aryl；Cinnamyl etc..Need
It is noted that the above-mentioned group with aliphatic carbon-to-carbon double bond is also included in 3 R ' in the group shown in above-mentioned formula (4)
At least one is to have group (for example, the C of aliphatic carbon-to-carbon double bond2-20Thiazolinyl, C3-12Cycloalkenyl group, C4-15Endocyclic insatiable hunger
With alkyl, C2-4Thiazolinyl substituted aryl, cinnamyl etc.) group.Wherein, preferably thiazolinyl, more preferably C2-20Thiazolinyl, excellent further
Select vinyl.
The number of the above-mentioned aliphatic carbon-to-carbon double bond of intramolecular (in a molecule) of ladder type silsesquioxane (B1) does not have spy
Different limit, but preferably more than 2 (for example, 2～50), be more preferably 2～30.Above-mentioned by having within the above range
Aliphatic carbon-to-carbon double bond, exists and is readily available the various physical property such as heat resistance, resistance to anti-thread breakage, excellent to the barrier of corrosive gas
The tendency of different solidfied material.
The content of the above-mentioned aliphatic carbon-to-carbon double bond in ladder type silsesquioxane (B1) is not particularly limited, but is preferably
0.7～5.5mmol/g, more preferably 1.1～4.4mmol/g.In addition, contained above-mentioned fat in ladder type silsesquioxane (B1)
The ratio (weight basis) of race's carbon-to-carbon double bond is not particularly limited, but preferably with vinyl be scaled 2.0～15.0 weight %,
More preferably 3.0～12.0 weight %.
Ladder type silsesquioxane (B1) is not particularly limited, and can also be able to be solid for liquid in normal temperature (about 25 DEG C),
Wherein, it is liquid preferably in normal temperature.More specifically, the viscosity when 25 DEG C for the ladder type silsesquioxane (B1) be preferably 100～
100000mPa s, more preferably 500～10000mPa s, more preferably 1000～8000mPa s.Viscosity is less than
During 100mPa s, the heat resistance of solidfied material may be led to reduce.On the other hand, when viscosity is more than 100000mPa s, may lead
The preparation of hardening resin composition, operation is caused to become difficult.It should be noted that viscosity when 25 DEG C for example can use rheology
Instrument (trade name " PhysicaUDS-200 ", AntonPaar company system) and cone-plate (cone diameter:16mm, cone angle=0 °), in temperature
Degree:25 DEG C, rotating speed:It is measured under conditions of 20rpm.
Silsesquioxane (B) comprise at normal temperatures be solid silsesquioxane (B1) when, exist to corrosive gas
The tendency that corrosion resistance, obdurability (particularly resistance to anti-thread breakage) improve.
[ladder type silsesquioxane (B2)]
As above-mentioned ladder type silsesquioxane it is also possible to comprise the ladder type silsesquioxane that such as intramolecular has Si -- H bond
(B2) (hereinafter also referred to as " ladder type silsesquioxane (B2) ").Above-mentioned ladder type silsesquioxane can also be ladder type silsesquioxane
Alkane (B2).As ladder type silsesquioxane (B2), as long as above-mentioned side chain or above-mentioned end group have hydrogen atom or comprise Si -- H bond
The compound of group be then not particularly limited.
As the above-mentioned group with Si -- H bond, it is not particularly limited, can enumerate for example, hydrosilyl, above-mentioned formula
(4) the middle at least one of 3 R ' in the group shown in is group of hydrogen atom etc..
The above-mentioned hydrogen atom of intramolecular (in a molecule) of ladder type silsesquioxane (B2) or the above-mentioned base comprising Si -- H bond
Group number be not particularly limited, but preferably more than 2 (for example, 2～50), be more preferably 2～30.By above-mentioned
In the range of there is above-mentioned hydrogen atom or the above-mentioned group comprising Si-H, there is the heat resistance of the solidfied material of hardening resin composition
The tendency improving.
The above-mentioned hydrogen atom comprising in ladder type silsesquioxane (B2) or the ratio (weight basis) of above-mentioned SiH base do not have spy
Different limit, but preferably with weight conversion (H conversion) of the H (hydride) in hydrogen atom or SiH base be 0.01～0.50 weight %,
More preferably 0.08～0.28 weight %.If the content of above-mentioned hydrogen atom or above-mentioned SiH base is very few (for example, be less than with H conversion
In the case of 0.01 weight %), the solidification of hardening resin composition may be led to cannot fully to carry out.On the other hand, if
The content of above-mentioned hydrogen atom or above-mentioned SiH base excessive (in the case of for example, being converted more than 0.50 weight % with H), then may lead
The hardness causing solidfied material uprises, easily ftractures.It should be noted that above-mentioned hydrogen atom in ladder type silsesquioxane (B2) or
The content of above-mentioned SiH base for example can be passed through1H-NMR etc. is measured.
The ratio of SiH base present in ladder type silsesquioxane (B2) is not particularly limited, but goes out from the viewpoint of flexibility
Send out, for example, with respect to the whole SiH bases being present in contained compound in the hardening resin composition of the present invention, (100 rub
You are %), preferably 0～80 mole %, more preferably 0～50 mole of %.
Ladder type silsesquioxane (B2) is not particularly limited, and can also be able to be solid for liquid in normal temperature (about 25 DEG C),
Wherein, it is liquid preferably in normal temperature.More specifically, the viscosity when 25 DEG C for the ladder type silsesquioxane (B2) be preferably 100～
100000mPa s, more preferably 500～10000mPa s, more preferably 1000～8000mPa s.Viscosity is less than
During 100mPa s, the heat resistance of solidfied material may be led to reduce.On the other hand, when viscosity is more than 100000mPa s, may lead
The preparation of hardening resin composition, operation is caused to become difficult.It should be noted that viscosity when 25 DEG C for example can be utilized and ladder
The method that the viscosity of type silsesquioxane (B1) is same is measured.
Silsesquioxane (B) comprise at normal temperatures be solid silsesquioxane (B2) when, exist to corrosive gas
The tendency that corrosion resistance, obdurability (particularly resistance to anti-thread breakage) improve.
[other ladder type silsesquioxane]
Above-mentioned ladder type silsesquioxane can also comprise the ladder type silsesquioxane that such as intramolecular has aryl.As point
There is in son the aryl in the ladder type silsesquioxane of aryl, can enumerate for example：The C such as phenyl, naphthyl6-14Aryl (particularly C6-10
Aryl) etc..These aryl can also be that the substituent that the silicon atom in polysiloxane (A) has is (direct with silicon atom
The group of bonding).
In addition, as above-mentioned ladder type silsesquioxane, can also comprise except ladder type silsesquioxane (B1), ladder type sesquialter silicon
Ladder type silsesquioxane beyond oxygen alkane (B2), intramolecular have the ladder type silsesquioxane of aryl is (hereinafter also referred to " other terraced
Type silsesquioxane ").Particularly, above-mentioned other ladder type silsesquioxane preferably with ladder type silsesquioxane (B1), ladder type sesquialter
Siloxanes (B2) is applied in combination.
Above-mentioned ladder type silsesquioxane is not particularly limited, but preferably comprises and be selected from ladder type polysiloxane
(B1), ladder type polysiloxane (B2) and intramolecular have at least a kind silsesquioxane in the ladder type silsesquioxane of aryl
Alkane, more preferably comprises ladder type silsesquioxane (B1) and/or ladder type silsesquioxane (B2).
The content of the above-mentioned ladder type silsesquioxane in silsesquioxane (B) is not particularly limited, but preferably for example relatively
More than silsesquioxane (B) total amount (100 weight %) is for 50 weight %, more than more preferably 70 weight %, further preferably
More than 90 weight %.Wherein, preferably silsesquioxane (B) is only above-mentioned ladder type silsesquioxane.That is, preferred silsesquioxane
(B) it is above-mentioned ladder type silsesquioxane.By making the content of ladder type silsesquioxane in above range, resistance to SOxCorrosivity is more
Excellent.
The content of the ladder type silsesquioxane (B1) in silsesquioxane (B) is not particularly limited, but preferably for example relatively
More than silsesquioxane (B) total amount (100 weight %) is for 20 weight %, more than more preferably 40 weight %, further preferably
For more than 50 weight %, more than particularly preferably 90 weight %.As the upper limit, preferably such as 100 weight % or 95
Weight %, 80 weight %, 60 weight %.Wherein, preferably silsesquioxane (B) is only above-mentioned ladder type silsesquioxane (B1).That is,
Silsesquioxane (B) can also be above-mentioned ladder type silsesquioxane (B1).
The content of the ladder type silsesquioxane (B2) in silsesquioxane (B) is not particularly limited, but preferably for example relatively
More than silsesquioxane (B) total amount (100 weight %) is for 10 weight %, more than more preferably 20 weight %, further preferably
More than 40 weight %.As the upper limit, preferably such as 100 weight %, more preferably 80 weight %, more preferably 60 weights
Amount %, particularly preferably 50 weight %.Silsesquioxane (B) may also be only above-mentioned ladder type silsesquioxane (B2).
From the viewpoint of from easily to hardening resin composition, the number of contained SiH base is controlled by, preferably will
Silsesquioxane (B2) is applied in combination with silsesquioxane (B1).Wherein, silsesquioxane (B1) and silsesquioxane (B2)
Ratio (silsesquioxane (B1):Silsesquioxane (B2)) it is preferably 2～8:8～2, more preferably 4～6:6～4.
Above-mentioned ladder type silsesquioxane can be using known manufacture method (for example, with 3 functional silane compounds as raw material
Hydrolytic condensation method) and manufacture.
In silsesquioxane (B), the contained number-average molecular weight of silsesquioxane and/or weight average molecular weight do not have special limit
Fixed, but preferably 100～800,000, more preferably 200～100,000, more preferably 300～30,000, particularly preferably 500～
20000.During less than 100, the heat resistance of solidfied material may be led to reduce, during more than 800,000, silsesquioxane (B) phase may be led to
Compatibility for other compositions reduces.It should be noted that silsesquioxane (B) can also be have above range various
The mixture of the silsesquioxane of molecular weight.
The intramolecular aliphatic of contained silsesquioxane (particularly ladder type silsesquioxane) in silsesquioxane (B)
The content (weight basis, vinyl conversion) of carbon-to-carbon double bond is not particularly limited, but from being readily available flexibility and excellent strength
Solidfied material from the viewpoint of, such as (such as 1.0～15.0 weight %) below preferably 15.0 weight %, more preferably 1.2
～12.0 weight %.The content of intramolecular aliphatic carbon-to-carbon double bond can be by for example1H-NMR is measured.
The intramolecular SiH base of contained silsesquioxane (particularly ladder type silsesquioxane) in silsesquioxane (B)
The content weight of the H (hydride) in SiH base (conversion) be not particularly limited, but from being readily available flexibility and excellent strength
Solidfied material from the viewpoint of, such as (such as 0.01～0.50 weight %) below preferably 0.50 weight %, more preferably
0.03～0.28 weight %.Above-mentioned SiH base content can be by for example1H-NMR etc. is measured.
In silsesquioxane (B), contained silsesquioxane (particularly ladder type silsesquioxane) is not particularly limited, but
From with the compatibility of organosiloxane (A) from the viewpoint of, preferably comprise methyl and vinyl and the ratio of methyl and vinyl
(mol ratio, methyl:Vinyl) 5:5～9.5:The silsesquioxane of 0.5 scope, more preferably 5.5:4.5～9:1 model
Enclose.Above-mentioned methyl, the content of vinyl can be passed through for example1H-NMR is measured.
Silsesquioxane (B) is not particularly limited, preferably such as water white transparency.Specifically, can preferably by ultraviolet
See spectrophotometric determination 400nm light transmittance be more than 90%.
Silsesquioxane (B) is not particularly limited, for example can be by mixing above-mentioned ladder type silsesquioxane etc. to homogeneous
And manufacture.
The content (use level) of the silsesquioxane (B) in the hardening resin composition of the present invention is not particularly limited,
But the total amount (100 weight %) preferably with respect to hardening resin composition is 5～45 weight %, more preferably 7～40 weights
Amount %, more preferably 10～35 weight %.When content is less than 5 weight %, possibly cannot fully obtain to SOxEtc. corrosivity
The gas barrier property of gas.On the other hand, resistance to anti-thread breakage reduction, the Wu Fachong of solidfied material may when content is more than 45 weight %, be led to
Separately win to obtain heat resistance.
The content of the silsesquioxane (B) in the hardening resin composition of the present invention is not particularly limited, but preference
As the total amount (100 weight portion) with respect to polysiloxane (A) and silsesquioxane (B) is 1～50 weight portion, is more preferably
5～40 weight portions, more preferably 8～30 weight portions.By making content in above range, corrosion-resistant to corrosive gas
Property (particularly resistance to SOxCorrosivity) excellent.
Polysiloxane (A) in the hardening resin composition of the present invention and total content of silsesquioxane (B)
It is not particularly limited, but be 60.000～100 weights preferably for example with respect to the total amount (100 weight %) of hardening resin composition
Amount %, more preferably 70.000～99.000 weight %.By making the total of polysiloxane (A) and silsesquioxane (B)
Content is in above range, corrosion resistance (the particularly resistance to SO to corrosive gasxCorrosivity) excellent.Particularly, by for 99
Below weight %, heat resistance and more excellent to the corrosion resistance of corrosive gas.
[isocyanurate compound (C)]
The hardening resin composition of the present invention comprises isocyanurate compound (C).By making the curability of the present invention
Resin combination comprises isocyanurate compound (C), particularly, exist cured and formed solidfied material to corrosive gas
Barrier improve and with respect to adherend adaptation improve tendency.
Isocyanurate compound (C) preferably comprises the isocyanurate compound shown in formula (1).In particular it is preferred that it is different
Cyanurate compound (C) is only the isocyanurate compound shown in formula (1).
[chemical formula 7]
In above-mentioned formula (1), Rx、Ry、RzIdentical or different, represent shown in the group shown in above-mentioned formula (2) or above-mentioned formula (3)
Group.Wherein, the R in preferably above-mentioned formula (1)x、Ry、RzIn any one is above (preferably 1 or 2, more preferably 1
Individual) it is the group shown in above-mentioned formula (3).
[chemical formula 8]
[chemical formula 9]
In above-mentioned formula (2) and above-mentioned formula (3), R1、R2Identical or different, represent the straight chain of hydrogen atom or carbon number 1～8
Shape or the alkyl of branched.Straight-chain as carbon number 1～8 or the alkyl of branched, can enumerate for example：Methyl, ethyl,
Propyl group, isopropyl, butyl, isobutyl group, sec-butyl, amyl group, hexyl, heptyl, octyl group, ethylhexyl etc..In abovementioned alkyl, preferably
The straight-chain of the carbon numbers such as methyl, ethyl, propyl group, isopropyl 1～3 or the alkyl of branched.Particularly preferably above-mentioned formula (2) and
R in above-mentioned formula (3)1、R2It is respectively hydrogen atom.
As the isocyanurate compound comprising in isocyanurate compound (C), it is not particularly limited, example can be enumerated
As：Isocyanuric acid monoallyl dimethyl esters, isocyanuric acid diallyl monomethyl ester, triallyl isocyanurate, isocyanide urea
Sour monoallyl 2-glycidyl base ester, isocyanuric acid diallyl list glycidyl esters, triglycidyl isocyanurate,
Isocyanuric acid monomethyl 2-glycidyl base ester, isocyanuric acid dimethyl list glycidyl esters, isocyanuric acid 1- pi-allyl -3,
5- double (2- methylglycidyl) ester, isocyanuric acid 1- (2- methylpropenyl) -3,5- 2-glycidyl base ester, isocyanuric acid 1-
(2- methylpropenyl) -3,5- double (2- methylglycidyl) ester, isocyanuric acid 1,3- diallyl -5- (2- methyl epoxy third
Base) ester, double (2- the methylpropenyl) -5- glycidyl esters of isocyanuric acid 1,3-, double (the 2- metering system of isocyanuric acid 1,3-
Base) -5- (2- methylglycidyl) ester, isocyanuric acid three (2- methylpropenyl) ester etc..Wherein, preferred isocyanuric acid monoene third
Base 2-glycidyl base ester.It should be noted that the isocyanurate compound in isocyanurate compound (C) can be independent
It is applied in combination using a kind or by two or more.
From the viewpoint of raising with the compatibility of other compositions, as described later, in advance, isocyanuric acid can be esterified
Compound (C) mix with silane coupler after again with other components matching.
The content of isocyanurate compound (C) is not particularly limited, but preferably with respect to hardening resin composition
Total amount (100 weight %) is 0.01～10 weight %, more preferably 0.05～5 weight %, more preferably 0.1～3 weight
Amount %.The content of above-mentioned isocyanurate compound be less than 0.01 weight % when, may lead to the barrier to corrosive gas,
Reduce with respect to the adaptation of adherend.On the other hand, when the content of above-mentioned isocyanurate compound is more than 10 weight %, can
Can lead to have solid to separate out in hardening resin composition or solidfied material occurs gonorrhoea.
[silane coupler (D)]
The hardening resin composition of the present invention can also comprise silane coupler (D).By comprising silane coupler
(D), there is the tendency improving with respect to the adaptation of adherend.
Because silane coupler (D) is good with the compatibility of above-mentioned silsesquioxane (B), isocyanurate compound (C) etc.
Good, thus, for example in order to improve the compatibility that isocyanurate compound is with respect to other compositions, being pre-formed isocyanuric acid
When on the basis of the composition of ester compounds (C) and silane coupler (D) again with other components matching, it is readily available homogeneous consolidating
The property changed resin combination.
As silane coupler (D), can be not particularly limited, example can be enumerated using known or usual silane coupler
As：3- glycidoxypropyltrime,hoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- epoxy third oxygen
Base hydroxypropyl methyl diethoxy silane, 3- glycidoxypropyl group triethoxysilane etc. contain the silane coupler of epoxy radicals；N-
2- (amino-ethyl) -3- amino propyl methyl dimethoxysilane, N-2- (amino-ethyl) -3- aminopropyl trimethoxy silicon
Alkane, N-2- (amino-ethyl)-APTES, 3- TSL 8330,3- aminopropyl three
Ethoxysilane, 3- triethoxysilyl-N- (1,3- dimethyl-fourth fork) propyl group amine, N- phenyl -3- aminopropyl front three
TMOS, the hydrochloride of N- (vinyl benzyl) -2- amino-ethyl -3- TSL 8330, N- (beta-amino second
Base) silane coupler containing amino such as-gamma-amino hydroxypropyl methyl diethoxy silane；Tetramethoxy-silicane, tetraethoxy-silicane
Alkane, MTES, dimethyldiethoxysilane, VTES, vinyltrimethoxy silane,
Vinyl three (methoxy-ethoxy-silane), phenyltrimethoxysila,e, dimethoxydiphenylsilane, vinyl triacetyl oxygen
Base silane, γ-(methyl) acryloxypropyl triethoxysilane, γ-(methyl) acryloxypropyl trimethoxy silicon
Alkane, γ-(methyl) acryloxypropyl dimethoxysilane, γ-(methyl) acryloxypropyl diethoxy
Base silane, sulfydryl propylidene trimethoxy silane, sulfydryl propylidene triethoxysilane etc..Wherein, preferably contain the silicon of epoxy radicals
Alkane coupling agent (particularly 3- glycidoxypropyltrime,hoxysilane).It should be noted that silane coupler (D) can be single
Solely it is applied in combination using a kind or by two or more.
The content of silane coupler (D) is not particularly limited, but the total amount preferably with respect to hardening resin composition
(100 weight %) is 0.01～15 weight %, more preferably 0.1～10 weight %, more preferably 0.5～5 weight %.On
When the content stating silane coupler is less than 0.01 weight %, may lead to reduce with respect to the adaptation of adherend, particularly exist
Compatible with isocyanurate compound (C) and when using, possibly cannot sufficiently be solidified.On the other hand, silane coupler
(D), when content is more than 15 weight %, may lead to solidify becomes insufficient, solidfied material toughness, heat resistance, barrier fall
Low.
[carboxylate (E) of rare earth]
The carboxylate (E) of rare earth is comprised in the hardening resin composition of the present invention.By comprising rare earth gold
Belong to the carboxylate (E) of atom, there is resistance to H2S corrosivity and the tendency of heat resistance raising.Institute in the carboxylate of rare earth
The rare earth containing can be a kind, can also be two or more.
In this manual, also the carboxylate of rare earth is referred to as rare earth carboxylate.
Rare earth metal in the carboxylate of rare earth comprising in carboxylate (E) as rare earth is former
Son, can enumerate for example：Yttrium, cerium, lanthanum, praseodymium, neodymium etc..As the carboxylate in the carboxylate of above-mentioned rare earth, preferably
The such as carboxylate of carboxylic acid of carbon number 1～20 (preferably 2～12, more preferably 4～10, more preferably 5～7),
The more preferably caproate such as 2 ethyl hexanoic acid salt.Wherein, as the carboxylate of above-mentioned rare earth, optimization acid's yttrium, carboxylic
Sour cerium, carboxylic acid lanthanum, carboxylic acid praseodymium, carboxylic acid neodymium (particularly the carboxylic acid yttrium of carbon number 1～20, the cerium carboxylate of carbon number 1～20,
The carboxylic acid lanthanum of carbon number 1～20, the carboxylic acid praseodymium of carbon number 1～20, the carboxylic acid neodymium of carbon number 1～20, more preferably 2- second
Base caproic acid yttrium, 2 ethyl hexanoic acid cerium, 2 ethyl hexanoic acid lanthanum, 2 ethyl hexanoic acid praseodymium, 2 ethyl hexanoic acid neodymium).
The carboxylate of the rare earth in the carboxylate (E) of rare earth can be used alone a kind or incites somebody to action
Two or more is applied in combination.
The carboxylate (E) of rare earth is preferably for example：Comprise the carboxylate of rare earth of cerium (for example,
The mixture of the carboxylate of at least two or more rare earth in cerium carboxylate, carboxylic acid lanthanum, carboxylic acid praseodymium and carboxylic acid neodymium
(cerium carboxylate, mixture of carboxylic acid lanthanum, carboxylic acid praseodymium and carboxylic acid neodymium etc.) or single cerium carboxylate (single compound) etc.) or comprise
The carboxylate (for example, single carboxylic acid yttrium etc.) of the rare earth of carboxylic acid yttrium, the rare earth metal more preferably comprising cerium is former
The 2 ethyl hexanoic acid salt of son is (for example, selected from 2 ethyl hexanoic acid cerium, 2 ethyl hexanoic acid lanthanum, 2 ethyl hexanoic acid praseodymium and 2 ethyl hexanoic acid
Mixture (2 ethyl hexanoic acid cerium, the 2 ethyl hexanoic acid of the 2 ethyl hexanoic acid salt of at least two or more rare earth in neodymium
Mixture of lanthanum, 2 ethyl hexanoic acid praseodymium and 2 ethyl hexanoic acid neodymium etc.) or single 2 ethyl hexanoic acid cerium (single compound) etc.),
Or 2 ethyl hexanoic acid yttrium.
Carboxylate (E) as rare earth, it is possible to use such as trade name " OCTOPE R " (Hope
Chemical Co. Ltd. system) etc. commercially available product.
The content of the rare earth in the hardening resin composition of the present invention is not particularly limited, but preferably for example
It is 5ppm less than 5000ppm, more preferably more than 7ppm with respect to hardening resin composition total amount (100 weight %)
And less than 1000ppm, more preferably 10ppm less than 300ppm.When the content of rare earth is less than 5ppm,
The effect of the carboxylate (E) of rare earth cannot be given full play of, may lead to H2The barrier of S gas reduces or resistance to
Hot reduction.On the other hand, when being more than 5000ppm, the transmitance of solidfied material may be led to reduce.
The content of the above-mentioned rare earth in hardening resin composition can utilize aftermentioned evaluation (rare earth metal is former
Sub- content (ppm)) described in method be measured.
The content of the rare earth in the hardening resin composition of the present invention is not particularly limited, but preferably for example
With respect to polysiloxane (A) and silsesquioxane (B) total content (100 weight %) be 5ppm less than
5000ppm, more preferably 7ppm are less than 1000ppm, more preferably 10ppm less than 300ppm.Pass through
The content making rare earth in above range, heat resistance and corrosion resistance (the particularly resistance to H to corrosive gas2S
Corrosivity) more excellent.
The content of the carboxylate (E) of rare earth is not particularly limited, but preferably for example with respect to curable resin
Total composition (100 weight %) is 0.008～1.000 weight %, more preferably 0.010～0.500 weight %, excellent further
Elect 0.015～0.400 weight % as.Particularly, the content by making rare earth in above range and makes rare earth metal
The content of the carboxylate of atom is in above range, heat resistance, more excellent to the corrosion resistance of corrosive gas.
[hydrosilylation catalysts]
The hardening resin composition of the present invention can comprise hydrosilylation catalysts further.By making the solidification of the present invention
Property resin combination comprises hydrosilylation catalysts, and curing reaction (silicon hydrogenation) can be made effectively to carry out.As above-mentioned silicon hydrogen
Change catalyst, can enumerate：The known silicon hydrogenation catalyst such as platinum group catalyst, rhodium series catalysts, palladium series catalyst.Tool
Body can be enumerated：Platinum micro mist, platinum black, the fine silica powder being loaded with platinum, the activated carbon being loaded with platinum, chloroplatinic acid, chloroplatinic acid with
The carbonyl complexes of platinum such as the complex compound of alcohol, aldehyde, ketone etc., the alkene complex of platinum, platinum-carbonyl ethylene ylmethyl complex compound, platinum-
The platinum vinyl methyl siloxane such as divinyl tetramethyl disiloxane complex compound, platinum-cyclovinylmethylsiloxane complex compound
Replace platinum former in the platinum group catalysts such as complex compound, platinum-phosphine complex compound, platinum-phosphite ester complex compound and above-mentioned platinum group catalyst
Son and the palladium series catalyst containing palladium atom or rhodium atom or rhodium series catalysts.It should be noted that above-mentioned hydrosilylation catalysts
Can be used alone a kind, or two or more is applied in combination.
The content of the above-mentioned hydrosilylation catalysts in the hardening resin composition of the present invention is not particularly limited, but preferably
For for example make platinum in hydrosilylation catalysts, palladium or rhodium with weight basis the amount in the range of 0.01～1,000ppm, enter one
Step preferably make platinum in hydrosilylation catalysts, palladium or rhodium with weight basis the amount in the range of 0.1～500ppm.Silicon hydrogenates
When the content of catalyst is in such scope, it is not result in that crosslinking rate significantly slows down, solidfied material occurs the problems such as colour
Hidden danger is few, therefore preferably.
[silicon hydrogenation inhibitor]
In order to adjust the speed of curing reaction (silicon hydrogenation), can also wrap in the hardening resin composition of the present invention
Silyl hydride reaction suppressor.As above-mentioned silicon hydrogenation inhibitor, can enumerate for example：3- methyl isophthalic acid-butine -3- alcohol, 3,
The alkynes alcohol such as 5- dimethyl -1- hexin -3- alcohol, phenylbutynol；3- methyl-pirylene, 3,5- dimethyl -3- hexene -
The yne compounds such as 1- alkynes；Thiazole, benzothiazole, BTA etc..Above-mentioned silicon hydrogenation inhibitor can be used alone 1
Kind, or two or more is applied in combination.As the content of above-mentioned silicon hydrogenation inhibitor, because of hardening resin composition
Cross linking conditions and different, but in practicality, as the content in hardening resin composition, preferably in 0.00001～5 weight %
In the range of.
[other silicone compounds]
In the hardening resin composition of the present invention, as other silicone compounds, molecule can also be comprised further
Interior (in a molecule) has the annular siloxane of more than 2 aliphatic carbon-to-carbon double bonds.In addition, the curable resin group of the present invention
In compound, as other silicone compounds it is also possible to comprise intramolecular (in a molecule) further there are more than 2 SiH bases
Annular siloxane.Above-mentioned annular siloxane can be used alone a kind or is applied in combination two or more.The solidification of the present invention
The content (use level) of the annular siloxane in property resin combination is not particularly limited, but preferably with respect to curable resin group
The total amount (100 weight %) of compound is 0.01～30 weight %, more preferably 0.1～20 weight %, more preferably 0.5～
10 weight %.
[other silane compound]
Other silane compounds can also be comprised in the hardening resin composition of the present invention and (for example, there is hydrogenation first silicon
The compound of alkyl).As above-mentioned other silane compound, can enumerate for example：Methyl (three dimethylsilyl bis) silane, four
(dimethylsilyl bis) silane, 1,1,3,3- tetramethyl disiloxane, 1,1,3,3,5,5- hexam ethylcyclotrisiloxane, 1,1,1,3,
5,5,5- heptamethyltrisiloxane, 1,1,3,3,5,5,7,7- octamethylcyclotetrasiloxane, 1,1,1,3,5,5,7,7,7- nine methyl
Tetrasiloxane, 1,1,3,3,5,5,7,7,9,9- decamethyl five siloxanes, 1,1,1,3,5,5,7,7,9,9,9- ten monomethyl five
Siloxanes etc. has straight-chain or branched siloxanes of SiH base etc..It should be noted that above-mentioned silane compound can be independent
It is applied in combination using a kind or by two or more.The content of above-mentioned silane compound is not particularly limited, but preferably with respect to solid
The total amount (100 weight %) of the property changed resin combination is 0～5 weight %, more preferably 0～1.5 weight %.
[solvent]
The hardening resin composition of the present invention can also comprise solvent.As above-mentioned solvent, can enumerate for example：Toluene,
The existing known solvent such as hexane, isopropanol, methyl iso-butyl ketone (MIBK), cyclopentanone, propylene glycol monomethyl ether.Above-mentioned solvent
Can be used alone a kind or two or more is applied in combination.
[additive]
In the hardening resin composition of the present invention, as other any conditions it is also possible to comprise to settle silica, wet
Formula silica, aerosil, fumed silica, titanium oxide, aluminum oxide, glass, quartz, manosil AS, iron oxide, oxygen
Change the inorganic fillers such as zinc, calcium carbonate, carbon black, carborundum, silicon nitride, boron nitride, these fillers are utilized halogenated organic silicon
The organo-silicon compound such as alkane, organoalkoxysilane, organosilazanes processed obtained from inorganic filler；Organosilicon tree
The organic resin micro mist such as fat, epoxy resin, fluororesin；The fillers such as the conductive metal powder such as silver, copper, stabilizer are (anti-oxidant
Agent, ultra-violet absorber, resistance to light stabilizer, heat stabilizer etc.), fire retardant (phosphorus flame retardant, halogen-system fire retardant, inorganic system
Fire retardant etc.), flame retardant, supporting material (other fillers etc.), nucleator, coupling agent, lubricant, wax, plasticizer, the demoulding
Agent, impact resistance modifying agent, form and aspect modifying agent, fluidity amendment, colouring agent (dyestuff, pigment etc.), dispersant, defoamer, de-
The usual additive such as infusion, antiseptic, preservative, viscosity modifier, tackifier.These additives can be used alone or
Two or more is applied in combination.
[hardening resin composition]
The hardening resin composition of the present invention is not particularly limited, but preferably makes to be present in hardening resin composition
In hydrosilyl in contained compound sum with respect to being present in contained chemical combination in hardening resin composition
The ratio (also for mol ratio) of the sum of the aliphatic carbon-to-carbon double bond with silicon atom bonding in thing is less than 1 (preferably more than 0.20
And less than 1.00, more preferably 0.50～0.98, more preferably 0.70～0.95) composition (cooperation composition).By making
The ratio of hydrosilyl and aliphatic carbon-to-carbon double bond, in above range, can make the hardness of solidfied material reduce, and therefore there is system
The tendency that the load of cable diminishes, improves with respect to the reliability of thermal shock is put on when becoming LED encapsulant.
It should be noted that in this manual, refer on silicon atom with the aliphatic carbon-to-carbon double bond of silicon atom bonding
Contained aliphatic carbon-to-carbon double bond in the substituent being had.In addition, including with the aliphatic carbon-to-carbon double bond of silicon atom bonding
Aliphatic carbon-to-carbon double bond beyond the end of the substituent having on silicon atom and end.
The hardening resin composition of the present invention is not particularly limited, can be by for example entering above-mentioned each composition at room temperature
Row stirring/mixing is preparing.It should be noted that for the hardening resin composition of the present invention, can be directly to use
The form of the composition of the single-component system of the mixture being pre-mixed by each composition is using it is also possible to for example will be each
Multicomponent system (for example, the bi-component body that two or more composition pre-saving is used in mixed way with given ratio before the use
System) composition form use.
The hardening resin composition of the present invention is not particularly limited, but is liquid preferably in (about 25 DEG C) of normal temperature.More
For body, for the hardening resin composition of the present invention, as the viscosity when 25 DEG C, preferably 300～
20000mPa s, more preferably 500～10000mPa s, more preferably 1000～8000mPa s.Viscosity is less than
During 300mPa s, the heat resistance of solidfied material may be led to reduce.On the other hand, when viscosity is more than 20000mPa s, may lead
The preparation of hardening resin composition, operation is caused to become in difficult, solidfied material easily entrapped air pockets.It should be noted that curability
The viscosity of resin combination for example can be utilized the method same with the viscosity of above-mentioned ladder type silsesquioxane (B1) to be measured.
[solidfied material]
Solidified by making the cured reaction of the hardening resin composition of the present invention (silicon hydrogenation), can be solidified
Thing (hereinafter also referred to " solidfied material of the present invention ").The condition of curing reaction is not particularly limited, can be from existing known bar
Suitably select in part, but from the viewpoint of such as reaction speed, temperature (solidification temperature) is preferably 25～180 DEG C (more preferably
For 60 DEG C～150 DEG C), the time (hardening time) is preferably 5～720 minutes.The heat resistance of the solidfied material of the present invention, the transparency,
The various physical properties excellent such as flexibility, and resistance to anti-thread breakage, to reflux-resisting welded property such as the adaptations of packaging part in Reflow Soldering operation
Excellent, also excellent to the barrier of corrosive gas.
The aging front A hardness of the solidfied material of the present invention is not particularly limited, preferably such as less than 70, more preferably 30～
69th, it is more preferably 40～68, be particularly preferably 45 less than 60.By making aging front A hardness in above range,
Even if there is (for example after 200 DEG C of heating 500 hours) to be after the heating not easy to the tendency leading to hardness to raise.Particularly, lead to
Cross and make A hardness be less than 60, there is the tendency that the hardness after can suppressing further to heat rises.Above-mentioned aging front A hardness is concrete
Refer to using in aftermentioned (evaluation) " (aging front A hardness, aging after A hardness) " described in method and measure
Value.
Above-mentioned aging front A hardness can be contained whole in the hardening resin composition before solidification according to being for example present in
The aliphatic carbon-to-carbon double bond with silicon atom bonding in compound is contained complete in hardening resin composition with respect to being present in
The ratio of the hydrosilyl in portion's compound, polysiloxane (A), the vinyl weight rate of silsesquioxane (B) or
Si-H weight rate, use level of silsesquioxane (B) etc. are adjusted.
The solidfied material of the present invention aging after the A hardness of (in 200 DEG C after aging 500 hours) be not particularly limited, preferably
Such as less than 90, more preferably 50～89, more preferably 60～85, particularly preferably 65～75.By make aging after A
Hardness is in above range, heat resistance, of excellent in reliability with respect to thermal shock.Particularly, by below 85, heat resistance and phase
Reliability for thermal shock is more excellent.Above-mentioned aging after A hardness refer specifically to using " aging in aftermentioned (evaluation)
Front A hardness, aging after A hardness) " described in method and the value that measures.
Above-mentioned aging after A hardness can be contained complete in the hardening resin composition before solidification according to for example, being present in
The aliphatic carbon-to-carbon double bond with silicon atom bonding in portion's compound is contained in hardening resin composition with respect to being present in
Contained vinyl in the ratio of hydrosilyl in whole compounds, polysiloxane (A), silsesquioxane (B)
Weight rate, SiH weight rate, hydrosilation catalyst dosage etc. are adjusted.
[encapsulant and semiconductor device]
The encapsulant of the present invention is the hardening resin composition that comprises the present invention encapsulant as neccessary composition.
Using encapsulant (solidfied material) obtained from the encapsulant (for example, making the encapsulant of the present invention solidify) of the present invention, resistance to
The various physical properties excellent such as hot, transparent, flexibility, and reflux-resisting welded property, excellent to the barrier of corrosive gas.Cause
This, the encapsulant of the present invention is preferably as the encapsulant of the semiconductor element in semiconductor device, particularly light is partly led
Encapsulant of optical semiconductor in the body device optical semiconductor of high brightness, short wavelength (particularly) etc. uses.Logical
Cross and using the encapsulant of the present invention, semiconductor element (particularly optical semiconductor) sealed, can get durability and
The semiconductor device (particularly optical semiconductor device) of excellent quality.
Embodiment
Hereinafter, in conjunction with the embodiments and comparative example is described in more detail to the present invention, but the present invention is completely unrestricted
In these embodiments.
Product and product1H-NMR analysis can be carried out using JEOL ECA500 (500MHz).
In addition, the mensure of the number-average molecular weight of product and product and weight average molecular weight can be based on Alliance HPLC
System 2695 (Waters system), Refractive Index Detector 2414 (Waters system), chromatographic column:Tskgel
GMHHR- M × 2 (eastern Cao's (strain) system), guard column:Tskgel guard column HHRL (eastern Cao's (strain) system), column oven:
COLUMN HEATER U-620 (Sugai system), solvent:THF, condition determination:40 DEG C, polystyrene conversion and carry out.
[polysiloxane (A)]
As polysiloxane (A), employ following product.
GD-1012A：Changxing chemical industrial company system, contents of ethylene 1.33 weight %, phenyl content 0 weight %, SiH
Base (hydride conversion) content 0 weight %, number-average molecular weight 5108, weight average molecular weight 23385
GD-1012B：Changxing chemical industrial company system, contents of ethylene 1.65 weight %, phenyl content 0 weight %, SiH
Base (hydride conversion) content 0.19 weight %, number-average molecular weight 4563, weight average molecular weight 21873
KER-2500A：SHIN-ETSU HANTOTAI's chemical industry (strain) system, contents of ethylene 1.53 weight %, phenyl content 0 weight %, SiH
Base (hydride conversion) content 0.03 weight %, number-average molecular weight 4453, weight average molecular weight 19355
KER-2500B：SHIN-ETSU HANTOTAI's chemical industry (strain) system, contents of ethylene 1.08 weight %, phenyl content 0 weight %, SiH
Base (hydride conversion) content 0.13 weight %, number-average molecular weight 4636, weight average molecular weight 18814
[synthesis of silsesquioxane (B)]
<Synthesis example 1>
Charging MTES (SHIN-ETSU HANTOTAI's chemical industry (strain) system) 30.06g, vinyl three second in reaction vessel
TMOS (Tokyo chemical conversion industry (strain) system) 21.39g and methyl iso-butyl ketone (MIBK) (MIBK) 17.69g, and the mixture by them
It is cooled to 10 DEG C.The hydrochloric acid 0.48g spending 1 hour dropping water 281 mmoles (5.06g) and 5N in said mixture is (with chlorination
Hydrogen is calculated as 2.4 mmoles).After dropping, their mixture is kept 1 hour in 10 DEG C.Thereafter, add MIBK 80.0g to dilute
Reaction solution.
Then, the temperature of reaction vessel is warming up to 70 DEG C, adds water 703 mmoles in the moment reaching 70 DEG C
(12.64g), nitrogen has carried out polycondensation reaction in 12 hours.
Then, add HMDO 15.0g in the reaction solution after above-mentioned polycondensation reaction, carry out in 70 DEG C
3 hours silylation reactive.Thereafter, cooled reaction solution, carries out washing until subnatant reaches neutrality, thereafter, in fractionation
Layer liquid.Then, solvent is distilled off from above-mentioned upper liquid under conditions of 1mmHg, 60 DEG C, is produced with water white solid-like
The form of thing has obtained the ladder type silsesquioxane 22.0g that end has trimethyl silyl.
The weight average molecular weight (Mw) of above-mentioned ladder type silsesquioxane is 5000, the content of the vinyl of every 1 molecule (averagely contains
Amount) for 11.68 weight %, methyl/vinyl (mol ratio) be 60/40.
Above-mentioned ladder type silsesquioxane1H-NMR spectrum is as described below.
1H-NMR(JEOL ECA500(500MHz、CDCl3))δ:0-0.3ppm(br)、5.8-6.1ppm(br)
<Synthesis example 2>
Charging MTES (SHIN-ETSU HANTOTAI's chemical industry (strain) system) 34.07g, phenyl three ethoxy in reaction vessel
Base silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system) 11.49g and methyl iso-butyl ketone (MIBK) (MIBK) 17.69g, and will be cold for their mixture
But to 10 DEG C.The hydrochloric acid 0.48g spending 1 hour dropping water 240 mmoles (4.33g) and 5N in said mixture is (with hydrogen chloride
It is calculated as 2.4 mmoles).After dropping, their mixture is kept 1 hour in 10 DEG C.Thereafter, add MIBK 80.0g anti-to dilute
Answer solution.
Then, the temperature of reaction vessel is warming up to 70 DEG C, adds water 606 mmoles in the moment reaching 70 DEG C
(10.91g), nitrogen has carried out polycondensation reaction in 9 hours.Then, add VTES (Tokyo chemical conversion industry
(strain) makes) 6.25g, and carried out reaction in 3 hours.
Then, add HMDO 15.0g in the reaction solution after above-mentioned polycondensation reaction, carry out in 70 DEG C
3 hours silylation reactive.Thereafter, cooled reaction solution, carries out washing until subnatant reaches neutrality, thereafter, in fractionation
Layer liquid.Then, solvent is distilled off from above-mentioned upper liquid under conditions of 1mmHg, 60 DEG C, with water white liquid product
Form obtained end there is the ladder type silsesquioxane of vinyl and trimethyl silyl (being equivalent to above-mentioned ladder type times
Half siloxanes (B1)).
The weight average molecular weight (Mw) of above-mentioned ladder type silsesquioxane is 3400, the content of the vinyl of every 1 molecule (averagely contains
Amount) for 3.96 weight %, phenyl/methyl/vinyl (mol ratio) be 17/68/15.
Above-mentioned ladder type silsesquioxane1H-NMR spectrum is as described below.
1H-NMR(JEOL ECA500(500MHz、CDCl3))δ:-0.3-0.3ppm(br)、5.7-6.2ppm(br)、7.1-
7.7ppm(br)
<Synthesis example 3>
Charging MTES (SHIN-ETSU HANTOTAI's chemical industry (strain) system) 31.06g, phenyl three ethoxy in reaction vessel
Base silane (SHIN-ETSU HANTOTAI's chemical industry (strain) system) 2.38g and methyl iso-butyl ketone (MIBK) (MIBK) 93.00g, and will be cold for their mixture
But to 10 DEG C.The hydrochloric acid 0.24g spending 1 hour dropping water 240 mmoles (4.33g) and 5N in said mixture is (with hydrogen chloride
It is calculated as 1.2 mmoles).After dropping, their mixture is kept 1 hour in 10 DEG C.
Then, the temperature of reaction vessel is warming up to 50 DEG C, adds water 120 mmoles (2.16g) in the moment reaching 50 DEG C,
Carried out polycondensation reaction in 4 hours in nitrogen.Then, add VTES (Tokyo chemical conversion industry (strain) system)
11.18g, and carried out reaction in 4 hours.
Then, add HMDO 19.5g in the reaction solution after above-mentioned polycondensation reaction, carry out in 50 DEG C
1 hour silylation reactive.Thereafter, cooled reaction solution, carries out washing until subnatant reaches neutrality, thereafter, in fractionation
Layer liquid.Then, solvent is distilled off from above-mentioned upper liquid under conditions of 1mmHg, 60 DEG C, with water white liquid product
Form obtained end there is the ladder type silsesquioxane of vinyl and trimethyl silyl (being equivalent to above-mentioned ladder type times
Half siloxanes (B1)).
The number-average molecular weight (Mn) of above-mentioned ladder type silsesquioxane is 879, weight average molecular weight (Mw) is 1116.
<Synthesis example 4>
Ladder type silsesquioxane 12g, 1,1,3,3- tetramethyl two silicon obtaining in synthesis example 2 is fed in reaction vessel
The vinylcyclosiloxanes of oxygen alkane (Tokyo chemical conversion industry (strain) system) 24g and 2.0% platinum-cyclic vinyl siloxane complex compound are molten
Liquid (and Wako Pure Chemical Industries (strain) system) 10 μ l.Then, heat 8 hours in 70 DEG C, so that reaction is completed.Thereafter, using rotary evaporation
Instrument is concentrated, and is then reduced pressure 3 hours in 0.2Torr using vavuum pump, the end having obtained liquid Product Form has containing SiH
The ladder type silsesquioxane (with respect to above-mentioned ladder type silsesquioxane (B2)) of group and trimethyl silyl.
The weight average molecular weight (Mw) of above-mentioned ladder type silsesquioxane is 3700, the content of the SiH base of every 1 molecule (averagely contains
Amount) 0.11 weight % is scaled with the weight of the H (hydride) in SiH base.
Above-mentioned ladder type silsesquioxane1H-NMR spectrum is as described below.
1H-NMR(JEOL ECA500(500MHz、CDCl3))δ:-0.3-0.3ppm(br)、4.7ppm(s)、7.1-
7.7ppm(br)
[isocyanurate compound (C)]
As isocyanurate compound (C), employ following product.
Isocyanuric acid monoallyl 2-glycidyl base ester：Four countries' chemical conversion industry (strain) is made
[silane coupler (D)]
As silane coupler (D), employ following product.
3- glycidoxypropyltrimewasxysilane：Toray Dow Corning (strain) makes
[carboxylate (E) of rare earth]
Carboxylate (E) as rare earth, employs following product.
OCTOPE R：(Hope Chemical (strain) makes 2 ethyl hexanoic acid rare earth metal salt；As rare earths, comprise cerium,
Lanthanum, neodymium, praseodymium.As solvent, comprise 2 ethyl hexanoic acid:8wt%, mineral spirits 68%)
2 ethyl hexanoic acid yttrium (and Wako Pure Chemical Industries (strain) system；2 ethyl hexanoic acid yttrium (III), 49% toluene solution)
2 ethyl hexanoic acid cerium (and Wako Pure Chemical Industries (strain) system；2 ethyl hexanoic acid cerium (III), 49%2- ethylhexanoic acid solution)
<Embodiment and comparative example>
Implement embodiment 1～9 and comparative example 1～4 according to following orders.
After isocyanurate compound (C) and silane coupler (D) being mixed with given weight rate according to table 1, mix
Close carboxylate (E) and the silsesquioxane (B) of rare earth, stir 2 hours in 70 DEG C.Thereafter, it is cooled to room temperature, mixing
Polysiloxane (A), and be stirred at room temperature 10 minutes, obtain hardening resin composition.
[table 1]
[evaluation]
For the sample obtaining in embodiment and comparative example, commented using following assay methods or evaluation method
Valency.
(rare earth content (ppm))
For with respect to the hardening resin composition (100 weight %) obtaining in embodiment 1～9, comparative example 1～4
The content of rare earth, the quantitative analysis of contained rare earth in the sample by using ICP-MS and carry out
Measure.
Device：Trade name " Agilent7500cs " (Yokogawa Analytical Systems system)
By the use of solvent, the solution that sample dilution is formulated will be detected liquid as ICP-MS mensure.Calibration curve is marked
Quasi- liquid is to add the atom extinction titer of each element suitably liquid of dilution to use in above-mentioned detection liquid.
(SiH/Vinyl (mol ratio))
Using1H-NMR, determine under the following conditions embodiment 1～9, obtain in comparative example 1～4 be present in solidification
Property resin combination in hydrosilyl in contained compound molal quantity with respect to being present in curable resin combination
The ratio (mol ratio) of 1 mole of the aliphatic carbon-to-carbon double bond with silicon atom bonding in contained compound in thing.
It should be noted that the ratio (weight basis) of hydrosilyl passes through the weight of the H (hydride) in SiH base
Convert (H conversion) and obtain.
Condition determination
Device：JEOL ECA500 (500MHz, solvent:CDCl3)δ:5.7-6.2ppm、δ:4.6-4.8ppm
(aging front A hardness, aging after A hardness)
Respectively the hardening resin composition obtaining in embodiment 1～9, comparative example 1～4 is injected the aluminium cup of diameter 6cm
In, heat 1 hour and then in 150 DEG C of heating 5 hours in 100 DEG C.Take out gained solidfied material from aluminium cup, and be used as 200
DEG C degradation sample.The thickness of gained sample is 6mm.
Determine the A hardness (aging front A hardness) of gained sample based on JIS K6253.
Gained sample is added the baking oven (Yamato Science Co. Ltd. system, model " DN4101 ") of 200 DEG C of temperature
In and took out after 500 hours, determined in 200 DEG C of A hardness (A after aging after aging 500 hours based on JIS K6253
Hardness).
(H2S corrosion test)
LED encapsulation piece (trade name " SMD LED (Top View Type 3528 Pre Mold Lead Frame) ",
SDI Corporation system) in injection embodiment 1～9, the hardening resin composition obtaining in comparative example 1～4, in 100 DEG C
Heat 1 hour and then heat 5 hours in 150 DEG C, be made for sample.
Said sample is put into the gas attack test being adjusted to concentration of hydrogen sulfide 12ppm, 40 DEG C of temperature, humidity 80%RH
Machine (Suga Test Instruments (strain) system, model " GS-UV "), after 24 hours to the silvery electrode in LED encapsulation piece
Corrosion condition observed.For the color of above-mentioned electrode, it is silvery white before test, and the carrying out with corrosion, become
For brown, black.
With regard to the metewand of corrosion test, it is evaluated as in the case that silvery electrode occurs variable color substantially not observing
" A ", it is evaluated as " B " in the case that somewhat variable color is brown or black, comments in the case that complete variable color is brown or black
Valency is " C ".
(SOxCorrosion test)
LED encapsulation piece (trade name " SMD LED (Top View Type 3528 Pre Mold Lead Frame) ",
SDI Corporation system) in injection embodiment 1～9, the hardening resin composition obtaining in comparative example 1～4, in 100 DEG C
Heat 1 hour and then heat 5 hours in 150 DEG C, be made for sample.
Said sample and sulfur powder (Kishida Chemical (strain) system) 0.3g are added in the vial of 450ml,
Further above-mentioned vial is added in aluminium vessel.Thereafter, above-mentioned aluminium vessel is put into baking oven (Yamato Science
(strain) system, model " DN-64 "), in 80 DEG C of temperature, through 24 hours afterwards, corrosion feelings to the silvery electrode in LED encapsulation piece
Condition is observed.For the color of above-mentioned electrode, it is silvery white before test, and the carrying out with corrosion, it is changed into brown, enter
And it is changed into black.
With regard to the metewand of corrosion test, with above-mentioned H2S corrosion tests are identical.
[result of the test]
In comparative example 1, due to being not added with the carboxylate (E) of rare earth, thus hardness is significantly after heat ageing
Raise, the heat resistance to solidfied material unconfirmed.In addition, not confirming resistance to H yet2S corrosivity.
In comparative example 2, with the addition of the carboxylate (E) of a small amount of rare earth, but hardness is significantly after heat ageing
Raise, the heat resistance to solidfied material unconfirmed.In addition, not confirming resistance to H yet2S corrosivity.
In comparative example 3 and comparative example 4, due to being not added with the carboxylate (E) of rare earth, thus after heat ageing
Hardness significantly raises, the heat resistance to solidfied material unconfirmed.In addition, not confirming resistance to H yet2The corrosive effect of S.Additionally,
Due to being not added with silsesquioxane (B) and isocyanurate compound (C), thus do not confirm resistance to SO yetxCorrosivity.
In embodiment 1～9, for comparative example 1～2, with the addition of the carboxylic acid of the rare earth of q.s
Salt (E), thus, is that the ascensional range of 200 DEG C of hardness after aging 500 hours is also less, heat resistance improves.And confirm,
Resistance to H2S corrosivity also improves.
By embodiment 4～5 and other embodiments are contrasted the carboxylate it has been confirmed that as rare earth
(E), when, adding OCTOPE R and adding 2 ethyl hexanoic acid yttrium and 2 ethyl hexanoic acid cerium, equivalent heat resistance, resistance to H are shown2S is rotten
Corrosion.
(with regard to SiH/Vinyl)
In comparative example 1 and comparative example 2, with respect to be present in contained compound in hardening resin composition with
1 mole of the aliphatic carbon-to-carbon double bond of silicon atom bonding, is present in the hydrogenation in contained compound in hardening resin composition
The molal quantity (mol ratio) of silicyl is less than 1, and therefore, aging front A hardness is low, less than 60.But compared to comparative example 3 and ratio
Compared with example 4, their ascensional range by 200 DEG C, the aging A hardness causing of 500 hours is larger, does not confirm solidfied material
Heat resistance.
On the other hand, in embodiment 1～7, with respect to being present in contained compound in hardening resin composition
1 mole of the aliphatic carbon-to-carbon double bond with silicon atom bonding, be present in contained whole compounds in hardening resin composition
In hydrosilyl molal quantity (mol ratio) be less than 1, therefore, aging front A hardness is low, less than 60.Embodiment 1～
In 7, by adding the carboxylate (E) of the rare earth of q.s, they by 200 DEG C, 500 hours aging cause
The ascensional range of A hardness is equal extent for embodiment 8～9.
By result above it has been confirmed that passing through to add the carboxylic acid of the rare earth of q.s with respect to organic siliconresin
Salt (E), can obtain with heat resistance and resistance to H2The corrosive composition of S.Further confirm that, by adding silsesquioxane (B)
And isocyanurate compound (C), can obtain that there is resistance to SOxCorrosive composition.
Industrial applicibility
The hardening resin composition of the present invention and solidfied material be applied to requirement heat resistance, the transparency, flexibility, to corrosion
The purposes such as the bonding agent of barrier of property gas, coating agent, encapsulant.Particularly, the hardening resin composition of the present invention
And solidfied material is suitable for use as the encapsulant of optical semiconductor (LED element).
Claims (13)
1. a kind of hardening resin composition, it comprises：
Polysiloxane (A),
Silsesquioxane (B),
Isocyanurate compound (C) and
The carboxylate (E) of rare earth,
As polysiloxane (A), comprise the polysiloxane without aryl,
As silsesquioxane (B), comprise ladder type silsesquioxane.
2. hardening resin composition according to claim 1, wherein, as described ladder type silsesquioxane, comprises point
There is in son the ladder type silsesquioxane of aliphatic carbon-to-carbon double bond.
3. hardening resin composition according to claim 1 and 2, wherein, as described ladder type silsesquioxane, comprises
Intramolecular has the ladder type silsesquioxane of Si -- H bond.
4. the hardening resin composition according to any one of claims 1 to 3, wherein, as described ladder type sesquialter silicon
Oxygen alkane, comprises the ladder type silsesquioxane that intramolecular has aryl.
5. the hardening resin composition according to any one of Claims 1 to 4, wherein, as isocyanuric acid ester chemical combination
Thing (C), the isocyanurate compound shown in contained (1),
In formula (1), Rx、Ry、RzIdentical or different, the group shown in expression (2) or the group shown in formula (3),
In formula (2) and formula (3), R1And R2Identical or different, represent the straight-chain of hydrogen atom or carbon number 1～8 or branched
Alkyl.
6. hardening resin composition according to claim 5, wherein, the described isocyanuric acid ester chemical combination shown in formula (1)
Thing is Rx、Ry、RzOne of above be the group shown in formula (3) isocyanurate compound.
7. the hardening resin composition according to any one of claim 1～6, wherein, as rare earth
Carboxylate (E), comprises carboxylic acid yttrium.
8. the hardening resin composition according to any one of claim 1～6, wherein, the carboxylic acid of rare earth
Salt (E) is cerium carboxylate, the mixture of carboxylic acid lanthanum, carboxylic acid praseodymium and carboxylic acid neodymium.
9. the hardening resin composition according to any one of claim 1～8, wherein, is present in curable resin group
The sum of the Si-H base in contained compound in compound is with respect to being present in contained compound in hardening resin composition
In the sum of the aliphatic carbon-to-carbon double bond with silicon atom bonding ratio be less than 1.
10. the hardening resin composition according to any one of claim 1～9, it also comprises silane coupler (D).
A kind of 11. solidfied materials, it is to obtain the hardening resin composition solidification any one of claim 1～10
's.
A kind of 12. encapsulants, its be usage right require 1～10 any one of hardening resin composition and obtain
's.
A kind of 13. semiconductor devices, it is obtained from the encapsulant that usage right requires described in 12.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014117841 | 2014-06-06 | ||
| JP2014-117841 | 2014-06-06 | ||
| PCT/JP2015/065989 WO2015186722A1 (en) | 2014-06-06 | 2015-06-03 | Curable resin composition, cured product, sealing material, and semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106459584A true CN106459584A (en) | 2017-02-22 |
Family
ID=54766791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580029165.4A Pending CN106459584A (en) | 2014-06-06 | 2015-06-03 | Curable resin composition, cured product, sealing material, and semiconductor device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6474801B2 (en) |
| KR (1) | KR20170016432A (en) |
| CN (1) | CN106459584A (en) |
| TW (1) | TW201604240A (en) |
| WO (1) | WO2015186722A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6496193B2 (en) * | 2015-06-02 | 2019-04-03 | 株式会社ダイセル | Curable silicone resin composition, cured product thereof, and optical semiconductor device |
| WO2017122712A1 (en) * | 2016-01-15 | 2017-07-20 | 株式会社ダイセル | Curable resin composition, cured object, encapsulation material, and semiconductor device |
| WO2018047633A1 (en) * | 2016-09-07 | 2018-03-15 | 株式会社ダイセル | Curable resin composition, cured product thereof, and semiconductor device |
| JP6988834B2 (en) * | 2019-01-10 | 2022-01-05 | 信越化学工業株式会社 | Method for manufacturing polysiloxane |
| KR20240044414A (en) * | 2021-08-11 | 2024-04-04 | 제이엔씨 주식회사 | Siloxane polymer compositions, cured products, electronic components, optical components and composite members |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013094625A1 (en) * | 2011-12-22 | 2013-06-27 | 株式会社ダイセル | Curable resin composition and curable product thereof |
| CN103221486A (en) * | 2010-11-18 | 2013-07-24 | 横滨橡胶株式会社 | Heat-curable silicone resin composition, silicone resin-ontaining structure, optical semiconductor element sealed body, and silanol condensation catalyst |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19506264A1 (en) * | 1994-03-04 | 1995-09-07 | Gen Electric | Silicone composition and manufacturing method |
| JP4275889B2 (en) | 2001-02-09 | 2009-06-10 | 株式会社カネカ | Light emitting diode and manufacturing method thereof |
| JP2006206721A (en) | 2005-01-27 | 2006-08-10 | Kansai Electric Power Co Inc:The | Highly heat-resistant synthetic polymer compound and semiconductor device of high dielectric strength coated with the same |
| JP4826160B2 (en) | 2005-07-28 | 2011-11-30 | ナガセケムテックス株式会社 | Optical element sealing resin composition |
| JP4788837B2 (en) | 2010-01-26 | 2011-10-05 | 横浜ゴム株式会社 | Silicone resin composition and method for using the same, silicone resin, silicone resin-containing structure, and optical semiconductor element sealing body |
| JP2011202154A (en) * | 2010-03-01 | 2011-10-13 | Yokohama Rubber Co Ltd:The | Heat-curable optical semiconductor-encapsulating silicone resin composition and optical semiconductor-encapsulated product using the same |
| JP5784618B2 (en) * | 2010-09-22 | 2015-09-24 | 株式会社カネカ | Modified polyhedral polysiloxane, polyhedral polysiloxane composition, cured product, and optical semiconductor device |
| JP2012111875A (en) * | 2010-11-25 | 2012-06-14 | Daicel Corp | Curable resin composition and cured article |
| JP5880556B2 (en) * | 2011-07-04 | 2016-03-09 | Jnc株式会社 | Compound containing organopolysiloxane or silsesquioxane skeleton having isocyanur skeleton, epoxy group and SiH group, and thermosetting resin composition, cured product, and optical semiconductor encapsulant containing the compound as an adhesion-imparting material |
| JP5778875B2 (en) * | 2013-01-09 | 2015-09-16 | 株式会社ダイセル | Curable resin composition and cured product thereof |
| MY170153A (en) * | 2013-08-01 | 2019-07-09 | Daicel Corp | Curable resin composition and semiconductor device using same |
| JP5736525B1 (en) * | 2013-08-02 | 2015-06-17 | 株式会社ダイセル | Curable resin composition and semiconductor device using the same |
| KR101631048B1 (en) * | 2013-08-06 | 2016-06-15 | 주식회사 다이셀 | Curing resin composition and semiconductor device employing same |
-
2015
- 2015-06-03 KR KR1020177000106A patent/KR20170016432A/en unknown
- 2015-06-03 WO PCT/JP2015/065989 patent/WO2015186722A1/en active Application Filing
- 2015-06-03 CN CN201580029165.4A patent/CN106459584A/en active Pending
- 2015-06-03 JP JP2016525196A patent/JP6474801B2/en not_active Expired - Fee Related
- 2015-06-04 TW TW104118067A patent/TW201604240A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103221486A (en) * | 2010-11-18 | 2013-07-24 | 横滨橡胶株式会社 | Heat-curable silicone resin composition, silicone resin-ontaining structure, optical semiconductor element sealed body, and silanol condensation catalyst |
| WO2013094625A1 (en) * | 2011-12-22 | 2013-06-27 | 株式会社ダイセル | Curable resin composition and curable product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6474801B2 (en) | 2019-02-27 |
| TW201604240A (en) | 2016-02-01 |
| KR20170016432A (en) | 2017-02-13 |
| WO2015186722A1 (en) | 2015-12-10 |
| JPWO2015186722A1 (en) | 2017-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104903404B (en) | Hardening resin composition and solidfied material thereof | |
| CN105008460B (en) | Hardening resin composition, solidfied material, encapsulant and semiconductor device | |
| CN105209549B (en) | Hardening resin composition and use its semiconductor device | |
| CN104583326B (en) | Curable resin composition and use its semiconductor device | |
| WO2015096570A1 (en) | Curable silicon rubber composition for led packaging | |
| CN108350275A (en) | Addition curable silicone resin component, the manufacturing method of the composition and optical semiconductor device | |
| CN106459584A (en) | Curable resin composition, cured product, sealing material, and semiconductor device | |
| CN104583325B (en) | Hardening resin composition and use its semiconductor device | |
| KR20150065672A (en) | Silicone composition for sealing optical semiconductor element, and optical semiconductor device | |
| CN105038253B (en) | Curable compositions and its preparation method | |
| CN106947258A (en) | Addition curing organosilicon resin composition and semiconductor device | |
| JP6313722B2 (en) | Addition-curing silicone composition and semiconductor device | |
| WO2017122712A1 (en) | Curable resin composition, cured object, encapsulation material, and semiconductor device | |
| KR101909914B1 (en) | Curable composition, semiconductor device, and ester-bond-containing organic silicon compound | |
| JP6998905B2 (en) | Additive-curable silicone compositions, cured products and opto-semiconductor devices | |
| JP5886773B2 (en) | Curable organopolysiloxane composition, optical element sealing material, and optical element | |
| JP2021169550A (en) | Curable organosilicon resin composition | |
| TW202010780A (en) | Curable organopolysiloxane composition, encapsulant, and semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170222 |
|
| WD01 | Invention patent application deemed withdrawn after publication |