JP7604931B2 - Method for producing room temperature curable organopolysiloxane composition, room temperature curable organopolysiloxane composition, adhesive, sealant, and article - Google Patents
Method for producing room temperature curable organopolysiloxane composition, room temperature curable organopolysiloxane composition, adhesive, sealant, and article Download PDFInfo
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- JP7604931B2 JP7604931B2 JP2021020328A JP2021020328A JP7604931B2 JP 7604931 B2 JP7604931 B2 JP 7604931B2 JP 2021020328 A JP2021020328 A JP 2021020328A JP 2021020328 A JP2021020328 A JP 2021020328A JP 7604931 B2 JP7604931 B2 JP 7604931B2
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- curable organopolysiloxane
- organopolysiloxane composition
- temperature
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- 239000000203 mixture Substances 0.000 title claims description 194
- 229920001296 polysiloxane Polymers 0.000 title claims description 100
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 230000001070 adhesive effect Effects 0.000 title claims description 14
- 239000000853 adhesive Substances 0.000 title claims description 12
- 239000000565 sealant Substances 0.000 title claims description 11
- 238000003860 storage Methods 0.000 claims description 64
- 239000007788 liquid Substances 0.000 claims description 43
- 238000007789 sealing Methods 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 29
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 claims description 24
- 230000014759 maintenance of location Effects 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 17
- 238000010998 test method Methods 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- 125000004434 sulfur atom Chemical group 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 13
- 125000005842 heteroatom Chemical group 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 150000001282 organosilanes Chemical class 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011324 bead Substances 0.000 claims description 8
- 239000003566 sealing material Substances 0.000 claims description 7
- 125000006850 spacer group Chemical group 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001723 curing Methods 0.000 description 37
- -1 hydroxy(dimethyl)siloxy group Chemical group 0.000 description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 230000007423 decrease Effects 0.000 description 15
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 14
- 229910000077 silane Inorganic materials 0.000 description 14
- WXWYJCSIHQKADM-ZNAKCYKMSA-N (e)-n-[bis[[(e)-butan-2-ylideneamino]oxy]-ethenylsilyl]oxybutan-2-imine Chemical compound CC\C(C)=N\O[Si](O\N=C(/C)CC)(O\N=C(/C)CC)C=C WXWYJCSIHQKADM-ZNAKCYKMSA-N 0.000 description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 7
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- 230000035800 maturation Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 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
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- ZUEIRGBMFHHKAC-UHFFFAOYSA-N 1,1,3,3-tetramethyl-2-(3-trimethoxysilylpropyl)guanidine Chemical compound CO[Si](OC)(OC)CCCN=C(N(C)C)N(C)C ZUEIRGBMFHHKAC-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- GBFVZTUQONJGSL-UHFFFAOYSA-N ethenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C=C GBFVZTUQONJGSL-UHFFFAOYSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- ZKALVNREMFLWAN-VOTSOKGWSA-N (ne)-n-(4-methylpentan-2-ylidene)hydroxylamine Chemical compound CC(C)C\C(C)=N\O ZKALVNREMFLWAN-VOTSOKGWSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013005 condensation curing Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 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 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 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 2
- 239000012943 hotmelt Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
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- 125000005504 styryl group Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
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- 125000003944 tolyl group Chemical group 0.000 description 2
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- 239000010457 zeolite Substances 0.000 description 2
- OGZPYBBKQGPQNU-DABLZPOSSA-N (e)-n-[bis[[(e)-butan-2-ylideneamino]oxy]-methylsilyl]oxybutan-2-imine Chemical compound CC\C(C)=N\O[Si](C)(O\N=C(/C)CC)O\N=C(/C)CC OGZPYBBKQGPQNU-DABLZPOSSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- NZZYRBJEGRIYIF-UHFFFAOYSA-N 1-propan-2-yloxyoctane-1,8-diol;titanium Chemical compound [Ti].CC(C)OC(O)CCCCCCCO NZZYRBJEGRIYIF-UHFFFAOYSA-N 0.000 description 1
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- MYYOABOTICLXRY-UHFFFAOYSA-N N-[bis(dimethylamino)-(trimethylsilylmethylimino)-lambda5-phosphanyl]-N-methylmethanamine Chemical compound CN(P(N(C)C)(N(C)C)=NC[Si](C)(C)C)C MYYOABOTICLXRY-UHFFFAOYSA-N 0.000 description 1
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- 239000004965 Silica aerogel Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
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- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- YNSTXWACVFMCBI-UHFFFAOYSA-N [SiH4].C(C(O)C)(=O)O Chemical class [SiH4].C(C(O)C)(=O)O YNSTXWACVFMCBI-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 1
- NNVDGGDSRRQJMV-UHFFFAOYSA-L [dioctyl(2,2,5,5-tetramethylhexanoyloxy)stannyl] 2,2,5,5-tetramethylhexanoate Chemical compound CCCCCCCC[Sn](OC(=O)C(C)(C)CCC(C)(C)C)(OC(=O)C(C)(C)CCC(C)(C)C)CCCCCCCC NNVDGGDSRRQJMV-UHFFFAOYSA-L 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
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- KEBBHXFLBGHGMA-UHFFFAOYSA-K aluminum;4-ethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O KEBBHXFLBGHGMA-UHFFFAOYSA-K 0.000 description 1
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- WBQJELWEUDLTHA-UHFFFAOYSA-M benzyl(triethyl)azanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC1=CC=CC=C1 WBQJELWEUDLTHA-UHFFFAOYSA-M 0.000 description 1
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
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- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 description 1
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- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 1
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- 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 1
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- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- VEVVRTWXUIWDAW-UHFFFAOYSA-N dodecan-1-amine;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCN VEVVRTWXUIWDAW-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
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- 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
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HVGYYRCQMTYPPY-UHFFFAOYSA-N methyl-tri(propan-2-yl)silane Chemical compound CC(C)[Si](C)(C(C)C)C(C)C HVGYYRCQMTYPPY-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- YRLNLEDCGGGGRS-UHFFFAOYSA-N pentoxysilane Chemical compound CCCCCO[SiH3] YRLNLEDCGGGGRS-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- XGIZTLFJCDBRDD-UHFFFAOYSA-N phenyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)C1=CC=CC=C1 XGIZTLFJCDBRDD-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 1
- 150000003839 salts Chemical class 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
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、シリコーン系シーリング材や接着剤として有用な室温硬化性オルガノポリシロキサン組成物、特には硬化性が速く、なおかつ、保存安定性及び生産性に優れる縮合硬化型の室温硬化性オルガノポリシロキサン組成物の製造方法及び室温硬化性オルガノポリシロキサン組成物、接着剤、シーリング材並びに物品に関するものである。 The present invention relates to a room-temperature curable organopolysiloxane composition useful as a silicone-based sealant or adhesive, in particular to a method for producing a room-temperature curable condensation-curable organopolysiloxane composition that is fast curing and has excellent storage stability and productivity, and to a room-temperature curable organopolysiloxane composition, adhesive, sealant, and article.
大気中の湿気（水分）により室温（２３℃±１５℃）で架橋・硬化する室温硬化性（ＲＴＶ）シリコーンゴム組成物は、その取り扱いが容易な上に耐熱性、接着性、電気特性に優れるため、建材用のシーリング材、電気電子分野での接着剤など様々な分野で利用されている。 Room temperature vulcanizable (RTV) silicone rubber compositions crosslink and harden at room temperature (23°C ± 15°C) due to atmospheric moisture (water), and are easy to handle and have excellent heat resistance, adhesive properties, and electrical properties, so they are used in a variety of fields, such as sealing materials for building materials and adhesives in the electrical and electronics fields.
縮合反応型の室温硬化性ポリオルガノシロキサン組成物の中で、空気中の水分と接触することにより硬化反応が進行する１成分型（１包装型）の組成物は、使用直前にベースポリマーと架橋剤や触媒等とを秤量したり混合したりする煩雑さがなく、取り扱いが簡単である。しかしながら、１成分型の組成物は、硬化が表面から徐々に内部へと進行するものであるため、硬化速度が遅い欠点がある。
また深部硬化性も悪いという難点がある。
Among the condensation reaction type room temperature curable polyorganosiloxane compositions, the one-component type (one-package type) composition in which the curing reaction proceeds by contacting with moisture in the air is easy to handle without the trouble of weighing and mixing the base polymer with the crosslinking agent, catalyst, etc. immediately before use. However, the one-component type composition has the disadvantage of slow curing speed because the curing proceeds gradually from the surface to the inside.
Another drawback is that deep curing is poor.
その欠点を改善する手段として、硬化触媒を増量する方法は一定の効果があるが、この方法は硬化物（シリコーンゴム硬化物）の接着力の低下や耐熱性、耐湿性等の長期耐久性の悪化を招く。 To remedy this shortcoming, increasing the amount of curing catalyst has some effect, but this method leads to a decrease in the adhesive strength of the cured product (silicone rubber cured product) and a deterioration in long-term durability such as heat resistance and moisture resistance.
また、従来用いられている３官能性の硬化剤より反応性の高い４官能性硬化剤を用いた組成物（特許第５７６８６７４号公報：特許文献１）が開示されている。しかし、該組成物の保存安定性に関する記述はなく、保存後の硬化性が低下する可能性がある。一方、ホットメルトシリコーン組成物（特許第３６４２５８４号公報、特許第４８１１５６２号公報：特許文献２，３）が開示されている。しかし、これらの組成物を使用するためには、ホットメルトの吐出機など特殊な装置が必要である。また、縮合反応型の室温硬化性ポリオルガノシロキサン組成物として二成分型の縮合硬化性シリコーン系接着剤組成物（特許第２９６６２５７号公報：特許文献４）も開示されているが、該二成分型の組成物は保存安定性（保存後の硬化性）に問題がある。そのため、組成物中の架橋剤、接着助剤、触媒を予め温度を掛けて熟成することにより保存安定性（保存後の硬化性）を改善することが提案されている（特許第５３５９４０６号公報：特許文献５）。しかしながら、熟成温度が低温で熟成の効果が表れるまでの時間が長く、組成物の生産性が悪かった。また、長期保管後のシール性（耐圧性）が劣る場合があった。 In addition, a composition using a tetrafunctional curing agent that is more reactive than the conventionally used trifunctional curing agent (JP Patent No. 5768674: Patent Document 1) has been disclosed. However, there is no description of the storage stability of the composition, and the curing property after storage may decrease. On the other hand, a hot melt silicone composition (JP Patent No. 3642584, JP Patent No. 4811562: Patent Documents 2 and 3) has been disclosed. However, in order to use these compositions, a special device such as a hot melt dispenser is required. In addition, a two-component condensation curable silicone adhesive composition (JP Patent No. 2966257: Patent Document 4) has also been disclosed as a condensation reaction type room temperature curable polyorganosiloxane composition, but the two-component composition has a problem with storage stability (curing property after storage). Therefore, it has been proposed to improve the storage stability (curing property after storage) by aging the crosslinking agent, adhesive assistant, and catalyst in the composition by applying temperature in advance (JP Patent No. 5359406: Patent Document 5). However, the maturation temperature was low, and it took a long time for the maturation effect to appear, which resulted in poor productivity of the composition. In addition, the sealing property (pressure resistance) after long-term storage was sometimes poor.
本発明は、上記事情に鑑みなされたもので、硬化性、保存性及び生産性に優れた室温硬化性オルガノポリシロキサン組成物の製造方法及び室温硬化性オルガノポリシロキサン組成物を提供することを目的とするものである。更に、該室温硬化性オルガノポリシロキサン組成物からなる接着剤及びシーリング材、並びに該室温硬化性オルガノポリシロキサン組成物の硬化物で接着及びシールの少なくともいずれかを施した物品を提供することを目的とする。 The present invention has been made in consideration of the above circumstances, and aims to provide a method for producing a room-temperature curable organopolysiloxane composition that is excellent in curability, storage stability, and productivity, and a room-temperature curable organopolysiloxane composition. It also aims to provide an adhesive and a sealant made from the room-temperature curable organopolysiloxane composition, and an article that is at least bonded and sealed with a cured product of the room-temperature curable organopolysiloxane composition.
本発明者らは、上記目的を達成するために鋭意検討した結果、組成物中の架橋剤と接着助剤を特定の割合で混合し、更に必要に応じて硬化触媒を添加し、これらを予め所定温度の範囲で熟成（熟成とは、一定の加熱温度、時間で予め混合することを言う）することで、硬化性、保存性、生産性に優れた室温硬化性オルガノポリシロキサン組成物が得られることを見出し、本発明をなすに至ったものである。 As a result of extensive research into achieving the above object, the inventors discovered that by mixing the crosslinking agent and adhesive aid in a specific ratio in the composition, and further adding a curing catalyst as necessary, and maturing these in advance at a predetermined temperature range (maturing means mixing in advance at a certain heating temperature for a certain period of time), a room temperature curable organopolysiloxane composition with excellent curability, storage stability, and productivity can be obtained, which led to the present invention.
即ち、本発明は、下記の室温硬化性オルガノポリシロキサン組成物の製造方法及び室温硬化性オルガノポリシロキサン組成物、更に該室温硬化性オルガノポリシロキサン組成物からなる接着剤及びシーリング材、並びに物品等を提供する。
［１］
（Ａ）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～３０質量部、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～１５質量部、
（Ｒ1Ｏ）aＳｉＲ2
3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～１５質量部
を含有する室温硬化性オルガノポリシロキサン組成物の製造方法であって、
上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、更に上記（Ｃ－３）成分を添加し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を（Ａ）成分、（Ｂ）成分に添加するものである室温硬化性オルガノポリシロキサン組成物の製造方法。
［２］
下記の第一液を調製する工程と第二液を調製する工程とを有し、更に該第一液と第二液を１００：１０～１００：１００の質量比で混合して室温硬化性オルガノポリシロキサン組成物（ただし、下記の（Ａ－１）成分と（Ａ－２）成分の合計１００質量部に対して、（Ｂ－１）成分と（Ｂ－２）成分の合計配合量は０．１～８００質量部であり、（Ｃ－１）成分の配合量は０．５～３０質量部であり、（Ｃ－２）成分の配合量は０．１～１５質量部であり、（Ｃ－３）成分の配合量は０．００１～１５質量部である。）を得るものである二液混合型の室温硬化性オルガノポリシロキサン組成物の製造方法。
［第一液調製工程］
（Ａ－１）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ－１）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～６０質量部、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～３０質量部、
（Ｒ1Ｏ）aＳｉＲ2
3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～３０質量部
を含有する第一液の調製工程であって、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、更に上記（Ｃ－３）成分を添加し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を（Ａ－１）成分、（Ｂ－１）成分に添加して第一液を調製する。
［第二液調製工程］
（Ａ－２）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ－２）充填剤 ０．１～８００質量部
を混合して第二液を調製する（ただし、上記（Ｃ－１）、（Ｃ－２）、（Ｃ－３）成分を添加しない）。
［３］
下記初期シール性試験方法で測定される、製造直後の室温硬化性オルガノポリシロキサン組成物の初期シール性に対する４０℃２ヶ月間保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性の保持率が９０％以上である室温硬化性オルガノポリシロキサン組成物を製造するものである［１］又は［２］に記載の室温硬化性オルガノポリシロキサン組成物の製造方法。
［初期シール性試験方法］
試験装置としてＪＩＳ Ｋ ６８２０に規定されている耐圧試験用フランジ圧力容器に準ずる、内径５８ｍｍ、外径８０ｍｍ、厚さ１０ｍｍの上側フランジを有する上側容器と、上側フランジと同寸法の下側フランジを有する下側容器からなり、下側フランジのシール面のインナー側縁部には、幅３ｍｍ、深さ３ｍｍの環状の切り欠きが円周に沿って設けられている圧力容器を用い、該圧力容器の下側のフランジのシール面を洗浄した後、室温硬化性オルガノポリシロキサン組成物をシール面が十分に満たされるだけの塗布量で、下側のシール面中央部にビード状に塗布し、塗布後直ちに上側容器を上側フランジと下側フランジのシール面とが当接するように下側容器に載せ、上下フランジのシール面間の距離を規定するための高さ２１．０ｍｍのスペーサーを設置して４本の締め付けボルトを組み付ける。その後、２３℃、５０％ＲＨで３０分間硬化させた後、上側の加圧口から加圧気体を挿入し、上記組成物の硬化物であるシール材が耐えうる気体圧の最大値を初期シール性（ｋＰａ）として測定する。
［４］
（Ａ）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～３０質量部、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～１５質量部、
（Ｒ1Ｏ）aＳｉＲ2
3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～１５質量部
を含有する室温硬化性オルガノポリシロキサン組成物であって、
上記（Ｃ－１）、（Ｃ－２）及び（Ｃ－３）成分を、加熱熟成混合物（Ｃ）として含有し、
上記加熱熟成混合物（Ｃ）は、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で含み、更に（Ｃ－３）成分を含む１００℃超１５０℃以下で３０分～２４時間の加熱熟成混合物（Ｃ）である、室温硬化性オルガノポリシロキサン組成物。
［５］
下記初期シール性試験方法で測定される、製造直後の室温硬化性オルガノポリシロキサン組成物の初期シール性に対する４０℃２ヶ月間保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性の保持率が９０％以上である［４］に記載の室温硬化性オルガノポリシロキサン組成物。
［初期シール性試験方法］
試験装置としてＪＩＳ Ｋ ６８２０に規定されている耐圧試験用フランジ圧力容器に準ずる、内径５８ｍｍ、外径８０ｍｍ、厚さ１０ｍｍの上側フランジを有する上側容器と、上側フランジと同寸法の下側フランジを有する下側容器からなり、下側フランジのシール面のインナー側縁部には、幅３ｍｍ、深さ３ｍｍの環状の切り欠きが円周に沿って設けられている圧力容器を用い、該圧力容器の下側のフランジのシール面を洗浄した後、室温硬化性オルガノポリシロキサン組成物をシール面が十分に満たされるだけの塗布量で、下側のシール面中央部にビード状に塗布し、塗布後直ちに上側容器を上側フランジと下側フランジのシール面とが当接するように下側容器に載せ、上下フランジのシール面間の距離を規定するための高さ２１．０ｍｍのスペーサーを設置して４本の締め付けボルトを組み付ける。その後、２３℃、５０％ＲＨで３０分間硬化させた後、上側の加圧口から加圧気体を挿入し、上記組成物の硬化物であるシール材が耐えうる気体圧の最大値を初期シール性（ｋＰａ）として測定する。
［６］
［４］又は［５］に記載の室温硬化性オルガノポリシロキサン組成物からなる接着剤。
［７］
［４］又は［５］に記載の室温硬化性オルガノポリシロキサン組成物からなるシーリング材。
［８］
［４］又は［５］に記載の室温硬化性オルガノポリシロキサン組成物を硬化させることにより得られる硬化物で接着及び／又はシールされた物品。
That is, the present invention provides the following room-temperature-curable organopolysiloxane composition, a room-temperature-curable organopolysiloxane composition, and further adhesives and sealants, articles, etc., each of which comprises the room-temperature-curable organopolysiloxane composition.
[1]
(A) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 30 parts by mass of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 15 parts by mass of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
A method for producing a room-temperature-curable organopolysiloxane composition comprising: (C-3) 0.001 to 15 parts by mass of a curing catalyst,
A method for producing a room-temperature curable organopolysiloxane composition, comprising mixing the above-mentioned components (C-1) and (C-2) in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, adding the above-mentioned component (C-3), and heat-aging the mixture at a temperature higher than 100°C and not higher than 150°C for 30 minutes to 24 hours to obtain a heat-aged mixture (C), and adding this heat-aged mixture (C) to components (A) and (B).
[2]
The method for producing a two-part mixing type room temperature curable organopolysiloxane composition includes the steps of preparing a first liquid and preparing a second liquid, and further mixing the first liquid and the second liquid in a mass ratio of 100:10 to 100:100 to obtain a room temperature curable organopolysiloxane composition (wherein, relative to 100 parts by mass of the combined total of components (A-1) and (A-2) below, the combined amount of components (B-1) and (B-2) is 0.1 to 800 parts by mass, the combined amount of component (C-1) is 0.5 to 30 parts by mass, the combined amount of component (C-2) is 0.1 to 15 parts by mass, and the combined amount of component (C-3) is 0.001 to 15 parts by mass) .
[First liquid preparation step]
(A-1) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B-1) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 60 parts by mass of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 30 parts by mass of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
A step of preparing a first liquid containing 0.001 to 30 parts by mass of a curing catalyst (C-3), in which the above-mentioned components (C-1) and (C-2) are mixed in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, the above-mentioned component (C-3) is further added, and the mixture is heated and aged at a temperature higher than 100° C. and not higher than 150° C. for 30 minutes to 24 hours to obtain a heat-aged mixture (C), and the heat-aged mixture (C) is added to the components (A-1) and (B-1) to prepare the first liquid.
[Second liquid preparation step]
(A-2) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B-2) 0.1 to 800 parts by mass of a filler is mixed to prepare a second liquid (without adding the above components (C-1), (C-2), and (C-3)).
[3]
The method for producing a room-temperature-curable organopolysiloxane composition according to [1] or [2], which produces a room-temperature-curable organopolysiloxane composition in which the retention of the initial sealability of the room-temperature-curable organopolysiloxane composition after storage at 40°C for 2 months is 90% or more relative to the initial sealability of the room-temperature-curable organopolysiloxane composition immediately after production, as measured by the initial sealability test method described below.
[Initial sealability test method]
The test apparatus used was a pressure vessel conforming to the flanged pressure vessels for pressure tests specified in JIS K 6820, consisting of an upper vessel having an upper flange with an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange of the same dimensions as the upper flange, with a 3 mm wide and 3 mm deep annular notch provided around the circumference on the inner side edge of the sealing surface of the lower flange. After cleaning the sealing surface of the lower flange of the pressure vessel, a room-temperature-curable organopolysiloxane composition was applied in the form of a bead to the center of the lower sealing surface in an amount sufficient to fully fill the sealing surface. Immediately after application, the upper vessel was placed on the lower vessel so that the sealing surfaces of the upper and lower flanges were in contact, a spacer 21.0 mm high was installed to define the distance between the sealing surfaces of the upper and lower flanges, and four tightening bolts were attached. After that, it is cured at 23°C and 50% RH for 30 minutes, and then pressurized gas is introduced from the upper pressure port, and the maximum gas pressure that the sealing material, which is the cured product of the above composition, can withstand is measured as the initial sealability (kPa).
[4]
(A) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 30 parts by mass of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 15 parts by mass of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
(C-3) a room temperature curable organopolysiloxane composition containing 0.001 to 15 parts by mass of a curing catalyst,
The above components (C-1), (C-2) and (C-3) are contained as a heat-ripened mixture (C),
The heat-aged mixture (C) is a room- temperature-curable organopolysiloxane composition that contains the above-mentioned components (C-1) and (C-2) in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, and further contains component (C-3), and is heated to a temperature higher than 100° C. and not higher than 150° C. for 30 minutes to 24 hours.
[5]
The room-temperature-curable organopolysiloxane composition according to [4], wherein the retention of the initial sealability of the room-temperature-curable organopolysiloxane composition after storage at 40°C for 2 months is 90% or more relative to the initial sealability of the room-temperature-curable organopolysiloxane composition immediately after production, as measured by the initial sealability test method described below.
[Initial sealability test method]
The test apparatus used was a pressure vessel conforming to the flanged pressure vessels for pressure tests specified in JIS K 6820, consisting of an upper vessel having an upper flange with an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange of the same dimensions as the upper flange, with a 3 mm wide and 3 mm deep annular notch provided around the circumference on the inner side edge of the sealing surface of the lower flange. After cleaning the sealing surface of the lower flange of the pressure vessel, a room-temperature-curable organopolysiloxane composition was applied in the form of a bead to the center of the lower sealing surface in an amount sufficient to fully fill the sealing surface. Immediately after application, the upper vessel was placed on the lower vessel so that the sealing surfaces of the upper and lower flanges were in contact, a spacer 21.0 mm high was installed to define the distance between the sealing surfaces of the upper and lower flanges, and four tightening bolts were attached. After that, it is cured at 23°C and 50% RH for 30 minutes, and then pressurized gas is introduced from the upper pressure port, and the maximum gas pressure that the sealing material, which is the cured product of the above composition, can withstand is measured as the initial sealability (kPa).
[6]
An adhesive comprising the room-temperature-curable organopolysiloxane composition according to [4] or [5].
[7]
A sealant comprising the room-temperature-curable organopolysiloxane composition according to [4] or [5].
[8]
An article bonded and/or sealed with a cured product obtained by curing the room-temperature-curable organopolysiloxane composition according to [4] or [5].
本発明の製造方法によれば、大気中の湿気にて室温下で極めて速やかに硬化し、保存性（保存後の硬化性及びシール性）も良好な室温硬化性オルガノポリシロキサン組成物が効率よく（生産性よく）得られる。 The manufacturing method of the present invention makes it possible to efficiently (productively) obtain a room-temperature curable organopolysiloxane composition that cures extremely quickly at room temperature due to atmospheric moisture and has good storage stability (curability and sealability after storage).
＜室温硬化性オルガノポリシロキサン組成物の製造方法＞
本発明に係る室温硬化性オルガノポリシロキサン組成物の製造方法の第１の実施形態は、
（Ａ）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～３０質量部、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～１５質量部、
（Ｒ1Ｏ）aＳｉＲ2
3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～１５質量部
を含有する室温硬化性オルガノポリシロキサン組成物の製造方法であって、
上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を配合する工程を含むものである。
<Method for producing room temperature curable organopolysiloxane composition>
A first embodiment of the method for producing a room temperature curable organopolysiloxane composition according to the present invention comprises the steps of:
(A) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 30 parts by mass of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 15 parts by mass of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
A method for producing a room-temperature-curable organopolysiloxane composition comprising: (C-3) 0.001 to 15 parts by mass of a curing catalyst,
The method includes a step of mixing the above-mentioned (C-1) and (C-2) components in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, heat-aging the mixture at a temperature higher than 100° C. and not higher than 150° C. for 30 minutes to 24 hours to obtain a heat-aged mixture (C), and blending the heat-aged mixture (C).
以下、本発明を詳細に説明する。
［（Ａ）成分］
（Ａ）成分は、分子鎖両末端がケイ素原子に結合した水酸基（シラノール基）で封鎖されたジオルガノポリシロキサンであり、本発明のオルガノポリシロキサン組成物の主成分（ベースポリマー）である。該ジオルガノポリシロキサンの分子構造は特に制限されるものでなく、直鎖状、分岐状、分岐構造を有する直鎖状（分岐鎖状）のいずれであってもよいが、好ましくは、主鎖が基本的にジオルガノシロキサン単位の繰り返しからなり、分子鎖両末端がケイ素原子に結合した水酸基（シラノール基）で封鎖された直鎖状のジオルガノポリシロキサンである。該直鎖状ジオルガノポリシロキサンは、分岐構造を少量有している分岐鎖状であってもよい。また、該ジオルガノポリシロキサンは分子鎖中（特には、分子鎖両末端のシラノール基と主鎖を構成するジオルガノシロキサン単位の繰り返し構造との連結部等）にシルアルキレン構造（－ＳｉＲ4Ｓｉ－）などを有するものであってもよい。前記Ｒ4は、炭素数１～２０、好ましくは炭素数２～６の２価炭化水素基（例えば、直鎖状又は分岐状のアルキレン基等）である。また、炭素原子に結合する水素原子の一部又は全部がハロゲン原子、又はシアノ基で置換されているものであってもよい。
The present invention will be described in detail below.
[Component (A)]
The (A) component is a diorganopolysiloxane whose molecular chain ends are blocked with hydroxyl groups (silanol groups) bonded to silicon atoms, and is the main component (base polymer) of the organopolysiloxane composition of the present invention.The molecular structure of the diorganopolysiloxane is not particularly limited, and may be any of linear, branched, and linear (branched) with branched structure, but preferably is a linear diorganopolysiloxane whose main chain is basically composed of repeating diorganosiloxane units, and whose molecular chain ends are blocked with hydroxyl groups (silanol groups) bonded to silicon atoms.The linear diorganopolysiloxane may be a branched chain with a small amount of branched structure. The diorganopolysiloxane may also have a silalkylene structure (-SiR 4 Si-) in the molecular chain (particularly at the link between the silanol groups at both ends of the molecular chain and the repeating structure of diorganosiloxane units constituting the main chain). The R 4 is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 6 carbon atoms (for example, a linear or branched alkylene group). Some or all of the hydrogen atoms bonded to the carbon atoms may be substituted with halogen atoms or cyano groups.
なお、ケイ素原子に結合した水酸基（シラノール基）は、通常、ヒドロキシ（ジメチル）シロキシ基、ヒドロキシ（ジフェニル）シロキシ基、ヒドロキシ（メチルフェニル）シロキシ基などのヒドロキシ（ジオルガノ）シロキシ基等の形態で分子鎖末端に存在することが好ましい。 In addition, the hydroxyl group (silanol group) bonded to the silicon atom is preferably present at the molecular chain end in the form of a hydroxy(diorgano)siloxy group, such as a hydroxy(dimethyl)siloxy group, a hydroxy(diphenyl)siloxy group, or a hydroxy(methylphenyl)siloxy group.
ここで、ジオルガノポリシロキサンのケイ素原子に結合する水酸基以外の有機基としては、炭素数１～１０、好ましくは炭素数１～６の非置換又は置換の１価炭化水素基であることが好ましく、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ヘキシル基、２－エチルヘキシル基、オクチル基等のアルキル基、シクロヘキシル基等の環状アルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、フェニル基、トリル基等のアリール基、及びこれらの基の水素原子が部分的にハロゲン原子で置換された基、例えば３，３，３－トリフルオロプロピル基などである。これらの中では、特にメチル基、フェニル基、３，３，３－トリフルオロプロピル基等が好ましい。これらは同一の基であっても異種の基であってもよい。 Here, the organic group other than the hydroxyl group bonded to the silicon atom of the diorganopolysiloxane is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, and octyl groups, cyclic alkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl, allyl, and propenyl groups, aryl groups such as phenyl and tolyl groups, and groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms, such as 3,3,3-trifluoropropyl groups. Of these, methyl, phenyl, and 3,3,3-trifluoropropyl groups are particularly preferred. These groups may be the same or different.
（Ａ）成分のジオルガノポリシロキサンは、２３℃における粘度が好ましくは２０～１，０００，０００ｍＰａ・ｓ、より好ましくは１００～３００，０００ｍＰａ・ｓ、更に好ましくは５００～２００，０００ｍＰａ・ｓ、特に７００～１００，０００ｍＰａ・ｓであるものがよい。ジオルガノポリシロキサンの粘度が上記下限値（２０ｍＰａ・ｓ）未満であると、硬化物に十分な機械特性が得られない場合がある。また、ジオルガノポリシロキサンの粘度が上記上限値（１，０００，０００ｍＰａ・ｓ）超では、作業性が低下するので、好ましくない。なお、粘度は回転粘度計（例えば、ＢＬ型、ＢＨ型、ＢＳ型、コーンプレート型、レオメータ等）などによって測定した値である。 The diorganopolysiloxane of component (A) preferably has a viscosity at 23°C of 20 to 1,000,000 mPa·s, more preferably 100 to 300,000 mPa·s, even more preferably 500 to 200,000 mPa·s, and particularly preferably 700 to 100,000 mPa·s. If the viscosity of the diorganopolysiloxane is less than the lower limit (20 mPa·s), the cured product may not have sufficient mechanical properties. If the viscosity of the diorganopolysiloxane exceeds the upper limit (1,000,000 mPa·s), workability decreases, which is not preferable. The viscosity is measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.).
また、（Ａ）成分のジオルガノポリシロキサンは、上記と同様な理由で、該ジオルガノポリシロキサンの主鎖を構成する２価のジオルガノシロキサン単位の繰り返し数（又は重合度）が、通常、２０～２，０００、好ましくは５０～１，５００、より好ましくは１００～１，２００、更に好ましくは２００～１，０００程度であることが望ましい。なお、本発明において、重合度（又は分子量）は、例えば、トルエン等を展開溶媒としてゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析におけるポリスチレン換算の数平均重合度（又は数平均分子量）等として求めることができる。
上記（Ａ）成分のジオルガノポリシロキサンは、従来公知の方法で製造することができる。
For the same reasons as above, it is desirable that the diorganopolysiloxane of component (A) has a repeat number (or degree of polymerization) of the divalent diorganosiloxane unit constituting the main chain of the diorganopolysiloxane of usually about 20 to 2,000, preferably 50 to 1,500, more preferably 100 to 1,200, and even more preferably about 200 to 1,000. In the present invention, the degree of polymerization (or molecular weight) can be determined, for example, as the polystyrene-equivalent number average degree of polymerization (or number average molecular weight) in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent.
The diorganopolysiloxane of component (A) above can be produced by a conventional method.
［（Ｂ）成分］
（Ｂ）成分は充填剤（無機質充填剤及び／又は有機樹脂充填剤）であり、この組成物から形成される硬化物に十分な機械的強度を与えるために使用される。この充填剤としては公知のものを使用することができ、例えば、微粉末シリカ、煙霧質シリカ、沈降性シリカ、これらのシリカ表面を有機ケイ素化合物で疎水化処理したシリカ、ガラスビーズ、ガラスバルーン、透明樹脂ビーズ、シリカエアロゲル、珪藻土、酸化鉄、酸化亜鉛、酸化マグネシウム、酸化チタン、煙霧状金属酸化物などの金属酸化物、湿式シリカあるいはこれらの表面をシラン処理したもの、石英粉末、カーボンブラック、タルク、ゼオライト及びベントナイト等の補強剤、アスベスト、ガラス繊維、炭素繊維、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛などの金属炭酸塩、ガラスウール、微粉マイカ、溶融シリカ粉末、ポリスチレン、ポリ塩化ビニル、ポリプロピレンなどの合成樹脂粉末等が使用される。また、表面は、処理の有無によらず、使用できる。表面処理剤としては、脂肪酸類、パラフィン類、シラン類、シラザン類、低重合度シロキサン類、有機化合物などが使用できる。これらの充填剤のうち、シリカ、炭酸カルシウム、カーボンブラック、ゼオライトなどの無機質充填剤が好ましく、特に、煙霧質シリカ、炭酸カルシウム（無処理の重質炭酸カルシウム、脂肪酸で処理されたコロイダル炭酸カルシウム）、カーボンブラックが好ましい。
[Component (B)]
The (B) component is a filler (inorganic filler and/or organic resin filler), and is used to give sufficient mechanical strength to the cured product formed from this composition. Known fillers can be used as this filler, and examples include fine powder silica, fumed silica, precipitated silica, silica whose surface has been hydrophobized with an organic silicon compound, glass beads, glass balloons, transparent resin beads, silica aerogel, diatomaceous earth, metal oxides such as iron oxide, zinc oxide, magnesium oxide, titanium oxide, and fumed metal oxide, wet silica or those whose surface has been silane-treated, quartz powder, carbon black, talc, zeolite, and bentonite, reinforcing agents such as asbestos, glass fiber, carbon fiber, metal carbonates such as calcium carbonate, magnesium carbonate, and zinc carbonate, glass wool, fine powder mica, fused silica powder, and synthetic resin powders such as polystyrene, polyvinyl chloride, and polypropylene. In addition, the filler can be used regardless of whether the surface is treated or not. Examples of surface treatment agents that can be used include fatty acids, paraffins, silanes, silazanes, low-polymerization siloxanes, organic compounds, etc. Among these fillers, inorganic fillers such as silica, calcium carbonate, carbon black, and zeolite are preferred, and fumed silica, calcium carbonate (untreated heavy calcium carbonate, colloidal calcium carbonate treated with fatty acid), and carbon black are particularly preferred.
（Ｂ）成分の配合量は、前記（Ａ）成分１００質量部に対して０．１～８００質量部であり、特に０．３～６００質量部とすることが好ましい。０．１質量部未満では、この組成物から得られる硬化物に十分な機械的強度が発現せず、また８００質量部よりも多量に使用すると、組成物の粘度が増大して作業性が悪くなるばかりでなく、硬化後のゴム強度が低下してゴム弾性が得難くなる傾向がある。 The amount of component (B) to be blended is 0.1 to 800 parts by mass, and preferably 0.3 to 600 parts by mass, per 100 parts by mass of component (A). If it is less than 0.1 part by mass, the cured product obtained from this composition will not exhibit sufficient mechanical strength, and if more than 800 parts by mass is used, not only will the viscosity of the composition increase, making workability difficult, but the rubber strength after curing will decrease, making it difficult to obtain rubber elasticity.
［（Ｃ－１）成分］
（Ｃ－１）成分は、ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる、一分子中に３個以上（通常、３個又は４個）の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物（即ち、該加水分解性オルガノシランを部分的に加水分解・縮合して生成する分子中に残存加水分解性基を３個以上有するオルガノシロキサンオリゴマー）であり、本発明の組成物において架橋剤（硬化剤）として作用するものである。なお、本発明において（Ｃ－１）成分は、後述する（Ｃ－２）成分のシランカップリング剤を含まない。即ち、（Ｃ－１）成分は、分子中に窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基を含有しないものである点において、後述する（Ｃ－２）成分のシランカップリング剤とは明確に区別されるものである。
[Component (C-1)]
The component (C-1) is a hydrolyzable organosilane containing three or more (usually three or four) hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof (i.e., an organosiloxane oligomer having three or more residual hydrolyzable groups in the molecule produced by partially hydrolyzing and condensing the hydrolyzable organosilane), and acts as a crosslinking agent (curing agent) in the composition of the present invention. Note that the component (C-1) in the present invention does not include the silane coupling agent of the component (C-2) described later. That is, the component (C-1) is clearly distinguished from the silane coupling agent of the component (C-2) described later in that it does not contain a functional group containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom in the molecule.
上記加水分解性オルガノシラン及びその部分加水分解縮合物が有する加水分解性基は、ケトオキシム基、アシロキシ基、アルケノキシ基、ラクタート基（乳酸アルキル基）である。具体的には、ジメチルケトオキシム基、メチルエチルケトオキシム基、メチルイソブチルケトオキシム基等の炭素数３～８のケトオキシム基、アセトキシ基、プロピオノキシ基等の炭素数２～４のアシロキシ基、ビニルオキシ基、アリルオキシ基、プロペノキシ基、イソプロペノキシ基等の炭素数２～４のアルケノキシ（アルケニルオキシ）基、－Ｏ－ＣＨ（ＣＨ3）－Ｃ（＝Ｏ）Ｏ－Ｒ’（Ｒ’は炭素数１～３のアルキル基）で示されるラクタート基が挙げられる。 The hydrolyzable groups contained in the hydrolyzable organosilanes and their partial hydrolysis condensates are ketoxime, acyloxy, alkenoxy and lactate groups (alkyl lactate groups). Specific examples include ketoxime groups having 3 to 8 carbon atoms, such as dimethylketoxime, methylethylketoxime and methylisobutylketoxime, acyloxy groups having 2 to 4 carbon atoms, such as acetoxy and propionoxy, alkenoxy (alkenyloxy) groups having 2 to 4 carbon atoms, such as vinyloxy, allyloxy, propenoxy and isopropenoxy, and lactate groups represented by -O-CH( CH3 )-C(=O)O-R'(R' is an alkyl group having 1 to 3 carbon atoms).
また、ケイ素原子に結合する加水分解性基以外の有機基としては、炭素数１～１０、好ましくは１～８の非置換又はハロゲン置換の１価炭化水素基であり、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基等のアルキル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基等のアルケニル基、フェニル基、トリル基、キシリル基等のアリール基、フェニルエチル基等のアラルキル基が挙げられ、好ましくは、メチル基、エチル基、ビニル基、フェニル基であり、該非置換又はハロゲン置換の１価炭化水素基には、アミノ基、イミノ基、エポキシ基、スチリル基、メタクリロキシ基、アクリロキシ基、イソシアネート基、メルカプト基等の窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基を含まない。 In addition, organic groups other than hydrolyzable groups bonded to silicon atoms are unsubstituted or halogen-substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, such as alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl, vinyl, allyl, propenyl, isopropenyl, and butyl. Examples of the alkyl groups include alkenyl groups such as thenyl groups, aryl groups such as phenyl groups, tolyl groups, and xylyl groups, and aralkyl groups such as phenylethyl groups. Of these, methyl groups, ethyl groups, vinyl groups, and phenyl groups are preferred. The unsubstituted or halogen-substituted monovalent hydrocarbon groups do not include functional groups containing at least one heteroatom selected from nitrogen atoms, sulfur atoms, and oxygen atoms, such as amino groups, imino groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, isocyanate groups, and mercapto groups.
このような（Ｃ－１）成分の具体例としては、テトラキス（メチルエチルケトオキシム）シラン、メチルトリス（ジメチルケトオキシム）シラン、メチルトリス（メチルエチルケトオキシム）シラン、エチルトリス（メチルエチルケトオキシム）シラン、メチルトリス（メチルイソブチルケトオキシム）シラン、ビニルトリス（メチルエチルケトオキシム）シランなどのケトオキシムシラン類、メチルトリアセトキシシラン、ビニルトリアセトキシシランなどのアシロキシシラン類、メチルトリイソプロペノキシシラン、ビニルトリイソプロペノキシシラン、フェニルトリイソプロペノキシシラン、メチルトリプロペノキシシラン、ビニルトリプロペノキシシランなどのアルケノキシシラン類、メチルトリス（エチルラクタート）シラン、ビニルトリス（エチルラクタート）シラン、メチルトリス（メチルラクタート）シラン、ビニルトリス（メチルラクタート）シラン、ビニルトリス（ｎ－プロピルラクタート）シランなどのラクタートシラン類並びにこれらのシランの部分加水分解縮合物が挙げられる。これらは単独で用いても複数種を併用してもよい。 Specific examples of such component (C-1) include ketoxime silanes such as tetrakis(methylethylketoxime)silane, methyltris(dimethylketoxime)silane, methyltris(methylethylketoxime)silane, ethyltris(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, and vinyltris(methylethylketoxime)silane; acyloxysilanes such as methyltriacetoxysilane and vinyltriacetoxysilane; and methyltriisopropyl silane. Examples of the silane include alkenoxysilanes such as pentoxysilane, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, methyltripenoxysilane, and vinyltripenoxysilane; lactate silanes such as methyltris(ethyllactate)silane, vinyltris(ethyllactate)silane, methyltris(methyllactate)silane, vinyltris(methyllactate)silane, and vinyltris(n-propyllactate)silane; and partial hydrolysis condensates of these silanes. These may be used alone or in combination.
（Ｃ－１）成分の配合量は、（Ａ）成分１００質量部に対して０．５～３０質量部であり、好ましくは１～１５質量部の範囲である。０．５質量部未満では十分な架橋が進行せず、目的とするゴム弾性を有する硬化物が得られない場合があり、３０質量部を超えると得られる硬化物の柔軟性に劣る場合がある。 The amount of component (C-1) to be blended is 0.5 to 30 parts by mass, and preferably 1 to 15 parts by mass, per 100 parts by mass of component (A). If the amount is less than 0.5 parts by mass, crosslinking will not proceed sufficiently and a cured product with the desired rubber elasticity may not be obtained, while if the amount is more than 30 parts by mass, the flexibility of the resulting cured product may be poor.
［（Ｃ－２）成分］
（Ｃ－２）成分は、（Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤（即ち、分子中に窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基を有する１価炭化水素基と、２個又は３個の加水分解性基とを有するヘテロ官能性基含有加水分解性シラン化合物あるいは、いわゆるカーボンファンクショナルシラン）及び／又はその部分加水分解縮合物であり、本発明の組成物において接着助剤として作用するものである。
（Ｒ1Ｏ）aＳｉＲ2
3-aＲ3 （１）
[Component (C-2)]
Component (C-2) is a silane coupling agent represented by the following general formula (1) other than component (C-1) (i.e., a heterofunctional group-containing hydrolyzable silane compound having a monovalent hydrocarbon group having a functional group containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom in the molecule, and two or three hydrolyzable groups, or a so-called carbon functional silane) and/or a partial hydrolysis condensate thereof, which acts as an adhesion promoter in the composition of the present invention.
(R 1 O) a SiR 2 3-a R 3 (1)
上記式（１）中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基である。これらの中でも、Ｒ1としてはメチル基、エチル基が好ましく、Ｒ2としてはメチル基、エチル基が好ましい。また、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（例えば、アミノ基、イミノ基、エポキシ基、スチリル基、メタクリロキシ基、アクリロキシ基、イソシアネート基、メルカプト基等、ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基）であり、ａは２又は３である。 In the above formula (1), R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Among these, R 1 is preferably a methyl group or an ethyl group, and R 2 is preferably a methyl group or an ethyl group. R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom (e.g., an amino group, an imino group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an isocyanate group, a mercapto group, etc., excluding a guanidyl group), and a is 2 or 3.
（Ｃ－２）成分の加水分解性シランカップリング剤の具体例としては、数多くのシランカップリング剤を例示することが可能であるが、その中でも窒素原子、硫黄原子、または酸素原子の中の少なくとも１つ以上から選ばれる原子を含む炭素数１～１０の非置換１価炭化水素基であることが好ましく、その中でも特に、下記一般式（２）～（６）で示されるアミノ基含有シランカップリング剤を使用すると、良好な接着性を得ることができる。また、これらは１種類に限定されず、その２種以上を使用してもよい。
（Ｒ5Ｏ）3-bＲ5
bＳｉＲ6ＮＨ2 （２）
（Ｒ5Ｏ）3-bＲ5
bＳｉＲ6ＮＨＣ2Ｈ4ＮＨ2 （３）
（Ｒ5Ｏ）3-bＲ5
bＳｉＲ6ＮＨＣ2Ｈ4ＮＨＲ6ＣＯＯＲ5ＳｉＲ5
b（ＯＲ5）3-b（４）
（Ｒ5Ｏ）3-bＲ5
bＳｉＲ6ＮＨＲ6ＮＨＲ5ＳｉＲ5
b（ＯＲ5）3-b （５）
（Ｒ5Ｏ）3-bＲ5
bＳｉＲ6ＮＨＲ7ＮＨ2 （６）
（式中、Ｒ5は炭素数１～１０の非置換１価炭化水素基からなり、Ｒ6は炭素数１～１０の２価炭化水素基であり、Ｒ6は互いに同一又は異種の基であってもよい。Ｒ7はアルキレン基と芳香環を含む炭素数７～１０の２価炭化水素基であり、ｂは０，１，２の中から選ばれる整数である。）
Specific examples of the hydrolyzable silane coupling agent of component (C-2) include many silane coupling agents, among which unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms containing at least one atom selected from nitrogen atoms, sulfur atoms, and oxygen atoms are preferred, and among these, particularly, amino group-containing silane coupling agents represented by the following general formulas (2) to (6) can be used to obtain good adhesion. Moreover, these are not limited to one type, and two or more types may be used.
(R 5 O) 3-b R 5 b SiR 6 NH 2 (2)
(R 5 O) 3-b R 5 b SiR 6 NHC 2 H 4 NH 2 (3)
(R 5 O) 3-b R 5 b SiR 6 NHC 2 H 4 NHR 6 COOR 5 SiR 5 b (OR 5 ) 3-b (4)
(R 5 O) 3-b R 5 b SiR 6 NHR 6 NHR 5 SiR 5 b (OR 5 ) 3-b (5)
(R 5 O) 3-b R 5 b SiR 6 NHR 7 NH 2 (6)
(In the formula, R5 is an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R6 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R6 may be the same or different groups. R7 is a divalent hydrocarbon group having 7 to 10 carbon atoms containing an alkylene group and an aromatic ring, and b is an integer selected from 0, 1, and 2.)
また、（Ｃ－２）成分の配合量は、（Ａ）成分１００質量部に対して０．１～１５質量部であり、好ましくは０．２～１０質量部、より好ましくは０．５～８質量部である。（Ｃ－２）成分の配合量が少なすぎると、硬化物の接着性が低下する場合があり、多すぎると得られる硬化物の耐熱性や耐薬品性などの耐久性が低下する場合がある。 The amount of component (C-2) is 0.1 to 15 parts by mass, preferably 0.2 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass, per 100 parts by mass of component (A). If the amount of component (C-2) is too small, the adhesive properties of the cured product may decrease, and if the amount is too large, the durability of the obtained cured product, such as heat resistance and chemical resistance, may decrease.
［（Ｃ－３）成分］
（Ｃ－３）成分は、硬化触媒（非金属系有機触媒及び／又は金属系触媒）であり、本発明の室温硬化性オルガノポリシロキサン組成物の硬化（架橋反応）を促進するために作用する。
[Component (C-3)]
The component (C-3) is a curing catalyst (a non-metallic organic catalyst and/or a metallic catalyst) that acts to accelerate the curing (crosslinking reaction) of the room temperature curable organopolysiloxane composition of the present invention.
該硬化触媒の非金属系有機触媒としては、縮合硬化型オルガノポリシロキサン組成物の硬化促進剤として公知のものを使用することができ、特に制限されるものではない。例えば、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ''，Ｎ''－ヘキサメチル－Ｎ'''－（トリメチルシリルメチル）－ホスホリミディックトリアミド等のホスファゼン含有化合物、ヘキシルアミン、オクチルアミン、リン酸ドデシルアミン等のアミン化合物又はその塩、ベンジルトリエチルアンモニウムアセテート等の第４級アンモニウム塩、ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等のジアルキルヒドロキシルアミン、テトラメチルグアニジルプロピルトリメトキシシラン（別名：Ｎ，Ｎ，Ｎ’，Ｎ’‐テトラメチル‐Ｎ''‐［３－（トリメトキシシリル）プロピル］グアニジン、１，１，３，３－テトラメチル－２－［３－（トリメトキシシリル）プロピル］グアニジン）、テトラメチルグアニジルプロピルメチルジメトキシシラン、テトラメチルグアニジルプロピルトリス（トリメチルシロキシ）シラン等のグアニジル基を含有する加水分解性シラン及びシロキサン等が例示されるが、非金属系有機触媒はこれらに限定されない。また、非金属系有機触媒は１種でも２種以上を混合して使用してもよい。 The non-metallic organic catalyst used as the curing catalyst may be any known curing accelerator for condensation curing organopolysiloxane compositions, and is not particularly limited. Examples of the non-metallic organic catalyst include, but are not limited to, phosphazene-containing compounds such as N,N,N',N',N'',N''-hexamethyl-N'''-(trimethylsilylmethyl)-phosphorimidic triamide, amine compounds or salts thereof such as hexylamine, octylamine, and dodecylamine phosphate, quaternary ammonium salts such as benzyltriethylammonium acetate, dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine, hydrolyzable silanes and siloxanes containing a guanidyl group such as tetramethylguanidylpropyltrimethoxysilane (also known as N,N,N',N'-tetramethyl-N''-[3-(trimethoxysilyl)propyl]guanidine, 1,1,3,3-tetramethyl-2-[3-(trimethoxysilyl)propyl]guanidine), tetramethylguanidylpropylmethyldimethoxysilane, and tetramethylguanidylpropyltris(trimethylsiloxy)silane. In addition, non-metallic organic catalysts may be used alone or in combination of two or more.
該硬化触媒の金属系触媒としては、縮合硬化型オルガノポリシロキサン組成物の硬化促進剤として公知のものを使用することができ、特に制限されるものではない。例えば、ジブチルスズジアセテート、ジブチルスズジラウレート、ジブチルスズジオクトエート、ジオクチルスズジネオデカノエート、ジ－ｎ－ブチル－ジメトキシスズ等のアルキルスズエステル化合物、テトライソプロポキシチタン、テトラ－ｎ－ブトキシチタン、テトラキス（２－エチルヘキソキシ）チタン、ジプロポキシビス（アセチルアセトナト）チタン、チタニウムイソプロポキシオクチレングリコール等のチタン酸エステル又はチタンキレート化合物、ナフテン酸亜鉛、ステアリン酸亜鉛、亜鉛－２－エチルオクトエート、鉄－２－エチルヘキソエート、コバルト－２－エチルヘキソエート、マンガン－２－エチルヘキソエート、ナフテン酸コバルト、アルミニウムイソプロピレート、アルミニウムセカンダリーブチレートなどのアルコレートアルミニウム化合物、アルミニウムアルキルアセテート・ジイソプロピレート、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート等のアルミニウムキレート化合物、ネオデカン酸ビスマス（ＩＩＩ）、２－エチルヘキサン酸ビスマス（ＩＩＩ）、クエン酸ビスマス（ＩＩＩ）、オクチル酸ビスマス等の有機金属化合物、酢酸カリウム、酢酸ナトリウム、シュウ酸リチウム等のアルカリ金属の低級脂肪酸塩が例示されるが、金属系触媒はこれらに限定されない。また、金属系触媒は１種類でも２種類以上を混合して使用してもよい。 As the metal catalyst of the curing catalyst, those known as curing accelerators for condensation curing type organopolysiloxane compositions can be used, and are not particularly limited. For example, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dineodecanoate, and di-n-butyl-dimethoxytin, titanate esters or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, and titanium isopropoxyoctylene glycol, zinc naphthenate, zinc stearate, zinc-2-ethyloctoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, and manganese-2 Examples of metal catalysts include, but are not limited to, aluminum alcoholate compounds such as ethylhexoate, cobalt naphthenate, aluminum isopropylate, and aluminum secondary butylate; aluminum chelate compounds such as aluminum alkyl acetate diisopropylate and aluminum bisethylacetoacetate monoacetylacetonate; organometallic compounds such as bismuth neodecanoate, bismuth 2-ethylhexanoate (III), bismuth citrate (III), and bismuth octylate; and lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, and lithium oxalate. Metal catalysts may be used alone or in combination of two or more types.
（Ｃ－３）成分の配合量は、上記（Ａ）成分１００質量部に対して０．００１～１５質量部であり、０．０１～１０質量部が好ましい。（Ｃ－３）成分が少なすぎると十分な硬化性が得られず、多すぎると硬化性が速すぎる結果、十分な作業時間が得られず、また経済的に不利になる。 The amount of component (C-3) is 0.001 to 15 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of component (A). If the amount of component (C-3) is too small, sufficient curing properties will not be obtained, and if the amount is too large, the curing properties will be too fast, resulting in insufficient working time and being economically disadvantageous.
本発明の製造方法においては、上記（Ｃ－１）成分と（Ｃ－２）成分と、必要に応じて（Ｃ－３）成分とを予め加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を配合する。詳しくは、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を配合するものである。また、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、更に上記（Ｃ－３）成分を添加し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を（Ａ）成分、（Ｂ）成分に添加するものであることが好ましい。 In the manufacturing method of the present invention, the above-mentioned components (C-1) and (C-2), and optionally the component (C-3), are preliminarily heated and aged to obtain a heat-aged mixture (C), which is then blended. Specifically, the above-mentioned components (C-1) and (C-2) are mixed in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, and then heated and aged at a temperature higher than 100°C and not higher than 150°C for 30 minutes to 24 hours to obtain a heat-aged mixture (C), which is then blended. It is also preferable to mix the above (C-1) and (C-2) components in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, add the above (C-3) component, heat and age at a temperature higher than 100°C and not higher than 150°C for 30 minutes to 24 hours to obtain a heat-aged mixture (C), and then add the heat-aged mixture (C) to the components (A) and (B).
ここで、（Ｃ－１）成分と（Ｃ－２）成分との配合割合は、（Ｃ－１）／（Ｃ－２）のモル比が１．７～３．５であることが必要であり、好ましくは１．８～３．３である。このモル比が１．７未満では十分な保存安定性（保存後の硬化性）が得られず、３．５を超えると深部硬化性が劣る。
（Ｃ－１）成分と（Ｃ－２）成分を合計した配合量は、（Ａ）成分１００質量部に対して０．６～４５質量部が好ましく、１．２～３５質量部がより好ましい。この合計配合量が少なすぎると目的とするゴム弾性を有する硬化物が得られず硬化物の接着性が低下する可能性があり、多すぎると硬化物の柔軟性が劣り耐熱性や耐薬品性などの耐久性が低下するおそれがある。
Here, the blending ratio of the (C-1) component to the (C-2) component, that is, the molar ratio (C-1)/(C-2) must be 1.7 to 3.5, and is preferably 1.8 to 3.3. If this molar ratio is less than 1.7, sufficient storage stability (curability after storage) cannot be obtained, and if it exceeds 3.5, deep curability is poor.
The combined amount of components (C-1) and (C-2) is preferably 0.6 to 45 parts by mass, and more preferably 1.2 to 35 parts by mass, per 100 parts by mass of component (A). If this combined amount is too small, a cured product having the desired rubber elasticity may not be obtained, and the adhesiveness of the cured product may decrease, whereas if the combined amount is too large, the flexibility of the cured product may decrease, and durability such as heat resistance and chemical resistance may decrease.
なお、（Ｃ－３）成分は（Ｃ－１）成分と（Ｃ－２）成分の加熱熟成の際、一緒に添加しなくても組成物の保存安定性（保存後の良好な硬化性及びシール性）は確保できるが、一緒に添加して加熱熟成すると生産性がより高まり好ましい。
（Ｃ－１）、（Ｃ－２）、（Ｃ－３）成分を合計した配合量は、（Ａ）成分１００質量部に対して０．６０１～６０質量部が好ましく、１．２１～４０質量部がより好ましい。この合計配合量が少なすぎると目的とするゴム弾性を有する硬化物が得られず硬化物の接着性が低下する可能性があり、多すぎると硬化物の柔軟性が劣り耐熱性や耐薬品性などの耐久性が低下するおそれがある。
In addition, the storage stability of the composition (good curing properties and sealability after storage) can be ensured even if the component (C-3) is not added together with the component (C-1) and the component (C-2) during heat-aging. However, adding the components (C-3) together and heat-aging them increases productivity and is therefore preferred.
The combined amount of components (C-1), (C-2), and (C-3) is preferably 0.601 to 60 parts by mass, and more preferably 1.21 to 40 parts by mass, per 100 parts by mass of component (A). If this combined amount is too small, a cured product having the desired rubber elasticity may not be obtained, and the adhesiveness of the cured product may decrease, whereas if the combined amount is too large, the flexibility of the cured product may decrease, and durability such as heat resistance and chemical resistance may decrease.
（Ｃ－１）成分と（Ｃ－２）成分、必要に応じて添加する（Ｃ－３）成分の熟成方法としては、各成分が加水分解性を有するため、各成分の所定量を密閉容器に計量し、混合した上で加熱養生する（これを加熱熟成と称する。以下、同じ）。
加熱温度としては、１００℃超１５０℃以下、好ましくは１００℃超１４０℃以下であり、加熱時間としては、３０分以上、好ましくは１時間以上である。時間の上限は、２４時間以内、好ましくは１８時間以内である。１００℃以下であると十分な熟成に長時間要するため生産性が悪くなり、保管後のシール性が悪くなる。また、１５０℃を超える温度では、加水分解性基が反応しゲル化するおそれがある。また、３０分未満であると、十分な熟成ができず、２４時間を超えると生産性に劣る。
As for the method of aging the components (C-1) and (C-2) and, if necessary, the component (C-3), since each component is hydrolyzable, predetermined amounts of each component are weighed into a sealed container, mixed, and then heat-aged (this is referred to as heat-aging; the same applies hereinafter).
The heating temperature is more than 100°C and less than 150°C, preferably more than 100°C and less than 140°C, and the heating time is 30 minutes or more, preferably 1 hour or more. The upper limit of the time is within 24 hours, preferably within 18 hours. If it is less than 100°C, it takes a long time to sufficiently mature, which reduces productivity and deteriorates the sealability after storage. In addition, at a temperature exceeding 150°C, the hydrolyzable group may react and gel. In addition, if it is less than 30 minutes, sufficient maturation cannot be achieved, and if it exceeds 24 hours, productivity is poor.
［その他の成分］
本発明の組成物には、上記（Ａ）～（Ｃ）成分のほかに、本発明の目的を阻害しない限り、種々の添加剤を添加することもできる。例えば、添加剤として、顔料、染料、老化防止剤、酸化防止剤、帯電防止剤、酸化アンチモン、塩化パラフィン等の難燃剤、トリメトキシシリル基で封鎖されたジメチルポリシロキサン等の可塑剤、トリオルガノシロキシ単位及びＳｉＯ2単位からなる網状ポリシロキサン等の液状補強剤など公知の添加剤を配合することができる。更に、チクソ性向上剤としてのポリエーテル、防かび剤、抗菌剤を配合することもできる。これらの使用量は、本発明の目的を阻害しない限り任意である。
[Other ingredients]
In addition to the above components (A) to (C), various additives can be added to the composition of the present invention, so long as they do not impede the object of the present invention. For example, known additives can be added, such as pigments, dyes, antioxidants, antioxidants, antistatic agents, flame retardants such as antimony oxide and paraffin chloride, plasticizers such as dimethylpolysiloxanes blocked with trimethoxysilyl groups, and liquid reinforcing agents such as network polysiloxanes consisting of triorganosiloxy units and SiO2 units. In addition, polyethers as thixotropy improvers, fungicides, and antibacterial agents can be added. The amounts of these additives used are arbitrary, so long as they do not impede the object of the present invention.
本発明の室温硬化性オルガノポリシロキサン組成物の製造方法では、上述した（Ｃ－１）成分と（Ｃ－２）成分、必要に応じて（Ｃ－３）成分を予め加熱熟成させたものと、上記（Ａ）成分、（Ｂ）成分及び必要に応じてその他の成分と（加熱熟成に（Ｃ－３）成分を添加しない場合には（Ｃ－３）成分と）を、品川ミキサー、プラネタリーミキサー、ニーダー等の混合機を用いて乾燥、もしくは減圧雰囲気中で均一に混合することにより目的の室温硬化性オルガノポリシロキサン組成物が得られる。 In the method for producing the room temperature curable organopolysiloxane composition of the present invention, the above-mentioned components (C-1) and (C-2), and optionally component (C-3), which have been previously heated and aged, are mixed with the above-mentioned components (A) and (B) and optionally other components (component (C-3) if component (C-3) is not added to the heat-aging process) in a mixer such as a Shinagawa mixer, planetary mixer, or kneader, and then dried or mixed uniformly in a reduced pressure atmosphere to obtain the desired room temperature curable organopolysiloxane composition.
また、本発明に係る室温硬化性オルガノポリシロキサン組成物の製造方法の第２の実施形態は、
下記の第一液を調製する工程と第二液を調製する工程とを有し、更に該第一液と第二液を１００：１０～１００：１００の質量比で混合して室温硬化性オルガノポリシロキサン組成物を得るものである。
［第一液調製工程］
（Ａ－１）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ－１）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～６０質量部（好ましくは０．５５～３０質量部）、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～３０質量部（好ましくは０．１１～１５質量部）、
（Ｒ1Ｏ）aＳｉＲ2
3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～３０質量部（好ましくは０．００１１～１５質量部）
を含有する第一液の調製工程であって、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を配合して第一液を調製する。
［第二液調製工程］
（Ａ－２）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ－２）充填剤 ０．１～８００質量部
を混合して第二液を調製する（ただし、上記（Ｃ－１）、（Ｃ－２）、（Ｃ－３）成分を添加しない）。
A second embodiment of the method for producing a room-temperature-curable organopolysiloxane composition according to the present invention comprises the steps of:
The method includes the steps of preparing a first liquid and preparing a second liquid described below, and further includes mixing the first liquid and the second liquid in a mass ratio of 100:10 to 100:100 to obtain a room-temperature-curable organopolysiloxane composition.
[First liquid preparation step]
(A-1) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B-1) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 60 parts by mass (preferably 0.55 to 30 parts by mass) of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 30 parts by mass (preferably 0.11 to 15 parts by mass) of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
(C-3) Curing catalyst: 0.001 to 30 parts by mass (preferably 0.0011 to 15 parts by mass)
The above-mentioned components (C-1) and (C-2) are mixed in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, and are heated and aged at a temperature higher than 100° C. and not higher than 150° C. for 30 minutes to 24 hours to obtain a heat-aged mixture (C), and the heat-aged mixture (C) is blended to prepare the first liquid.
[Second liquid preparation step]
(A-2) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B-2) 0.1 to 800 parts by mass of a filler is mixed to prepare a second liquid (without adding the above components (C-1), (C-2), and (C-3)).
ここで、（Ａ－１）、（Ａ－２）成分は、第１の実施形態でいう（Ａ）成分と同じであり、（Ｂ－１）、（Ｂ－２）成分は、第１の実施形態でいう（Ｂ）成分と同じであり、（Ｃ－１）、（Ｃ－２）、（Ｃ－３）成分は第１の実施形態で示したもの（成分及び組成物全体における添加量）と同じである。また、第１の実施形態と同様にその他の成分を配合してもよい。 Here, components (A-1) and (A-2) are the same as component (A) in the first embodiment, components (B-1) and (B-2) are the same as component (B) in the first embodiment, and components (C-1), (C-2), and (C-3) are the same as those shown in the first embodiment (components and amounts added in the entire composition). In addition, other components may be blended in the same way as in the first embodiment.
第一液調製工程では、上記（Ｃ－１）成分と（Ｃ－２）成分と、必要に応じて（Ｃ－３）成分とを予め加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を配合する。詳しくは、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を配合するものである。また、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、更に上記（Ｃ－３）成分を添加し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を（Ａ－１）成分、（Ｂ－１）成分に添加して第一液を調製するものであることが好ましい。 In the first liquid preparation step, the above-mentioned (C-1) and (C-2) components, and optionally the (C-3) component, are preliminarily heated and aged to obtain a heat-aged mixture (C), which is then blended. In detail, the above-mentioned (C-1) and (C-2) components are mixed in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, and then heated and aged at a temperature higher than 100°C and not higher than 150°C for 30 minutes to 24 hours to obtain a heat-aged mixture (C), which is then blended. It is also preferable to mix the above (C-1) and (C-2) components in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, add the above (C-3) component, heat and age at a temperature higher than 100°C and not higher than 150°C for 30 minutes to 24 hours to obtain a heat-aged mixture (C), and then add the heat-aged mixture (C) to the (A-1) and (B-1) components to prepare the first liquid.
本実施形態における（Ｃ－１）成分と（Ｃ－２）成分との配合割合は、（Ｃ－１）／（Ｃ－２）のモル比が１．７～３．５であることが必要であり、好ましくは１．８～３である。このモル比が１．７未満では十分な保存安定性（保存後の硬化性）が得られず、３．５を超えると深部硬化性が劣る。なお、（Ｃ－３）成分は（Ｃ－１）成分と（Ｃ－２）成分の加熱熟成の際、一緒に添加しなくても組成物の保存安定性（保存後の良好な硬化性及びシール性）は確保できるが、一緒に添加して加熱熟成すると生産性がより高まり好ましい。また、（Ｃ－３）成分の一部を（Ｃ－１）成分と（Ｃ－２）成分の加熱熟成の際、一緒に添加して加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を（Ｃ－３）成分の残り、（Ａ－１）成分、（Ｂ－１）成分に添加して第一液としてもよい。 In this embodiment, the blending ratio of the (C-1) component and the (C-2) component must be 1.7 to 3.5, preferably 1.8 to 3, in terms of the molar ratio (C-1)/(C-2). If the molar ratio is less than 1.7, sufficient storage stability (curability after storage) cannot be obtained, and if it exceeds 3.5, the deep curing property is poor. Note that, even if the (C-3) component is not added together with the (C-1) component and the (C-2) component during heat maturation, the storage stability of the composition (good curability and sealability after storage) can be ensured, but adding them together and heat maturing increases productivity, which is preferable. Also, a part of the (C-3) component may be added together with the (C-1) component and the (C-2) component during heat maturation to form a heat maturation mixture (C), and the heat maturation mixture (C) may be added to the remainder of the (C-3) component, the (A-1) component, and the (B-1) component to form the first liquid.
また、加熱熟成における加熱温度としては、１００℃超１５０℃以下、好ましくは１００℃超１４０℃以下であり、加熱時間としては、３０分以上、好ましくは１時間以上である。時間の上限は、２４時間以内、好ましくは１８時間以内である。１００℃以下であると十分な熟成に長時間要するため生産性が悪くなり、保管後のシール性が悪くなる。また、１５０℃を超える温度では、加水分解性基が反応しゲル化するおそれがある。また、３０分未満であると、十分な熟成ができず、２４時間を超えると生産性に劣る。 The heating temperature for heat aging is more than 100°C and less than 150°C, preferably more than 100°C and less than 140°C, and the heating time is 30 minutes or more, preferably 1 hour or more. The upper limit of the time is 24 hours or less, preferably 18 hours or less. If the temperature is less than 100°C, a long time is required for sufficient aging, which reduces productivity and deteriorates the sealability after storage. If the temperature exceeds 150°C, the hydrolyzable groups may react and gel. If the temperature is less than 30 minutes, sufficient aging cannot be achieved, and if the temperature exceeds 24 hours, productivity is poor.
第二液調製工程では、上記（Ａ－２）成分と（Ｂ－２）成分を混合して第二液を調製する。このとき、上記（Ｃ－１）、（Ｃ－２）、（Ｃ－３）成分を添加しない点で第一液と相違する。なお、シクロヘキサノン等の有機溶剤を少量添加してもよい。 In the second liquid preparation step, the above-mentioned (A-2) and (B-2) components are mixed to prepare the second liquid. This step differs from the first liquid in that the above-mentioned (C-1), (C-2), and (C-3) components are not added. A small amount of an organic solvent such as cyclohexanone may be added.
次いで、得られた第一液と第二液を１００：１０～１００：１００の質量比で混合して室温硬化性オルガノポリシロキサン組成物を得る。このとき、第一液と第二液の混合比率（質量比）は、希釈剤（有機溶剤）を除いた有効成分として１００：１０～１００：１００である。二液型とする目的は深部硬化性を向上させるためである。 Then, the first and second liquids are mixed in a mass ratio of 100:10 to 100:100 to obtain a room temperature curable organopolysiloxane composition. At this time, the mixing ratio (mass ratio) of the first and second liquids is 100:10 to 100:100 in terms of active ingredients excluding the diluent (organic solvent). The purpose of making it a two-part type is to improve deep curing properties.
上記第一液と第二液とを混合して得られる室温硬化性オルガノポリシロキサン組成物における（Ａ－１）成分と（Ａ－２）成分の合計１００質量部に対する各成分の配合量として、（Ｂ－１）成分と（Ｂ－２）成分の合計配合量は０．１～８００質量部が好ましく、０．３～６００質量部がより好ましい。また、（Ｃ－１）成分の配合量は、０．５～３０質量部が好ましく、１～１５質量部がより好ましい。（Ｃ－２）成分の配合量は、０．１～１５質量部が好ましく、０．２～１０質量部がより好ましく、０．５～８質量部が更に好ましい。（Ｃ－３）成分の配合量は、０．００１～１５質量部が好ましく、０．０１～１０質量部がより好ましい。 In the room temperature curable organopolysiloxane composition obtained by mixing the first liquid and the second liquid, the total amount of the (B-1) and (B-2) components is preferably 0.1 to 800 parts by mass, more preferably 0.3 to 600 parts by mass, relative to 100 parts by mass of the (A-1) and (A-2) components combined. The amount of the (C-1) component is preferably 0.5 to 30 parts by mass, more preferably 1 to 15 parts by mass. The amount of the (C-2) component is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass. The amount of the (C-3) component is preferably 0.001 to 15 parts by mass, more preferably 0.01 to 10 parts by mass.
なお、上記第１及び第２の実施形態のいずれにおいても、下記初期シール性試験方法で測定される、製造直後の室温硬化性オルガノポリシロキサン組成物の初期シール性に対する４０℃２ヶ月間保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性の保持率が９０％以上である室温硬化性オルガノポリシロキサン組成物を製造するものであることが好ましく、９２％以上である室温硬化性オルガノポリシロキサン組成物を製造するものであることがより好ましい。
なお、製造直後の室温硬化性オルガノポリシロキサン組成物の初期シール性Ｐ１に対する４０℃２ヶ月間保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性Ｐ２の保持率は以下の式で求められる（以下、同じ）。
（保持率）＝Ｐ２／Ｐ１×１００（％）
In both the first and second embodiments, it is preferable to produce a room-temperature-curable organopolysiloxane composition in which the retention of the initial sealability of the room-temperature-curable organopolysiloxane composition after storage at 40° C. for 2 months relative to the initial sealability of the room-temperature-curable organopolysiloxane composition immediately after production, as measured by the initial sealability test method described below, is 90% or more, and it is more preferable to produce a room-temperature-curable organopolysiloxane composition in which the retention of the initial sealability is 92% or more.
The retention rate of the initial sealability P2 of a room-temperature-curable organopolysiloxane composition after storage at 40° C. for 2 months relative to the initial sealability P1 of the room-temperature-curable organopolysiloxane composition immediately after production is calculated using the following formula (the same applies hereinafter).
(Retention rate) = P2/P1 x 100 (%)
［初期シール性試験方法］
試験装置としてＪＩＳ Ｋ ６８２０に規定されている耐圧試験用フランジ圧力容器に準ずる、内径５８ｍｍ、外径８０ｍｍ、厚さ１０ｍｍの上側フランジを有する上側容器と、上側フランジと同寸法の下側フランジを有する下側容器からなり、下側フランジのシール面のインナー側縁部には、幅３ｍｍ、深さ３ｍｍの環状の切り欠きが円周に沿って設けられている圧力容器を用い、該圧力容器の下側のフランジのシール面を洗浄した後、室温硬化性オルガノポリシロキサン組成物をシール面が十分に満たされるだけの塗布量で、下側のシール面中央部にビード状に塗布し、塗布後直ちに上側容器を上側フランジと下側フランジのシール面とが当接するように下側容器に載せ、上下フランジのシール面間の距離を規定するための高さ２１．０ｍｍのスペーサーを設置して４本の締め付けボルトを組み付ける。その後、２３℃、５０％ＲＨで３０分間硬化させた後、上側の加圧口から加圧気体を挿入し、上記組成物の硬化物であるシール材が耐えうる気体圧の最大値を初期シール性（ｋＰａ）として測定する。
[Initial sealability test method]
The test apparatus used was a pressure vessel conforming to the flanged pressure vessels for pressure tests specified in JIS K 6820, consisting of an upper vessel having an upper flange with an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange of the same dimensions as the upper flange, with a 3 mm wide and 3 mm deep annular notch provided around the circumference on the inner side edge of the sealing surface of the lower flange. After cleaning the sealing surface of the lower flange of the pressure vessel, a room-temperature-curable organopolysiloxane composition was applied in the form of a bead to the center of the lower sealing surface in an amount sufficient to fully fill the sealing surface. Immediately after application, the upper vessel was placed on the lower vessel so that the sealing surfaces of the upper and lower flanges were in contact, a spacer 21.0 mm high was installed to define the distance between the sealing surfaces of the upper and lower flanges, and four tightening bolts were attached. After that, it is cured at 23°C and 50% RH for 30 minutes, and then pressurized gas is introduced from the upper pressure port, and the maximum gas pressure that the sealing material, which is the cured product of the above composition, can withstand is measured as the initial sealability (kPa).
更に、上記第１及び第２の実施形態のいずれにおいても、下記初期シール性試験方法で測定される、製造直後の室温硬化性オルガノポリシロキサン組成物の初期シール性に対する２３℃６ヶ月間保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性の保持率が８０％以上である室温硬化性オルガノポリシロキサン組成物を製造するものであることが好ましい。
なお、製造直後の室温硬化性オルガノポリシロキサン組成物の初期シール性Ｐ１に対する２３℃６ヶ月間保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性Ｐ３の保持率は以下の式で求められる（以下、同じ）。
（保持率）＝Ｐ３／Ｐ１×１００（％）
Furthermore, in both the first and second embodiments, it is preferable to produce a room-temperature-curable organopolysiloxane composition in which the retention of the initial sealability of the room-temperature-curable organopolysiloxane composition after storage at 23° C. for 6 months is 80% or more relative to the initial sealability of the room-temperature-curable organopolysiloxane composition immediately after production, as measured by the initial sealability test method described below.
The retention rate of the initial sealability P3 of a room-temperature-curable organopolysiloxane composition after storage at 23° C. for 6 months relative to the initial sealability P1 of the room-temperature-curable organopolysiloxane composition immediately after production is calculated using the following formula (the same applies hereinafter).
(Retention rate) = P3/P1 x 100 (%)
＜室温硬化性オルガノポリシロキサン組成物＞
上述した本発明の室温硬化性オルガノポリシロキサン組成物の製造方法で得られる本発明の室温硬化性オルガノポリシロキサン組成物は、第１の実施形態（一液型）及び第２の実施形態（二液型）のいずれにおいても、最終的な本発明の組成物の組成としては、
（Ａ）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～３０質量部、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～１５質量部、
（Ｒ1Ｏ）aＳｉＲ2
3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～１５質量部
を含有する室温硬化性オルガノポリシロキサン組成物であって、
上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で含む１００℃超１５０℃以下の加熱熟成混合物（Ｃ）として含有するものである。
<Room-temperature-curable organopolysiloxane composition>
In both the first embodiment (one-part type) and the second embodiment (two-part type) of the room-temperature-curable organopolysiloxane composition of the present invention obtained by the above-mentioned method for producing a room-temperature-curable organopolysiloxane composition of the present invention, the final composition of the composition of the present invention is as follows:
(A) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 30 parts by mass of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 15 parts by mass of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
(C-3) a room temperature curable organopolysiloxane composition containing 0.001 to 15 parts by mass of a curing catalyst,
The mixture (C) contains the above-mentioned components (C-1) and (C-2) in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5 and is aged at a temperature higher than 100° C. and not higher than 150° C.
ここで、（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））が１．７～３．５であり、好ましくは１．８～３．３である。 Here, the molar ratio ((C-1)/(C-2)) of the (C-1) component and the (C-2) component is 1.7 to 3.5, preferably 1.8 to 3.3.
また、上記（Ｃ－１）、（Ｃ－２）及び（Ｃ－３）成分を、該（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で含み、更に（Ｃ－３）成分を含む１００℃超１５０℃以下の加熱熟成混合物（Ｃ）として含有するものであることが好ましい。 It is also preferable that the above-mentioned (C-1), (C-2) and (C-3) components are contained as a heat-aged mixture (C) at a temperature higher than 100°C and not higher than 150°C, which contains the (C-1) component and the (C-2) component in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5 and further contains the (C-3) component.
本発明の室温硬化性オルガノポリシロキサン組成物において、下記初期シール性試験方法で測定される、製造直後の室温硬化性オルガノポリシロキサン組成物の初期シール性に対する４０℃２ヶ月間保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性の保持率が９０％以上であることが好ましく、９２％以上であることがより好ましい。
更に本発明の室温硬化性オルガノポリシロキサン組成物において、下記初期シール性試験方法で測定される、製造直後の室温硬化性オルガノポリシロキサン組成物の初期シール性に対する２３℃６ヶ月間保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性の保持率が８０％以上であることが好ましい。
In the room-temperature-curable organopolysiloxane composition of the present invention, the retention of the initial sealability of the room-temperature-curable organopolysiloxane composition after storage at 40° C. for 2 months relative to the initial sealability of the room-temperature-curable organopolysiloxane composition immediately after production, as measured by the initial sealability test method described below, is preferably 90% or more, and more preferably 92% or more.
Furthermore, in the room-temperature-curable organopolysiloxane composition of the present invention, it is preferred that the retention of the initial sealability of the room-temperature-curable organopolysiloxane composition after storage at 23° C. for 6 months relative to the initial sealability of the room-temperature-curable organopolysiloxane composition immediately after production, as measured by the initial sealability test method described below, is 80% or more.
［初期シール性試験方法］
試験装置としてＪＩＳ Ｋ ６８２０に規定されている耐圧試験用フランジ圧力容器に準ずる、内径５８ｍｍ、外径８０ｍｍ、厚さ１０ｍｍの上側フランジを有する上側容器と、上側フランジと同寸法の下側フランジを有する下側容器からなり、下側フランジのシール面のインナー側縁部には、幅３ｍｍ、深さ３ｍｍの環状の切り欠きが円周に沿って設けられている圧力容器を用い、該圧力容器の下側のフランジのシール面を洗浄した後、室温硬化性オルガノポリシロキサン組成物をシール面が十分に満たされるだけの塗布量で、下側のシール面中央部にビード状に塗布し、塗布後直ちに上側容器を上側フランジと下側フランジのシール面とが当接するように下側容器に載せ、上下フランジのシール面間の距離を規定するための高さ２１．０ｍｍのスペーサーを設置して４本の締め付けボルトを組み付ける。その後、２３℃、５０％ＲＨで３０分間硬化させた後、上側の加圧口から加圧気体を挿入し、上記組成物の硬化物であるシール材が耐えうる気体圧の最大値を初期シール性（ｋＰａ）として測定する。
[Initial sealability test method]
The test apparatus used was a pressure vessel conforming to the flanged pressure vessels for pressure tests specified in JIS K 6820, consisting of an upper vessel having an upper flange with an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange of the same dimensions as the upper flange, with a 3 mm wide and 3 mm deep annular notch provided around the circumference on the inner side edge of the sealing surface of the lower flange. After cleaning the sealing surface of the lower flange of the pressure vessel, a room-temperature-curable organopolysiloxane composition was applied in the form of a bead to the center of the lower sealing surface in an amount sufficient to fully fill the sealing surface. Immediately after application, the upper vessel was placed on the lower vessel so that the sealing surfaces of the upper and lower flanges were in contact, a spacer 21.0 mm high was installed to define the distance between the sealing surfaces of the upper and lower flanges, and four tightening bolts were attached. After that, it is cured at 23°C and 50% RH for 30 minutes, and then pressurized gas is introduced from the upper pressure port, and the maximum gas pressure that the sealing material, which is the cured product of the above composition, can withstand is measured as the initial sealability (kPa).
本発明の室温硬化性オルガノポリシロキサン組成物は、空気中に暴露されると、水分により架橋硬化され、ゴム状弾性体となる。
また得られた硬化物は良好な柔軟性を示し、ゴム弾性を有することから、本発明の室温硬化性オルガノポリシロキサン組成物からなる接着剤、あるいはシーリング材（例えば、建築用シーラント等）として有用である。本発明の室温硬化性オルガノポリシロキサン組成物を接着剤、シーリング材として使用する方法は、従来公知の使用方法に従えばよく、特に制限されるものでない。
本発明の室温硬化性オルガノポリシロキサン組成物の硬化物で接着及び／又はシールされる物品としては、例えば、ガラス類、各種金属類等で構成された物品などが例示できるが、基材の材質及び形状については特に限定されない。
When the room temperature curable organopolysiloxane composition of the present invention is exposed to air, it undergoes crosslinking and curing due to moisture, becoming a rubber-like elastomer.
In addition, the obtained cured product exhibits good flexibility and has rubber elasticity, and is therefore useful as an adhesive or sealant (e.g., a construction sealant) made from the room-temperature-curable organopolysiloxane composition of the present invention. The method of using the room-temperature-curable organopolysiloxane composition of the present invention as an adhesive or sealant may be any method known in the art and is not particularly limited.
Examples of articles that can be adhered and/or sealed with a cured product of the room-temperature-curable organopolysiloxane composition of the present invention include articles made of glass, various metals, etc., but there are no particular limitations on the material and shape of the substrate.
次に、実施例及び比較例を挙げて、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、下記例中の粘度は回転粘度計による２３℃での測定値である。 Next, the present invention will be specifically described with examples and comparative examples, but the present invention is not limited to the following examples. Note that the viscosity in the following examples is measured at 23°C using a rotational viscometer.
［実施例１］
分子鎖両末端が水酸基で封鎖され、粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン１００質量部、無処理の重質炭酸カルシウム１００質量部、煙霧質シリカ５質量部を均一になるまで混合した。次いで、ビニルトリス（メチルエチルケトオキシム）シラン７質量部、３－アミノプロピルトリエトキシシラン２質量部、ジブチルスズジラウレート０．３質量部を１０５℃×６時間加熱熟成させたものを加熱熟成混合物として添加し、減圧下で混合して、室温硬化性オルガノポリシロキサン組成物（組成物１）を得た。なお、本組成物におけるビニルトリス（メチルエチルケトオキシム）シランと３－アミノプロピルトリエトキシシランのモル比は２．５である。
[Example 1]
100 parts by mass of dimethylpolysiloxane with both molecular chain ends blocked with hydroxyl groups and a viscosity of 50,000 mPa·s, 100 parts by mass of untreated heavy calcium carbonate, and 5 parts by mass of fumed silica were mixed until uniform. Next, 7 parts by mass of vinyltris(methylethylketoxime)silane, 2 parts by mass of 3-aminopropyltriethoxysilane, and 0.3 parts by mass of dibutyltin dilaurate were added as a heat-aged mixture that had been heated and aged at 105°C for 6 hours, and mixed under reduced pressure to obtain a room temperature curable organopolysiloxane composition (composition 1). The molar ratio of vinyltris(methylethylketoxime)silane to 3-aminopropyltriethoxysilane in this composition was 2.5.
［実施例２］
実施例１の熟成条件を１２０℃×２時間に変えた以外は、実施例１と同じ条件にて調製し、組成物２を得た。
[Example 2]
Composition 2 was obtained by preparing the composition under the same conditions as in Example 1, except that the aging conditions in Example 1 were changed to 120° C.×2 hours.
［実施例３］
実施例１の熟成条件を１４０℃×２時間に変えた以外は、実施例１と同じ条件にて調製し、組成物３を得た。
[Example 3]
Composition 3 was obtained under the same conditions as in Example 1, except that the aging conditions in Example 1 were changed to 140° C.×2 hours.
［比較例１］
実施例１の熟成を行わずに加熱熟成混合物を構成する各成分を添加した以外は、実施例１と同じ条件にて調製し、組成物４を得た。
[Comparative Example 1]
Composition 4 was obtained by preparing the composition under the same conditions as in Example 1, except that the aging step in Example 1 was not carried out and each component constituting the heat-aged mixture was added.
［比較例２］
実施例１の熟成条件を７０℃×２４時間に変えた以外は、実施例１と同じ条件にて調製し、組成物５を得た。
[Comparative Example 2]
Composition 5 was obtained under the same conditions as in Example 1, except that the aging conditions in Example 1 were changed to 70° C.×24 hours.
調製した直後の組成物１～５を用いて、以下の初期シール性を測定した。また、保存性確認試験として、実施例及び比較例で調製された各組成物を密閉容器に入れて、４０℃で２ヶ月間放置（保管）したもの及び２３℃で６ヶ月間放置（保管）したものをそれぞれ同様に初期シール性を測定した。合わせて、調製（製造）直後の室温硬化性オルガノポリシロキサン組成物の初期シール性Ｐ１に対する上記保管後の室温硬化性オルガノポリシロキサン組成物の初期シール性（４０℃２ヶ月間保管後の初期シール性Ｐ２、２３℃６ヶ月間保管後の初期シール性Ｐ３）の保持率を以下の式で求めた。
（調製直後の初期シール性に対する４０℃２ヶ月間保管後の初期シール性の保持率）＝Ｐ２／Ｐ１×１００（％）
（調製直後の初期シール性に対する２３℃６ヶ月間保管後の初期シール性の保持率）＝Ｐ３／Ｐ１×１００（％）
これらの結果を表１に示す。
The following initial sealability was measured using compositions 1 to 5 immediately after preparation. In addition, as a storage stability test, each composition prepared in the Examples and Comparative Examples was placed in a sealed container, and left (stored) at 40° C. for 2 months and at 23° C. for 6 months, and the initial sealability was measured in the same manner. In addition, the retention rate of the initial sealability of the room-temperature curable organopolysiloxane composition after the above storage (initial sealability P2 after storage at 40° C. for 2 months, initial sealability P3 after storage at 23° C. for 6 months) relative to the initial sealability P1 of the room-temperature curable organopolysiloxane composition immediately after preparation (manufacture) was calculated by the following formula.
(Retention rate of initial sealability after storage at 40°C for 2 months relative to the initial sealability immediately after preparation) = P2/P1 x 100 (%)
(Retention rate of initial sealability after storage at 23°C for 6 months relative to the initial sealability immediately after preparation) = P3/P1 x 100 (%)
The results are shown in Table 1.
（初期シール性試験方法）
初期シール性（耐圧性）の試験方法は、試験装置としてＪＩＳ Ｋ ６８２０に規定されている耐圧試験用フランジ圧力容器に準ずる圧力容器を用い、耐圧試験を行った。該圧力容器は、内径５８ｍｍ、外径８０ｍｍ、厚さ１０ｍｍの上側フランジを有する上側容器と、上側フランジと同寸法の下側フランジを有する下側容器からなり、下側フランジのシール面のインナー側縁部には、幅３ｍｍ、深さ３ｍｍの環状の切り欠きが円周に沿って設けられている。この下側のフランジのシール面をトルエンにより洗浄した。その後、上記組成物をシール面が十分に満たされるだけの塗布量で、下側のシール面中央部にビード状に塗布した。塗布後直ちに、上側容器を、上側フランジと下側フランジのシール面とが当接するように、下側容器に載せ、上下フランジのシール面間の距離を規定するための（上記フランジの厚さ方向の）高さ２１．０ｍｍの鉄製スペーサーを設置して４本の締め付けボルトを組み付けた。当該スペーサーによりシール面間に１．０ｍｍの間隔が生じているが、これはシール材に対する耐圧試験をより過酷にする、いわゆる促進試験とするためである。その後、２３℃、５０％ＲＨで３０分間硬化させた後、上側の加圧口から加圧気体を挿入し、上記組成物の硬化物であるシール材が耐えうる気体圧の最大値を初期シール性（ｋＰａ）として測定した。
(Initial sealability test method)
The initial sealability (pressure resistance) test method was performed using a pressure vessel conforming to the flange pressure vessel for pressure resistance test specified in JIS K 6820 as a test device, and a pressure resistance test was performed. The pressure vessel was composed of an upper vessel having an upper flange with an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange with the same dimensions as the upper flange, and a ring-shaped notch with a width of 3 mm and a depth of 3 mm was provided along the circumference at the inner side edge of the seal surface of the lower flange. The seal surface of this lower flange was washed with toluene. Then, the composition was applied in a bead shape to the center of the lower seal surface in an amount sufficient to fully fill the seal surface. Immediately after application, the upper vessel was placed on the lower vessel so that the seal surfaces of the upper and lower flanges were in contact with each other, and an iron spacer with a height of 21.0 mm (in the thickness direction of the flange) to define the distance between the seal surfaces of the upper and lower flanges was installed, and four tightening bolts were installed. The spacer creates a gap of 1.0 mm between the sealing surfaces, which is intended to make the pressure resistance test for the sealant more severe, i.e., to perform a so-called accelerated test. After curing for 30 minutes at 23°C and 50% RH, pressurized gas was introduced from the upper pressure port, and the maximum gas pressure that the sealant, which is the cured product of the composition, could withstand was measured as the initial sealability (kPa).
上記結果から、本発明の室温硬化性オルガノポリシロキサン組成物は、調製直後から３０分という短時間の硬化時間にもかかわらず高い初期シール性を示し、更に４０℃で２ヶ月間保管、２３℃で６ヶ月間保管したものでも初期シール性に大きな低下は見られなかった。具体的には４０℃２ヶ月間保管後の初期シール性の保持率が９４％以上であり、２３℃６ヶ月間保管後の初期シール性の保持率が８８％以上であった。
一方、熟成をしていない比較例１では初期のシール性は高いものの保管後のものでは初期シール性が大きく低下し、保存安定性に劣る結果となった。また、比較例２では保管後の初期シール性の保持率の低下がみられ、４０℃２ヶ月間保管後の初期シール性の保持率が９０％未満であり、２３℃６ヶ月間保管後の初期シール性の保持率が８０％未満であった。また、比較例２では熟成時間が２４時間と長く、生産性に劣っていた。
From the above results, the room temperature curable organopolysiloxane composition of the present invention exhibited high initial sealability despite the short curing time of only 30 minutes immediately after preparation, and furthermore, no significant decrease in initial sealability was observed even after storage for 2 months at 40° C. or 6 months at 23° C. Specifically, the retention of initial sealability after storage at 40° C. for 2 months was 94% or more, and the retention of initial sealability after storage at 23° C. for 6 months was 88% or more.
On the other hand, in Comparative Example 1, which was not aged, the initial sealability was high, but after storage, the initial sealability was significantly reduced, resulting in poor storage stability. In Comparative Example 2, the retention of the initial sealability after storage was reduced, with the retention of the initial sealability being less than 90% after storage at 40°C for 2 months and less than 80% after storage at 23°C for 6 months. In Comparative Example 2, the aging time was long at 24 hours, and the productivity was poor.
［実施例４］
分子鎖両末端が水酸基で封鎖され、粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン１００質量部、無処理の重質炭酸カルシウム１００質量部、煙霧質シリカ５質量部を均一になるまで混合した。次いで、ビニルトリス（メチルエチルケトオキシム）シラン７質量部、３－アミノプロピルトリエトキシシラン２．７質量部、ジブチルスズジラウレート０．３質量部を１２０℃×２時間加熱熟成させたものを加熱熟成混合物として添加し、減圧下で混合して、室温硬化性オルガノポリシロキサン組成物（組成物６）を得た。なお、本組成物におけるビニルトリス（メチルエチルケトオキシム）シランと３－アミノプロピルトリエトキシシランのモル比は１．８である。
[Example 4]
100 parts by mass of dimethylpolysiloxane with both ends of the molecular chain blocked with hydroxyl groups and a viscosity of 50,000 mPa·s, 100 parts by mass of untreated heavy calcium carbonate, and 5 parts by mass of fumed silica were mixed until uniform. Next, 7 parts by mass of vinyltris(methylethylketoxime)silane, 2.7 parts by mass of 3-aminopropyltriethoxysilane, and 0.3 parts by mass of dibutyltin dilaurate were heated and aged at 120°C for 2 hours, and then added as a heat-aged mixture, and mixed under reduced pressure to obtain a room temperature curable organopolysiloxane composition (composition 6). The molar ratio of vinyltris(methylethylketoxime)silane to 3-aminopropyltriethoxysilane in this composition was 1.8.
［実施例５］
実施例４のビニルトリ（メチルエチルケトオキシム）シランと３－アミノプロピルトリエトキシシランのモル比が３．４なるように、３－アミノプロピルトリエトキシシランを１．５質量部に変えた以外は、実施例４と同じ条件にて調製し、組成物７を得た。
[Example 5]
Composition 7 was obtained by preparing under the same conditions as in Example 4, except that the amount of 3-aminopropyltriethoxysilane was changed to 1.5 parts by mass so that the molar ratio of vinyltri(methylethylketoxime)silane to 3-aminopropyltriethoxysilane in Example 4 was 3.4.
［実施例６］
分子鎖両末端が水酸基で封鎖され、粘度が５０，０００ｍＰａ・ｓのジメチルポリシロキサン１００質量部、脂肪酸で処理されたコロイダル炭酸カルシウム１００質量部、煙霧質シリカ３質量部を均一になるまで混合した。次いで、ビニルトリイソプロペノキシシラン５．５質量部、３－アミノプロピルトリエトキシシラン２質量部、１，１，３，３－テトラメチル－２－［３－（トリメトキシシリル）プロピル］グアニジン１質量部を１２０℃×２時間加熱熟成させたものを加熱熟成混合物として添加し、減圧下で混合して、組成物８を得た。なお、本組成物におけるビニルトリイソプロペノキシシランと３－アミノプロピルトリエトキシシランのモル比は２．７である。
[Example 6]
100 parts by mass of dimethylpolysiloxane with both ends of the molecular chain blocked with hydroxyl groups and a viscosity of 50,000 mPa·s, 100 parts by mass of colloidal calcium carbonate treated with a fatty acid, and 3 parts by mass of fumed silica were mixed until uniform. Next, 5.5 parts by mass of vinyltriisopropenoxysilane, 2 parts by mass of 3-aminopropyltriethoxysilane, and 1 part by mass of 1,1,3,3-tetramethyl-2-[3-(trimethoxysilyl)propyl]guanidine were heated and aged at 120°C for 2 hours, and then added as a heat-aged mixture, and mixed under reduced pressure to obtain composition 8. The molar ratio of vinyltriisopropenoxysilane to 3-aminopropyltriethoxysilane in this composition was 2.7.
［比較例３］
実施例４のビニルトリス（メチルエチルケトオキシム）シランと３－アミノプロピルトリエトキシシランのモル比が１．２となるように、３－アミノプロピルトリエトキシシランを４．０質量部に変え、更に熟成条件を７０℃×２４時間に変えた以外は、実施例４と同じ条件にて調製し、組成物９を得た。
[Comparative Example 3]
Composition 9 was obtained under the same conditions as in Example 4, except that the amount of 3-aminopropyltriethoxysilane was changed to 4.0 parts by mass so that the molar ratio of vinyltris(methylethylketoxime)silane to 3-aminopropyltriethoxysilane in Example 4 was 1.2, and the aging conditions were changed to 70°C x 24 hours.
［比較例４］
実施例４のビニルトリス（メチルエチルケトオキシム）シランと３－アミノプロピルトリエトキシシランのモル比が１．４となるように、ビニルトリス（メチルエチルケトオキシム）シランの使用量を変更した以外は、実施例４と同じ条件にて調製したが、途中でゲル化したため組成物化できなかった。
[Comparative Example 4]
The same conditions as in Example 4 were used for preparation, except that the amount of vinyltris(methylethylketoxime)silane used was changed so that the molar ratio of vinyltris(methylethylketoxime)silane to 3-aminopropyltriethoxysilane in Example 4 was 1.4. However, gelation occurred during the preparation, and the composition could not be prepared.
［比較例５］
実施例４のビニルトリス（メチルエチルケトオキシム）シランと３－アミノプロピルトリエトキシシランのモル比が３．９となるように、ビニルトリス（メチルエチルケトオキシム）シランの使用量を変更した以外は、実施例４と同じ条件にて調製し、組成物１１を得た。
[Comparative Example 5]
Composition 11 was obtained by preparing under the same conditions as in Example 4, except that the amount of vinyltris(methylethylketoxime)silane used was changed so that the molar ratio of vinyltris(methylethylketoxime)silane to 3-aminopropyltriethoxysilane in Example 4 was 3.9.
調製した組成物６～９及び１１を用いて、実施例１と同様にして、調製直後、４０℃２ヶ月間保管後、２３℃６ヶ月間保管後の初期シール性を測定し、合わせて各保管後の初期シール性の保持率を求めた。
得られた結果を表２に示す。
Using the prepared compositions 6 to 9 and 11, the initial sealability was measured immediately after preparation, after storage at 40°C for 2 months, and after storage at 23°C for 6 months in the same manner as in Example 1, and the retention rate of the initial sealability after each storage period was also calculated.
The results obtained are shown in Table 2.
上記結果から、本発明の室温硬化性オルガノポリシロキサン組成物は、調製直後から３０分という短時間の硬化時間にもかかわらず高い初期シール性を示し、更に４０℃で２ヶ月間保管、２３℃で６ヶ月間保管したものでも初期シール性に大きな低下は見られなかった。具体的には４０℃２ヶ月間保管後の初期シール性の保持率が９３％以上であり、２３℃６ヶ月間保管後の初期シール性の保持率が８１％以上であった。
一方、（Ｃ－１）／（Ｃ－２）モル比が本発明の範囲から外れる比較例３と比較例５では保存後にシール性が低下し、比較例３の４０℃２ヶ月間保管後の場合を除き測定が出来ない状態となった。また、比較例４は組成物化することが出来なかった。
From the above results, the room temperature curable organopolysiloxane composition of the present invention exhibited high initial sealability despite the short curing time of only 30 minutes immediately after preparation, and furthermore, no significant decrease in initial sealability was observed even after storage for 2 months at 40° C. or 6 months at 23° C. Specifically, the retention of initial sealability after storage at 40° C. for 2 months was 93% or more, and the retention of initial sealability after storage at 23° C. for 6 months was 81% or more.
On the other hand, in Comparative Examples 3 and 5, in which the (C-1)/(C-2) molar ratio was outside the range of the present invention, the sealability decreased after storage, and measurement was impossible except for the case after storage at 40° C. for 2 months in Comparative Example 3. In addition, in Comparative Example 4, it was not possible to form a composition.
［実施例７］
分子鎖両末端が水酸基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン１００質量部、無処理の重質炭酸カルシウム１００質量部、煙霧質シリカ５質量部を均一になるまで混合した。次いで、ビニルトリス（メチルエチルケトオキシム）シラン９質量部、３－アミノプロピルトリエトキシシラン２質量部、ジブチルスズジラウレート０．３質量部を１２０℃×２時間加熱熟成させて加熱熟成混合物としたもの、更にオクチルアミン３．２質量部を添加し、減圧下で混合して、第一液を得た。なお、本組成物におけるビニルトリス（メチルエチルケトオキシム）シランと３－アミノプロピルトリエトキシシランのモル比は３．２である。
また、分子鎖両末端が水酸基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン１００質量部、無処理の重質炭酸カルシウム１００質量部、煙霧質シリカ５質量部を均一になるまで混合した。次いでシクロヘキサノン２．４質量部を添加し、減圧下で混合して、第二液を得た。
上記第一液と第二液を、調製した直後、４０℃２ヶ月間保管した後、２３℃６ヶ月間保管した後に、それぞれ初期シール性を測定する直前に、質量比１００：１００で混合し、組成物１２を得た。
[Example 7]
100 parts by mass of dimethylpolysiloxane with both ends of the molecular chain blocked with hydroxyl groups and a viscosity of 20,000 mPa·s, 100 parts by mass of untreated heavy calcium carbonate, and 5 parts by mass of fumed silica were mixed until homogeneous. Next, 9 parts by mass of vinyltris(methylethylketoxime)silane, 2 parts by mass of 3-aminopropyltriethoxysilane, and 0.3 parts by mass of dibutyltin dilaurate were heated and aged at 120°C for 2 hours to obtain a heat-aged mixture, to which 3.2 parts by mass of octylamine were further added and mixed under reduced pressure to obtain a first liquid. The molar ratio of vinyltris(methylethylketoxime)silane to 3-aminopropyltriethoxysilane in this composition was 3.2.
100 parts by mass of dimethylpolysiloxane, both ends of which are capped with hydroxyl groups and having a viscosity of 20,000 mPa·s, 100 parts by mass of untreated heavy calcium carbonate, and 5 parts by mass of fumed silica were mixed until homogeneous, followed by the addition of 2.4 parts by mass of cyclohexanone and mixing under reduced pressure to obtain a second liquid.
The above first and second liquids were mixed in a mass ratio of 100:100 immediately after preparation, after storage at 40°C for 2 months, and after storage at 23°C for 6 months, and immediately before measuring the initial sealing property, to obtain composition 12.
［比較例６］
実施例７の第一液において熟成を行わずに加熱熟成混合物を構成する各成分を添加した以外は、実施例７と同じ条件にて第一液及び第二液を調製し、調製した直後、４０℃２ヶ月間保管した後、２３℃６ヶ月間保管した後に、それぞれ初期シール性を測定する直前に、質量比１００：１００で混合し、組成物１３を得た。
[Comparative Example 6]
The first and second liquids were prepared under the same conditions as in Example 7, except that no aging was performed in the first liquid of Example 7 and each component constituting the heat-aged mixture was added. Immediately after preparation, after storage at 40°C for 2 months, and after storage at 23°C for 6 months, the liquids were mixed in a mass ratio of 100:100 just before measuring the initial sealing property, to obtain composition 13.
調製した組成物１２、１３を用いて、調製直後、４０℃２ヶ月間保管後、２３℃６ヶ月間保管後の初期シール性を測定し、合わせて各保管後の初期シール性の保持率を求めた。
得られた結果を表３に示す。
The initial sealability of the prepared compositions 12 and 13 was measured immediately after preparation, after storage at 40° C. for 2 months, and after storage at 23° C. for 6 months, and the retention of the initial sealability after each storage period was also calculated.
The results obtained are shown in Table 3.
上記結果から、二液型の組成物でも本発明の室温硬化性オルガノポリシロキサン組成物は、調製直後から３０分という短時間の硬化時間にもかかわらず高い初期シール性を示し、更に４０℃で２ヶ月間保管、２３℃で６ヶ月間保管したものでも初期シール性に大きな低下は見られなかった。
一方、熟成していない比較例６は、保存安定性（保管後の初期シール性）が悪い結果となった。
From the above results, it can be seen that the room temperature curable organopolysiloxane composition of the present invention, even though it is a two-part composition, exhibits high initial sealability despite the short curing time of only 30 minutes immediately after preparation, and furthermore, no significant decrease in initial sealability was observed even after storage at 40°C for 2 months or at 23°C for 6 months.
On the other hand, Comparative Example 6, which was not aged, showed poor storage stability (initial sealability after storage).
Claims (8)
（Ｂ）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～３０質量部、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～１５質量部、
（Ｒ1Ｏ）aＳｉＲ2 3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～１５質量部
を含有する室温硬化性オルガノポリシロキサン組成物の製造方法であって、
上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、更に上記（Ｃ－３）成分を添加し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を（Ａ）成分、（Ｂ）成分に添加するものである室温硬化性オルガノポリシロキサン組成物の製造方法。 (A) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 30 parts by mass of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 15 parts by mass of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
A method for producing a room-temperature-curable organopolysiloxane composition comprising: (C-3) 0.001 to 15 parts by mass of a curing catalyst,
A method for producing a room-temperature curable organopolysiloxane composition, comprising mixing the above-mentioned components (C-1) and (C-2) in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, adding the above-mentioned component (C-3), and heat-aging the mixture at a temperature higher than 100°C and not higher than 150°C for 30 minutes to 24 hours to obtain a heat-aged mixture (C), and adding this heat-aged mixture (C) to components (A) and (B).
［第一液調製工程］
（Ａ－１）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ－１）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～６０質量部、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～３０質量部、
（Ｒ1Ｏ）aＳｉＲ2 3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～３０質量部
を含有する第一液の調製工程であって、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で混合し、更に上記（Ｃ－３）成分を添加し、１００℃超１５０℃以下で３０分～２４時間加熱熟成させて加熱熟成混合物（Ｃ）とし、該加熱熟成混合物（Ｃ）を（Ａ－１）成分、（Ｂ－１）成分に添加して第一液を調製する。
［第二液調製工程］
（Ａ－２）ケイ素原子に結合した水酸基を分子鎖両末端に有するジオルガノポリシロキサン １００質量部、
（Ｂ－２）充填剤 ０．１～８００質量部
を混合して第二液を調製する（ただし、上記（Ｃ－１）、（Ｃ－２）、（Ｃ－３）成分を添加しない）。 The method for producing a two-part mixing type room temperature curable organopolysiloxane composition includes the steps of preparing a first liquid and preparing a second liquid, and further mixing the first liquid and the second liquid in a mass ratio of 100:10 to 100:100 to obtain a room temperature curable organopolysiloxane composition (wherein, relative to 100 parts by mass of the combined total of components (A-1) and (A-2) below, the combined amount of components (B-1) and (B-2) is 0.1 to 800 parts by mass, the combined amount of component (C-1) is 0.5 to 30 parts by mass, the combined amount of component (C-2) is 0.1 to 15 parts by mass, and the combined amount of component (C-3) is 0.001 to 15 parts by mass) .
[First liquid preparation step]
(A-1) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B-1) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 60 parts by mass of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 30 parts by mass of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
A step of preparing a first liquid containing 0.001 to 30 parts by mass of a curing catalyst (C-3), in which the above-mentioned components (C-1) and (C-2) are mixed in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, the above-mentioned component (C-3) is further added, and the mixture is heated and aged at a temperature higher than 100° C. and not higher than 150° C. for 30 minutes to 24 hours to obtain a heat-aged mixture (C), and the heat-aged mixture (C) is added to the components (A-1) and (B-1) to prepare the first liquid.
[Second liquid preparation step]
(A-2) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B-2) 0.1 to 800 parts by mass of a filler is mixed to prepare a second liquid (without adding the above components (C-1), (C-2), and (C-3)).
［初期シール性試験方法］
試験装置としてＪＩＳ Ｋ ６８２０に規定されている耐圧試験用フランジ圧力容器に準ずる、内径５８ｍｍ、外径８０ｍｍ、厚さ１０ｍｍの上側フランジを有する上側容器と、上側フランジと同寸法の下側フランジを有する下側容器からなり、下側フランジのシール面のインナー側縁部には、幅３ｍｍ、深さ３ｍｍの環状の切り欠きが円周に沿って設けられている圧力容器を用い、該圧力容器の下側のフランジのシール面を洗浄した後、室温硬化性オルガノポリシロキサン組成物をシール面が十分に満たされるだけの塗布量で、下側のシール面中央部にビード状に塗布し、塗布後直ちに上側容器を上側フランジと下側フランジのシール面とが当接するように下側容器に載せ、上下フランジのシール面間の距離を規定するための高さ２１．０ｍｍのスペーサーを設置して４本の締め付けボルトを組み付ける。その後、２３℃、５０％ＲＨで３０分間硬化させた後、上側の加圧口から加圧気体を挿入し、上記組成物の硬化物であるシール材が耐えうる気体圧の最大値を初期シール性（ｋＰａ）として測定する。 3. The method for producing a room-temperature-curable organopolysiloxane composition according to claim 1 or 2, which produces a room-temperature-curable organopolysiloxane composition in which the retention of the initial sealability of the room-temperature-curable organopolysiloxane composition after storage at 40°C for 2 months is 90% or more relative to the initial sealability of the room-temperature-curable organopolysiloxane composition immediately after production, as measured by the initial sealability test method described below.
[Initial sealability test method]
The test apparatus used was a pressure vessel conforming to the flanged pressure vessels for pressure tests specified in JIS K 6820, consisting of an upper vessel having an upper flange with an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange of the same dimensions as the upper flange, with a 3 mm wide and 3 mm deep annular notch provided around the circumference on the inner side edge of the sealing surface of the lower flange. After cleaning the sealing surface of the lower flange of the pressure vessel, a room-temperature-curable organopolysiloxane composition was applied in the form of a bead to the center of the lower sealing surface in an amount sufficient to fully fill the sealing surface. Immediately after application, the upper vessel was placed on the lower vessel so that the sealing surfaces of the upper and lower flanges were in contact, a spacer 21.0 mm high was installed to define the distance between the sealing surfaces of the upper and lower flanges, and four tightening bolts were attached. After that, it is cured at 23°C and 50% RH for 30 minutes, and then pressurized gas is introduced from the upper pressure port, and the maximum gas pressure that the sealing material, which is the cured product of the above composition, can withstand is measured as the initial sealability (kPa).
（Ｂ）充填剤 ０．１～８００質量部、
（Ｃ－１） ケトオキシムシラン類、アシロキシシラン類、アルケノキシシラン類及びラクタートシラン類から選ばれる一分子中に３個以上の加水分解性基を含有する加水分解性オルガノシラン及び／又はその部分加水分解縮合物 ０．５～３０質量部、
（Ｃ－２） （Ｃ－１）成分以外の、下記一般式（１）で示されるシランカップリング剤及び／又はその部分加水分解縮合物 ０．１～１５質量部、
（Ｒ1Ｏ）aＳｉＲ2 3-aＲ3 （１）
（式中、Ｒ1、Ｒ2はそれぞれ独立に炭素数１～１０の非置換１価炭化水素基であり、Ｒ3は窒素原子、硫黄原子及び酸素原子から選ばれる少なくとも１種のヘテロ原子を含有する官能性基（ただし、グアニジル基を除く）で置換された炭素数１～１０の置換１価炭化水素基であり、ａは２又は３である。）
（Ｃ－３）硬化触媒 ０．００１～１５質量部
を含有する室温硬化性オルガノポリシロキサン組成物であって、
上記（Ｃ－１）、（Ｃ－２）及び（Ｃ－３）成分を、加熱熟成混合物（Ｃ）として含有し、
上記加熱熟成混合物（Ｃ）は、上記（Ｃ－１）成分と（Ｃ－２）成分をモル比（（Ｃ－１）／（Ｃ－２））１．７～３．５の割合で含み、更に（Ｃ－３）成分を含む１００℃超１５０℃以下で３０分～２４時間の加熱熟成混合物（Ｃ）である、室温硬化性オルガノポリシロキサン組成物。 (A) 100 parts by mass of a diorganopolysiloxane having hydroxyl groups bonded to silicon atoms at both molecular chain terminals,
(B) Filler: 0.1 to 800 parts by mass,
(C-1) 0.5 to 30 parts by mass of a hydrolyzable organosilane containing three or more hydrolyzable groups in one molecule selected from ketoximesilanes, acyloxysilanes, alkenoxysilanes, and lactatosilanes, and/or a partial hydrolysis condensate thereof,
(C-2) 0.1 to 15 parts by mass of a silane coupling agent represented by the following general formula (1) and/or a partial hydrolysis condensate thereof other than the component (C-1),
(R 1 O) a SiR 2 3-a R 3 (1)
(In the formula, R 1 and R 2 are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R 3 is a substituted monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a functional group (excluding a guanidyl group) containing at least one heteroatom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and a is 2 or 3.)
(C-3) a room temperature curable organopolysiloxane composition containing 0.001 to 15 parts by mass of a curing catalyst,
The above components (C-1), (C-2) and (C-3) are contained as a heat-ripened mixture (C),
The heat-aged mixture (C) is a room- temperature-curable organopolysiloxane composition that contains the above-mentioned components (C-1) and (C-2) in a molar ratio ((C-1)/(C-2)) of 1.7 to 3.5, and further contains component (C-3), and is heated to a temperature higher than 100° C. and not higher than 150° C. for 30 minutes to 24 hours.
［初期シール性試験方法］
試験装置としてＪＩＳ Ｋ ６８２０に規定されている耐圧試験用フランジ圧力容器に準ずる、内径５８ｍｍ、外径８０ｍｍ、厚さ１０ｍｍの上側フランジを有する上側容器と、上側フランジと同寸法の下側フランジを有する下側容器からなり、下側フランジのシール面のインナー側縁部には、幅３ｍｍ、深さ３ｍｍの環状の切り欠きが円周に沿って設けられている圧力容器を用い、該圧力容器の下側のフランジのシール面を洗浄した後、室温硬化性オルガノポリシロキサン組成物をシール面が十分に満たされるだけの塗布量で、下側のシール面中央部にビード状に塗布し、塗布後直ちに上側容器を上側フランジと下側フランジのシール面とが当接するように下側容器に載せ、上下フランジのシール面間の距離を規定するための高さ２１．０ｍｍのスペーサーを設置して４本の締め付けボルトを組み付ける。その後、２３℃、５０％ＲＨで３０分間硬化させた後、上側の加圧口から加圧気体を挿入し、上記組成物の硬化物であるシール材が耐えうる気体圧の最大値を初期シール性（ｋＰａ）として測定する。 5. The room-temperature-curable organopolysiloxane composition according to claim 4, wherein the retention of the initial sealability of the room-temperature-curable organopolysiloxane composition after storage at 40°C for two months is 90% or more relative to the initial sealability of the room-temperature-curable organopolysiloxane composition immediately after production, as measured by the initial sealability test method described below.
[Initial sealability test method]
The test apparatus used was a pressure vessel conforming to the flanged pressure vessels for pressure tests specified in JIS K 6820, consisting of an upper vessel having an upper flange with an inner diameter of 58 mm, an outer diameter of 80 mm, and a thickness of 10 mm, and a lower vessel having a lower flange of the same dimensions as the upper flange, with a 3 mm wide and 3 mm deep annular notch provided around the circumference on the inner side edge of the sealing surface of the lower flange. After cleaning the sealing surface of the lower flange of the pressure vessel, a room-temperature-curable organopolysiloxane composition was applied in the form of a bead to the center of the lower sealing surface in an amount sufficient to fully fill the sealing surface. Immediately after application, the upper vessel was placed on the lower vessel so that the sealing surfaces of the upper and lower flanges were in contact, a spacer 21.0 mm high was installed to define the distance between the sealing surfaces of the upper and lower flanges, and four tightening bolts were attached. After that, it is cured at 23°C and 50% RH for 30 minutes, and then pressurized gas is introduced from the upper pressure port, and the maximum gas pressure that the sealing material, which is the cured product of the above composition, can withstand is measured as the initial sealability (kPa).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010209269A (en) | 2009-03-12 | 2010-09-24 | Shin-Etsu Chemical Co Ltd | Room temperature curable organopolysiloxane composition, method for producing the same, and automobile oil seal |
| JP2012036252A (en) | 2010-08-04 | 2012-02-23 | Shin-Etsu Chemical Co Ltd | Room temperature-curable organopolysiloxane composition and vehicle oil seal |
| CN103342715A (en) | 2013-07-26 | 2013-10-09 | 北京天山新材料技术股份有限公司 | Preparation method of aminopropyl-containing organic oximido-silicon compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS578247A (en) * | 1980-06-17 | 1982-01-16 | Toshiba Silicone Co Ltd | Room temperature curable polyorganosiloxane composition |
| WO1986005797A1 (en) * | 1985-04-04 | 1986-10-09 | Loctite Corporation | Auto-adhering one-component rtv silicone sealant composition utilizing glycidoxyalkyl substituted alkoxy-oxime silane as an adhesion promoter |
| US4701380A (en) * | 1987-01-02 | 1987-10-20 | Dow Corning Corporation | Curable silicone composition for corrosion protection |
| US5569750A (en) * | 1994-05-24 | 1996-10-29 | Alliedsignal Inc. | RTV silicone compositions using aminohydrocarbyl-substituted ketoximinosilanes |
| JPH09241510A (en) * | 1996-03-06 | 1997-09-16 | Toshiba Silicone Co Ltd | Room temperature curable polyorganosiloxane composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010209269A (en) | 2009-03-12 | 2010-09-24 | Shin-Etsu Chemical Co Ltd | Room temperature curable organopolysiloxane composition, method for producing the same, and automobile oil seal |
| JP2012036252A (en) | 2010-08-04 | 2012-02-23 | Shin-Etsu Chemical Co Ltd | Room temperature-curable organopolysiloxane composition and vehicle oil seal |
| CN103342715A (en) | 2013-07-26 | 2013-10-09 | 北京天山新材料技术股份有限公司 | Preparation method of aminopropyl-containing organic oximido-silicon compound |
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