WO2023234084A1 - Two-pack type room temperature curable organopolysiloxane composition and various articles containing said composition - Google Patents
Two-pack type room temperature curable organopolysiloxane composition and various articles containing said composition Download PDFInfo
- Publication number
- WO2023234084A1 WO2023234084A1 PCT/JP2023/018853 JP2023018853W WO2023234084A1 WO 2023234084 A1 WO2023234084 A1 WO 2023234084A1 JP 2023018853 W JP2023018853 W JP 2023018853W WO 2023234084 A1 WO2023234084 A1 WO 2023234084A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- carbon atoms
- groups
- room temperature
- mass
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 70
- -1 organosilane compound Chemical class 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- SRNLFSKWPCUYHC-UHFFFAOYSA-N ethynylsilane Chemical group [SiH3]C#C SRNLFSKWPCUYHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 11
- 125000000468 ketone group Chemical group 0.000 claims abstract description 5
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 56
- 238000002156 mixing Methods 0.000 claims description 21
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- 239000000565 sealant Substances 0.000 claims description 9
- 230000000704 physical effect Effects 0.000 claims description 7
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 9
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 14
- 238000009833 condensation Methods 0.000 abstract description 8
- 230000005494 condensation Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 125000005372 silanol group Chemical group 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 239000007859 condensation product Substances 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 25
- 150000002430 hydrocarbons Chemical group 0.000 description 24
- 239000004205 dimethyl polysiloxane Substances 0.000 description 19
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 19
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 239000004945 silicone rubber Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229920005601 base polymer Polymers 0.000 description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 229920002379 silicone rubber Polymers 0.000 description 8
- 125000005370 alkoxysilyl group Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 7
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 7
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 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 5
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 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 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- OACYKCIZDVVNJL-UHFFFAOYSA-N 3-Methyl-1,2-cyclopentanedione Chemical compound CC1CCC(=O)C1=O OACYKCIZDVVNJL-UHFFFAOYSA-N 0.000 description 2
- MVLRILUUXLBENA-UHFFFAOYSA-N 4-methylheptan-3-one Chemical compound CCCC(C)C(=O)CC MVLRILUUXLBENA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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 group CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 125000002960 margaryl 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])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 2
- 238000005259 measurement Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- NAQQTJZRCYNBRX-UHFFFAOYSA-N n-pentan-3-ylidenehydroxylamine Chemical group CCC(CC)=NO NAQQTJZRCYNBRX-UHFFFAOYSA-N 0.000 description 2
- 125000001196 nonadecyl 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])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])[H] 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 125000000913 palmityl 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])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
- 125000002958 pentadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 125000004079 stearyl 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])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])[H] 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- HEXHLHNCJVXPNU-UHFFFAOYSA-N 2-(trimethoxysilylmethyl)butane-1,4-diamine Chemical compound CO[Si](OC)(OC)CC(CN)CCN HEXHLHNCJVXPNU-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- ZYXNLVMBIHVDRH-UHFFFAOYSA-N 2-Methylpropyl 3-oxobutanoate Chemical compound CC(C)COC(=O)CC(C)=O ZYXNLVMBIHVDRH-UHFFFAOYSA-N 0.000 description 1
- PPTKUTYPOKHBTL-UHFFFAOYSA-N 2-ethylcyclopentan-1-one Chemical compound CCC1CCCC1=O PPTKUTYPOKHBTL-UHFFFAOYSA-N 0.000 description 1
- JQPFYXFVUKHERX-UHFFFAOYSA-N 2-hydroxy-2-cyclohexen-1-one Natural products OC1=CCCCC1=O JQPFYXFVUKHERX-UHFFFAOYSA-N 0.000 description 1
- 239000001837 2-hydroxy-3-methylcyclopent-2-en-1-one Substances 0.000 description 1
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 description 1
- JSYAQLZSGHPSJD-UHFFFAOYSA-N 3,3-dimethylcyclopentan-1-one Chemical compound CC1(C)CCC(=O)C1 JSYAQLZSGHPSJD-UHFFFAOYSA-N 0.000 description 1
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 1
- GOJOGRCNYATXLQ-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](OC(C)=C)(OC(C)=C)CCCOCC1CO1 GOJOGRCNYATXLQ-UHFFFAOYSA-N 0.000 description 1
- UJBOOUHRTQVGRU-UHFFFAOYSA-N 3-methylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1 UJBOOUHRTQVGRU-UHFFFAOYSA-N 0.000 description 1
- AOKRXIIIYJGNNU-UHFFFAOYSA-N 3-methylcyclopentan-1-one Chemical compound CC1CCC(=O)C1 AOKRXIIIYJGNNU-UHFFFAOYSA-N 0.000 description 1
- PRRBQHNMYJRHFW-UHFFFAOYSA-M 3-oxoheptanoate Chemical compound CCCCC(=O)CC([O-])=O PRRBQHNMYJRHFW-UHFFFAOYSA-M 0.000 description 1
- BDCLDNALSPBWPQ-UHFFFAOYSA-M 3-oxohexanoate Chemical compound CCCC(=O)CC([O-])=O BDCLDNALSPBWPQ-UHFFFAOYSA-M 0.000 description 1
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- CCCIYAQYQZQDIZ-UHFFFAOYSA-N 6-methylheptan-3-one Chemical compound CCC(=O)CCC(C)C CCCIYAQYQZQDIZ-UHFFFAOYSA-N 0.000 description 1
- REIYHFWZISXFKU-UHFFFAOYSA-N Butyl acetoacetate Chemical compound CCCCOC(=O)CC(C)=O REIYHFWZISXFKU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 1
- CIISBNCSMVCNIP-UHFFFAOYSA-N cyclopentane-1,2-dione Chemical compound O=C1CCCC1=O CIISBNCSMVCNIP-UHFFFAOYSA-N 0.000 description 1
- LOGSONSNCYTHPS-UHFFFAOYSA-N cyclopentane-1,3-dione Chemical compound O=C1CCC(=O)C1 LOGSONSNCYTHPS-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WOPKYMRPOKFYNI-UHFFFAOYSA-N hydroxycyclopentenone Natural products OC1=CCCC1=O WOPKYMRPOKFYNI-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide 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
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- OKXJFBREZUPSGZ-UHFFFAOYSA-N n'-benzyl-n'-(3-trimethoxysilylpropyl)methanediamine Chemical compound CO[Si](OC)(OC)CCCN(CN)CC1=CC=CC=C1 OKXJFBREZUPSGZ-UHFFFAOYSA-N 0.000 description 1
- HZGIOLNCNORPKR-UHFFFAOYSA-N n,n'-bis(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCC[Si](OC)(OC)OC HZGIOLNCNORPKR-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 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
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical compound [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
Definitions
- the present invention provides a room-temperature-curable organopolysiloxane composition (room-temperature-curable silicone rubber) that is cured at room temperature (23°C ⁇ 15°C) by atmospheric humidity (moisture) to give a cured silicone rubber product (silicone elastomer elastomer).
- the composition relates to a hydrolyzed polysiloxane having two hydrolyzable silyl-vinylene groups on the same silicon atom, using as a base polymer an organopolysiloxane in which both ends of the molecular chain are capped with hydrolyzable silyl groups.
- the first agent is a degradable organosilane compound as a crosslinking agent (curing agent)
- the base polymer is an organopolysiloxane in which both ends of the molecular chain are blocked with hydroxyl groups to produce a specific hydrolyzable organosilane containing an amino functional group.
- a two-component room temperature curable organopolysiloxane composition that has good curability (fast curability) and excellent adhesiveness, and is capable of providing a cured silicone rubber product that is highly durable even under moist heat conditions;
- the present invention also relates to adhesives, sealants, and coatings containing the composition.
- Room-temperature-curing (RTV) silicone rubber compositions room-temperature-curing organopolysiloxane compositions that crosslink and harden when exposed to moisture are easy to handle and have excellent weather resistance and electrical properties, so they are used as sealants for building materials. It is suitable for a variety of uses such as materials, adhesives and coating agents (sealants) in the electrical and electronic fields.
- a typical room-temperature curable organopolysiloxane composition consists of a diorganopolysiloxane (base polymer) having a silanol group (a hydroxyl group bonded to a silicon atom) or an alkoxysilyl group at the end of the molecular chain, a curing agent, an alkoxysiloxane group containing an aminoalkyl group, etc. It contains silane and a curing catalyst, and various fillers are added as necessary to impart flame retardancy, thermal conductivity, tensile strength, etc.
- Oxime-free room-temperature-curable organopolysiloxane compositions known as general architectural and structural sealants, are widely used due to their curability, durability, and adhesion to various adherends.
- acetic acid-depleted room-temperature-curable organopolysiloxane compositions are commonly used as sealants for buildings and structures, and are known to have excellent curability and adhesive properties, and to show slight discoloration when exposed to UV irradiation.
- workability is poor due to acetic acid generated during curing.
- a dealcoholization type room temperature curable organopolysiloxane composition is not easy to prepare compared to the above-mentioned oxime removal type or acetic acid removal type room temperature curable organopolysiloxane composition.
- an organopolysiloxane having silanol groups at both ends of the molecular chain is used as a base polymer, it is necessary to alkoxysilylate the silanol groups (terminate them with an alkoxysilyl group), but the reaction rate is slower than that of the above-mentioned deoxime type.
- An organic tin compound or an organic titanium compound is generally known as a curing catalyst for a dealcoholization type room temperature curable organopolysiloxane composition.
- organic tin compounds there are concerns about their adverse effects on the environment and the human body due to their toxicity.
- organic titanium compounds although no toxicity problems have been confirmed yet, there are still problems such as the prepared room-temperature-curable organopolysiloxanes turning yellow over time.
- Typical examples of dealcoholization-type room-temperature-curable organopolysiloxanes include compositions containing a silanol group-terminated polyorganosiloxane, an alkoxysilane, and an organic titanium compound, and an alkoxysilyl group-terminated polyorganosiloxane, an alkoxysilane, and an alkoxytitanium compound.
- a composition comprising a linear polyorganosiloxane terminal-capped with an alkoxysilyl group via a silethylene group, an alkoxysilane, and an alkoxytitanium, further comprising a silanol-terminated polyorganosiloxane or Examples include compositions containing an alkoxysilyl end-capped polyorganosiloxane and an alkoxy- ⁇ -silyl ester compound (Patent Documents 1 to 4).
- the room-temperature-curable organopolysiloxanes described in these patent documents have a certain degree of storage stability, water resistance, and humidity resistance, but do not yet satisfy all of these required properties. Furthermore, the fast curing properties were still insufficient.
- Patent Document 5 discloses a dealcoholization-type room-temperature-curable organosiloxane composition, which uses an organosilane compound having a hydrolyzable silyl-vinylene group as a crosslinking agent, and is a two-component type with excellent fast curing properties.
- organosiloxane composition that cures quickly at mold room temperature. Although there is discussion about quick curing properties, there is no discussion about durability to cured rubber.
- the purpose of the present invention is to provide excellent fast curing and adhesive properties as well as good durability without adding metal condensation catalysts that have a large environmental impact and are commonly used in conventional room temperature curable organopolysiloxane compositions.
- An object of the present invention is to provide a two-component room-temperature-curable organopolysiloxane composition, an adhesive, a sealing agent, and a coating agent that can provide a cured product having (heat resistance, moisture resistance).
- the main material is an organopolysiloxane in which both ends of the molecular chain are capped with hydrolyzable silyl groups with or without sylalkylene groups.
- the first agent is a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom as a crosslinking agent (curing agent), and the organosilane compound has two hydrolyzable silyl-vinylene groups on the same silicon atom.
- Polysiloxane is used as the main agent (base polymer), a specific amino-functional group-containing hydrolyzable organosilane compound is blended as a condensation catalyst, and a second component is further blended with an organic compound having a ketone group in a specific compounding ratio.
- RTV room temperature curable
- the present invention provides the following two-component room temperature curable organopolysiloxane composition, adhesive, sealant, and coating agent.
- R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms
- n is a number of 10 or more
- X is independently an oxygen atom or a halogen-substituted monovalent hydrocarbon group having 1 to 4 carbon atoms.
- R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is independently 0 or 1 for each bonded silicon atom.
- B 0.1 to 10 parts by mass of a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom represented by the following general formula (2), (In the formula, R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 is independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 3 to 20 carbon atoms.
- Y represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms containing two or more nitrogen atoms in its structure
- Z represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms that may contain a hetero atom.
- R is one or more selected from a hydrolyzable group having 1 to 6 carbon atoms and a monovalent hydrocarbon group having 1 to 6 carbon atoms. It is a monovalent group, and among the three R's bonded to the silicon atom, at least two R's are hydrolyzable groups.
- the present invention aims to provide a cured product with durability (heat resistance, moisture resistance) without adding a metal condensation catalyst that has a large environmental impact and is commonly used in conventional room temperature curable organopolysiloxane compositions. It is possible to provide a two-component room temperature curable (RTV) silicone rubber composition with excellent fast curing properties and adhesive properties. Accordingly, the compositions of the present invention are useful as adhesives, sealants, and coatings.
- Component (A) of the organopolysiloxane composition of the present invention acts as a main agent (base polymer) in the composition of the present invention, and is represented by the following general formula (1), and has both ends of the molecular chain silyl.
- Hydrolysis that has an organooxy group bonded to two or three silicon atoms as a hydrolyzable group through an alkylene group (when X is an alkylene group) or without (when X is an oxygen atom) It is a linear organopolysiloxane blocked with silyl groups.
- R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms
- n is a number of 10 or more
- X is independently an oxygen atom or a halogen-substituted monovalent hydrocarbon group having 1 to 4 carbon atoms.
- It is an alkylene group
- R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms
- a is independently 0 or 1 for each bonded silicon atom.
- R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group.
- alkyl groups such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group; cyclopentyl group , cycloalkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group; phenyl group, tolyl group, xylyl group, ⁇ - , ⁇ -naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and groups in which the hydrogen
- n in the above formula (1) is a number of 10 or more, preferably a number of 10 to 2,000, more preferably a number of 20 to 1,500, even more preferably a number of 30 to 1,000, and a number of 50 to 1,000. A number of 800 is particularly preferred.
- the value of n is a number such that the viscosity of the diorganopolysiloxane of component (A) at 23°C is in the range of 25 to 500,000 mPa ⁇ s, preferably in the range of 500 to 100,000 mPa ⁇ s. It is preferable.
- n( which is the repeating number of bifunctional diorganosiloxane units represented by ((R 1 ) 2 SiO 2/2 ) constituting the main chain of the diorganopolysiloxane of component (A)
- the degree of polymerization can usually be determined as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent. Further, the viscosity can usually be measured at 23° C. using a rotational viscometer (eg, BL type, BH type, BS type, cone plate type, rheometer, etc.).
- X is independently an oxygen atom or an alkylene group having 1 to 4 carbon atoms, and examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group.
- Straight-chain alkylene groups such as, and isomers thereof, such as branched alkylene groups such as propylene group (methylethylene group) and 2-methyl-trimethylene group, etc. are applicable.
- X an ethylene group is particularly preferable.
- ethylene group In the case of an ethylene group, it is very versatile because it can be easily produced by subjecting an ⁇ , ⁇ -divinyl-terminated organopolysiloxane to a hydrosilylation addition reaction of the corresponding hydrosilane in the presence of a metal catalyst.
- R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group.
- a is independently 0 or 1 for each bonded silicon atom, preferably 0.
- the linear organopolysiloxane having hydrolyzable silyl groups endblocked at both molecular chain ends of component (A) may be used alone or in combination of two or more.
- Component (B) of the organopolysiloxane composition of the present invention is a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom (i.e., Two silicon atoms of the hydrolyzable silyl group (-Si(R 3 ) b (OR 4 ) 3-b ) exist in the molecule, and the silicon atoms of the diorganosilylene group (-Si(R 3 )
- a hydrolyzable organotrisilane compound in which the silicon atom of 2- ) is linked with a vinylene group (-CH CH-), which acts as a crosslinking agent (curing agent) in the composition of the present invention. It is something.
- R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms
- R 4 is independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 3 to 20 carbon atoms. is an unsubstituted or substituted cycloalkyl group.
- b is an integer from 0 to 2.
- the substituted or unsubstituted monovalent hydrocarbon group of R 3 has about 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and is the same. or may be different, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group Alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group,
- Examples include groups substituted with halogen atoms, cyano groups, etc., such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group.
- groups substituted with halogen atoms, cyano groups, etc. such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group.
- methyl group, ethyl group, and phenyl group are preferable, and methyl group and phenyl group are particularly preferable from the viewpoint of availability, productivity, and cost.
- the unsubstituted or substituted alkyl group of R 4 has about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms, more preferably about 1 to 4 carbon atoms, and is, for example, a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group , dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and is, for example,
- the unsubstituted or substituted cycloalkyl group has about 3 to 20 carbon atoms, preferably about 4 to 8 carbon atoms, more preferably about 5 to 6 carbon atoms, and includes, for example, a cyclopentyl group and a cyclohexyl group. Further, some or all of the hydrogen atoms of these alkyl groups and cycloalkyl groups may be substituted with halogen atoms such as F, Cl, Br, etc., cyano groups, etc. Examples include propyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group. Among these, from the viewpoint of hydrolyzability, R 4 is preferably a methyl group or an ethyl group, and a methyl group is particularly preferable.
- b is each independently an integer of 0 to 2, but preferably 0 or 1 from the viewpoint of curability.
- component (B) is shown below.
- the hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom as component (B) is, for example, a silane having two ethynyl groups on the same silicon atom, and twice the mole of alkoxyhydrosilane.
- Hydrolyzable group-containing hydrosilanes such as the following can be easily produced by an addition reaction using a hydrosilylation reaction. This reaction formula is expressed, for example, by the following formula [1].
- the addition reaction catalyst used in adding the alkoxyhydrosilane includes platinum group metal catalysts, such as platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, with platinum-based catalysts being particularly preferred.
- platinum-based materials include platinum black, solid platinum supported on a carrier such as alumina or silica, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and an olefin, or a complex of platinum and vinylsiloxane. Examples include complexes of.
- the amount of platinum to be used may be a so-called catalytic amount, and for example, it can be used in a mass of 0.1 to 1,000 ppm, particularly 0.5 to 100 ppm in terms of platinum group metal, relative to the alkoxyhydrosilane.
- This reaction is generally carried out at a temperature of 50 to 120°C, particularly 60 to 100°C, for 0.5 to 12 hours, particularly 1 to 6 hours, and can be carried out without using a solvent, but as mentioned above.
- An appropriate solvent such as toluene or xylene may be used as necessary, as long as it does not adversely affect the addition reaction.
- component (B) used in the present invention also has Z-form (cis-form), which does not adversely affect its properties, so these can be separated. It can be used without.
- hydrolyzable organosilane compounds having two hydrolyzable silyl-vinylene groups such as alkoxysilyl-vinylene groups on the same silicon atom in the general formula (2) are, for example, those represented by the following structural formula:
- component (B) one type of these can be used alone or two or more types can be used in combination.
- the hydrolyzable organosilane compound as component (B) is used in an amount of 0.1 to 10 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of organopolysiloxane as component (A). If it is less than 0.1 parts by mass, sufficient crosslinking will not be obtained and the composition will not have the desired fast-curing properties, and if it exceeds 10 parts by mass, the mechanical properties of the resulting rubber will deteriorate, Problems such as being economically disadvantaged may occur. Note that the hydrolyzable organosilane compound as the component (B) may be used alone or in combination of two or more.
- the total amount of component (A) and component (B) in the first agent may be 100% by mass, but is preferably 20 to 95% by mass, more preferably 30 to 90% by mass. .
- Component (C) is a linear diorganopolysiloxane whose molecular chain ends are blocked with silanol groups (hydroxyl groups bonded to silicon atoms), and is the main component (base polymer) of the second component of the composition of the present invention. It acts as a.
- R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and specific examples are those exemplified for R 1 in general formula (1) of component (A). It is similar to n is a number of 10 or more, preferably a number of 10 to 2,000, more preferably a number of 50 to 1,500, and still more preferably a number of 100 to 1,000, particularly when the diorganopolysiloxane is heated at 23°C.
- the viscosity is 25 to 500,000 mPa ⁇ s, preferably 50 to 100,000 mPa ⁇ s, more preferably 100 to 50,000 mPa ⁇ s.
- the viscosity is a value measured at 23°C using a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer), etc.
- Component (C) may be used alone or in combination of two or more.
- Component (D) is an important compound that acts as a condensation catalyst in the present room temperature curable organopolysiloxane composition, and specifically contains 3 or more nitrogen atoms, preferably 3 to 6 nitrogen atoms in one molecule, More preferably a hydrolyzable organosilane compound containing 3 to 5 amino functional groups and/or a partially hydrolyzed condensate thereof, particularly a catalyst represented by the following general formula (4) or (4)'. Hydrolyzable organosilane compounds containing an amino functional group and/or partially hydrolyzed condensates thereof having a monovalent or divalent basic moiety (Y) that exhibits a function are preferred.
- Y represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms containing two or more nitrogen atoms in its structure, and Z does not contain a heteroatom.
- Z represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted or unsubstituted.
- R is one or more monovalent groups selected from a hydrolyzable group having 1 to 6 carbon atoms and a monovalent hydrocarbon group having 1 to 6 carbon atoms; At least two of R are hydrolyzable groups.
- the monovalent or divalent basic moiety (Y) that exhibits a catalytic function has 2 or more nitrogen atoms, preferably 2 to 5, or more, in its structure. It preferably represents a monovalent or divalent hydrocarbon group having 2 to 4 carbon atoms and having 1 to 15 carbon atoms, and among the basic moieties (Y), the monovalent group is, for example, represented by the following formula (5).
- divalent groups such as groups derived from 1,5,7-triazabicyclo[4.4.0]dec-5-ene include N-substituted or non-substituted groups represented by the following formula (6). Examples include substituted guanidyl groups. Note that in the following formulas (5) and (6), the wavy line portion indicates a bonding site with the nitrogen atom of formula (4) or formula (4)'.
- R 5 to R 8 each independently represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an aryl group, such as a methyl group
- examples include alkyl groups such as ethyl group and propyl group; cyclic alkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group and allyl group; and aryl groups such as phenyl group and tolyl group.
- methyl group, ethyl group, and phenyl group are preferred, and methyl group is particularly preferred.
- R 5 to R 8 may be the same or different.
- R is an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a vinyloxy group, an allyloxy group.
- an alkenyloxy group such as a propenoxy group, an isopropenoxy group, a ketoxime group such as a dimethylketoxime group, a diethylketoxime group, a methylethylketoxime group, an acyloxy group such as an acetoxy group, etc. having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms.
- hydrolyzable groups that is, groups that can bond to silicon atoms to form Si-O-C bonds
- alkyl groups such as methyl groups and ethyl groups
- alkenyl groups such as vinyl groups
- phenyl groups etc.
- at least two, preferably three R's are hydrolyzable groups.
- the hydrolyzable silyl group (-SiR 3 ) is, for example, trimethoxysilyl group, methyldimethoxysilyl group, vinyldimethoxysilyl group, phenyldimethoxysilyl group, trimethoxysilyl group, Alkoxysilyl group such as ethoxysilyl group; Penoxysilyl group: Ketoxime silyl groups such as tris(dimethylketoxime)silyl group, tris(diethylketoxime)silyl group, tris(ethylmethylketoxime)silyl group, and the like.
- Z is a straight chain, branched, carbon atom having 1 to 10 carbon atoms, particularly 3 to 6 carbon atoms, which may contain a hetero atom such as an oxygen atom or a nitrogen atom.
- it represents an unsubstituted or substituted divalent hydrocarbon group such as a cyclic alkylene group, alkenylene group, arylene group, or a combination thereof.
- Z examples include alkylene groups such as methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, and 2-methylpropylene group; arylene groups such as phenylene group; Examples include groups in which these alkylene groups and arylene groups are bonded, and the above-mentioned alkylene groups with intervening ketones, esters, amide, etc., but preferred are methylene groups, ethylene groups, trimethylene groups, propylene groups, and propylene groups via amide bonds. etc., and trimethylene group is particularly preferred.
- amino-functional group-containing hydrolyzable organosilane represented by general formula (4) or general formula (4)' include those shown by general formulas (7) to (12) below. can. Note that Me, Et, and Ph represent a methyl group, an ethyl group, and a phenyl group, respectively.
- the blending amount of component (D) is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (C). . If it is less than 0.1 part by mass, it may not function as the intended curing catalyst. If it exceeds 10 parts by mass, it is not preferable because it is disadvantageous in terms of cost and curability decreases.
- Component (E) is an organic compound (ketones) having a ketone group, and specific examples include linear ketone compounds such as acetone, 2-butanone, 3-pentanone, and 2-heptanone; methyl isobutyl ketone, 4- Branched ketone compounds such as methylhexan-2-one, 4-methylheptan-3-one, 6-methylheptan-3-one; cyclopentanone, cyclohexanone, cycloheptanone, 3-methylcyclopentan-1-one , 3,3-dimethylcyclopentan-1-one, 2-ethylcyclopentan-1-one, 3-methylcyclohexan-1-one, 4-methylcyclohexan-1-one, 2,5-dimethylcyclohexan-1-one Cyclic ketone compounds such as cyclopentane-1,3-dione, cyclopentane-1,2-dione, 3-methylcyclopentane-1,2-dione
- the blending amount of component (E) is 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.5 to 2 parts by mass, per 100 parts by mass of component (C). . If the amount is less than 0.1 part by mass, the desired curability may not be achieved. If it exceeds 5 parts by mass, it is not preferable because it is not only disadvantageous in terms of cost, but also causes strong bleeding and odor from the cured rubber.
- the total amount of component (C), component (D), and component (E) in the second agent may be 100% by mass, but preferably 20 to 95% by mass, and 30 to 90% by mass. It is more preferable that there be.
- a silane coupling agent from nitrogen, sulfur, and oxygen in one molecule
- a hydrolyzable silane compound such as an alkoxysilane having a monovalent hydrocarbon group having a functional group containing a selected heteroatom (however, excluding a guanidyl group), or a so-called carbon functional silane compound) is used as an adhesion imparting agent.
- silane coupling agent examples include silane compounds having an alkoxysilyl group or an alkenoxysilyl group as a hydrolyzable group, such as vinyltris( ⁇ -methoxyethoxy)silane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, N- ⁇ -(aminoethyl) ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 3-(N-aminomethylbenzylamino)propyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N-bis[3-
- a silane coupling agent When blending a silane coupling agent, it may be blended in either the first part or the second part, but it is preferably blended in the first part, and the blending amount is per 100 parts by mass of component (A). It is usually 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight. If it is less than 0.1 parts by mass, sufficient adhesiveness may not be obtained, and if it exceeds 20 parts by mass, good mechanical properties may not be obtained or it may be disadvantageous in terms of price.
- an inorganic filler may be added to the composition as an optional component.
- These inorganic fillers may not be surface-treated or may be surface-treated with a known treatment agent.
- a hydrolyzable group-containing polysiloxane described in JP-A No. 2000-256558 is preferred, but the treatment agent is not limited thereto.
- silica-based fillers such as ground silica, fumed silica, wet silica, and crystalline silica, or calcium carbonate are preferred.
- the blending amount is 1 to 400 parts by mass per 100 parts by mass of components (A) to (C). Parts by weight are preferred, more preferably 1 to 350 parts by weight, particularly preferably 1 to 300 parts by weight. If the amount is less than 1 part by mass, it may be difficult to obtain a cured product having the desired rubber strength and rubber elasticity. If the amount exceeds 400 parts by mass, it becomes difficult to knead with the components (A) to (C), and it may be difficult to prepare a good room-temperature-curable organopolysiloxane composition.
- the two-component room-temperature-curable organopolysiloxane composition of the present invention may contain various additives as optional components.
- additives known additives may be added within a range that does not impair the purpose of the present invention.
- polyether compounds as wetters and thixotropy improvers
- non-reactive dimethyl silicone oil dimethyl polysiloxane blocked with trialkylsilyl groups at both ends of the molecular chain
- isoparaffins trimethylsiloxy units as crosslinking density improvers [ (CH 3 ) 3 SiO 1/2 units]
- organopolysiloxane resin having a three-dimensional network structure consisting of SiO 2 units.
- colorants such as pigments, dyes, and optical brighteners; fungicides; antibacterial agents; non-reactive phenyl silicone oil (methylphenyl polysiloxane blocked with trialkylsilyl groups at both molecular chain ends), Bleed oil such as silicone oil (methyl (3,3,3-trifluoropropyl)polysiloxane blocked with trialkylsilyl groups at both ends of the molecular chain); Surface modifier such as organic liquid that is incompatible with silicone; and toluene Solvents such as , xylene, solvent volatile oils, cyclohexane, methylcyclohexane, and low boiling isoparaffins may also be added.
- phenyl silicone oil methylphenyl polysiloxane blocked with trialkylsilyl groups at both molecular chain ends
- Bleed oil such as silicone oil (methyl (3,3,3-trifluoropropyl)polysiloxane blocked with trialkylsilyl groups at
- the two-component room-temperature fast-curing organopolysiloxane composition of the present invention comprises a first part containing component (A) and component (B), component (C), component (D) and ( and a second agent containing component E). Both the first part and the second part can be prepared by mixing the respective components according to a conventional method. The mixing method may be a conventional method, and the respective components may be mixed under reduced pressure.
- the two-component room-temperature-curable organopolysiloxane composition of the present invention allows the first and second parts to be stored in an atmosphere that avoids moisture, and the first and second parts can be mixed in any desired combination.
- the optional component may be blended in either the first part or the second part, or may be blended in either one or both.
- the viscosity is a value measured by a rotational viscometer at 23° C.
- the degree of polymerization indicates the number average degree of polymerization in terms of polystyrene in gel permeation chromatography analysis using toluene as a developing solvent.
- compositions 1 to 6 were prepared by uniformly mixing the first agent and the second agent at a mixing ratio (volume ratio) of 1:1 using the combinations shown in Table 1 below.
- the mixing method used a 250 ml x 250 ml cartridge manufactured by Mixpac.
- compositions 1 to 6 were left to cure in a 23°C/50% RH environment for 3 days to a thickness of 3 mm to form a silicone rubber cured product (3 mm thick). ) was prepared, and a No. 2 dumbbell test piece was prepared according to JIS K 6249, and the hardness, elongation at cutting, and tensile strength were measured. In addition, the hardness was taken as the value of durometer A.
- the composition was sandwiched and left in an environment of 23° C./50% RH for 3 days to cure the composition. Thereafter, each of the two aluminum substrates was pulled in the shear direction at a speed of 500 mm/min to determine the shear adhesive strength. The results are shown in Table 2.
- compositions 1 to 4 all showed good adhesion.
- compositions 5 and 6 showed higher values for hardness and tensile strength than compositions 1 to 4, but had low shear adhesive strength and poor adhesion.
- compositions 1 to 4 had similar curability when compared with Compositions 5 and 6, both of which contained conventional organic tin.
- compositions 1 to 4 tend to have a slight decrease in hardness, but the elongation and tensile strength at cutting tend to decrease slightly. There was no major change in strength, and it can be judged that the moisture resistance is good. The rate of change in physical properties was within 50% in all items. On the other hand, in compositions 5 and 6 containing organic tin, although the change in hardness was small compared to compositions 1 to 4, the elongation at break and tensile strength decreased significantly, and the rate of change was It became more than 50%.
Abstract
The present invention provides a two-pack type room temperature curable organopolysiloxane composition which exhibits both excellent fast curing properties and excellent bonding properties without the addition of a metal-based condensation catalyst that has a high environmental load, and which is capable of providing a cured product hat has good durability (heat resistance and moisture resistance). The present invention provides a two-pack type room temperature curable organopolysiloxane composition which is composed of: a first agent that contains (A) an organopolysiloxane having both molecular chain ends blocked with organooxy groups and (B) a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom; and a second agent that contains (C) an organopolysiloxane having both molecular chain ends blocked with silanol groups, (D) an amino functional group-containing hydrolyzable organosilane compound having three or more nitrogen atoms in each molecule and/or a partial hydrolysis-condensation product thereof, and (E) 0.1 to 5 parts by mass of an organic compound having a ketone group.
Description
本発明は、大気中の湿気（水分）により室温（２３℃±１５℃）において硬化してシリコーンゴム硬化物（シリコーンエラストマー弾性体）を与える室温硬化性オルガノポリシロキサン組成物（室温硬化性シリコーンゴム組成物）に関するものであり、特には、分子鎖両末端が加水分解性シリル基で封鎖されたオルガノポリシロキサンをベースポリマーとして、同一ケイ素原子上に加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物を架橋剤（硬化剤）とした第一剤と、分子鎖両末端がヒドロキシル基で封鎖されたオルガノポリシロキサンをベースポリマーとして、特定のアミノ官能性基含有加水分解性オルガノシラン化合物を縮合触媒として配合した第二剤とを、任意の割合で混合することで従来の室温硬化性オルガノポリシロキサン組成物において常用されていた環境負荷の大きな金属系縮合触媒を添加することなしに、良好な硬化性（速硬化性）と優れた接着性を有すると共に、湿熱条件下においても耐久性に優れたシリコーンゴム硬化物を与えることのできる二成分型室温硬化性オルガノポリシロキサン組成物、並びに該組成物を含有する接着剤、シール剤及びコーティング剤に関する。
The present invention provides a room-temperature-curable organopolysiloxane composition (room-temperature-curable silicone rubber) that is cured at room temperature (23°C ± 15°C) by atmospheric humidity (moisture) to give a cured silicone rubber product (silicone elastomer elastomer). In particular, the composition relates to a hydrolyzed polysiloxane having two hydrolyzable silyl-vinylene groups on the same silicon atom, using as a base polymer an organopolysiloxane in which both ends of the molecular chain are capped with hydrolyzable silyl groups. The first agent is a degradable organosilane compound as a crosslinking agent (curing agent), and the base polymer is an organopolysiloxane in which both ends of the molecular chain are blocked with hydroxyl groups to produce a specific hydrolyzable organosilane containing an amino functional group. By mixing a second component containing a compound as a condensation catalyst in an arbitrary ratio, it is possible to eliminate the need to add a metal condensation catalyst that has a large environmental impact, which is commonly used in conventional room temperature curing organopolysiloxane compositions. , a two-component room temperature curable organopolysiloxane composition that has good curability (fast curability) and excellent adhesiveness, and is capable of providing a cured silicone rubber product that is highly durable even under moist heat conditions; The present invention also relates to adhesives, sealants, and coatings containing the composition.
湿気により架橋・硬化する室温硬化性（ＲＴＶ）シリコーンゴム組成物（室温硬化性オルガノポリシロキサン組成物）は、その取り扱いが容易な上、耐候性や電気特性に優れているため、建材用のシーリング材、電気・電子分野での接着剤やコーティング剤（封止剤）などの様々な用途に適している。一般的な室温硬化性オルガノポリシロキサン組成物は、分子鎖末端にシラノール基（ケイ素原子に結合した水酸基）やアルコキシシリル基を有するジオルガノポリシロキサン（ベースポリマー）、硬化剤、アミノアルキル基含有アルコキシシラン及び硬化触媒を含み、難燃性や熱伝導性、引張り強度等を付与するため、必要に応じて各種フィラーが添加される。
Room-temperature-curing (RTV) silicone rubber compositions (room-temperature-curing organopolysiloxane compositions) that crosslink and harden when exposed to moisture are easy to handle and have excellent weather resistance and electrical properties, so they are used as sealants for building materials. It is suitable for a variety of uses such as materials, adhesives and coating agents (sealants) in the electrical and electronic fields. A typical room-temperature curable organopolysiloxane composition consists of a diorganopolysiloxane (base polymer) having a silanol group (a hydroxyl group bonded to a silicon atom) or an alkoxysilyl group at the end of the molecular chain, a curing agent, an alkoxysiloxane group containing an aminoalkyl group, etc. It contains silane and a curing catalyst, and various fillers are added as necessary to impart flame retardancy, thermal conductivity, tensile strength, etc.
一般的な建築、構造用シーリング材として知られる脱オキシム型の室温硬化性オルガノポリシロキサン組成物は、硬化性、耐久性、各種被着体に対する接着性を有することで汎用的に用いられているが、得られる硬化物が高温高湿環境に置かれた際のゴム物性変化が大きく、耐久性に劣ることが知られている。また、建築、構造用シーリング材としては脱酢酸型の室温硬化性オルガノポリシロキサン組成物も汎用的に使用されており、硬化性、接着性に優れ、かつＵＶ照射に対する変色も僅かであることが知られているが、硬化中に発生する酢酸のため作業性が悪い。
Oxime-free room-temperature-curable organopolysiloxane compositions, known as general architectural and structural sealants, are widely used due to their curability, durability, and adhesion to various adherends. However, it is known that when the obtained cured product is placed in a high temperature and high humidity environment, the physical properties of the rubber change significantly and the durability is poor. In addition, acetic acid-depleted room-temperature-curable organopolysiloxane compositions are commonly used as sealants for buildings and structures, and are known to have excellent curability and adhesive properties, and to show slight discoloration when exposed to UV irradiation. Although known, workability is poor due to acetic acid generated during curing.
一方、脱アルコール型の室温硬化性オルガノポリシロキサン組成物は、上記脱オキシム型や脱酢酸型の室温硬化性オルガノポリシロキサン組成物と比べると調製方法が容易ではない。ベースポリマーとして分子鎖両末端にシラノール基を有するオルガノポリシロキサンを使用した場合、シラノール基をアルコキシシリル化する（アルコキシシリル基で末端封鎖する）必要が有るが、その反応速度は上記脱オキシム型や脱酢酸型の室温硬化性オルガノポリシロキサン組成物と比べて遅いことが、脱アルコール型の室温硬化性オルガノポリシロキサン組成物の調製方法が容易ではない理由として挙げられる。この問題を回避するためベースポリマーとして予め分子鎖両末端がアルコキシシリル化されたオルガノポリシロキサンを使用する方法が知られている。
On the other hand, a dealcoholization type room temperature curable organopolysiloxane composition is not easy to prepare compared to the above-mentioned oxime removal type or acetic acid removal type room temperature curable organopolysiloxane composition. When an organopolysiloxane having silanol groups at both ends of the molecular chain is used as a base polymer, it is necessary to alkoxysilylate the silanol groups (terminate them with an alkoxysilyl group), but the reaction rate is slower than that of the above-mentioned deoxime type. One of the reasons why the method for preparing a dealcoholization type room temperature curable organopolysiloxane composition is not easy is that it is slow compared to a deacetic acid type room temperature curable organopolysiloxane composition. In order to avoid this problem, a method is known in which an organopolysiloxane in which both ends of the molecular chain have been previously alkoxysilylated is used as a base polymer.
脱アルコール型の室温硬化性オルガノポリシロキサン組成物の硬化触媒としては、有機スズ化合物あるいは有機チタン化合物が一般的に知られている。しかし、有機スズ化合物に関しては、その毒性の問題から環境ないし人体への悪影響が懸念されている。一方、有機チタン化合物に関しては、いまだ毒性の問題は確認されていないものの、調製された室温硬化性オルガノポリシロキサンが経時で黄変する等の課題も残されている。
An organic tin compound or an organic titanium compound is generally known as a curing catalyst for a dealcoholization type room temperature curable organopolysiloxane composition. However, with regard to organic tin compounds, there are concerns about their adverse effects on the environment and the human body due to their toxicity. On the other hand, with regard to organic titanium compounds, although no toxicity problems have been confirmed yet, there are still problems such as the prepared room-temperature-curable organopolysiloxanes turning yellow over time.
脱アルコール型の室温硬化性オルガノポリシロキサンの代表例としては、シラノール基末端封鎖ポリオルガノシロキサンとアルコキシシランと有機チタン化合物とを含む組成物、アルコキシシリル基末端封鎖ポリオルガノシロキサンとアルコキシシランとアルコキシチタンとを含む組成物、末端がシルエチレン基を介してアルコキシシリル基で封鎖された直鎖状のポリオルガノシロキサンとアルコキシシランとアルコキシチタンとを含む組成物、更に、シラノール基末端封鎖ポリオルガノシロキサン又はアルコキシシリル基末端封鎖ポリオルガノシロキサンとアルコキシ－α－シリルエステル化合物とを含む組成物が挙げられる（特許文献１～４）。
これらの特許文献に記載された室温硬化性オルガノポリシロキサンは、ある程度の保存安定性、耐水性、耐湿性が得られているが、これらの要求特性を全て満足するには至っていない。さらに、速硬化性に関しては、まだ不十分であった。 Typical examples of dealcoholization-type room-temperature-curable organopolysiloxanes include compositions containing a silanol group-terminated polyorganosiloxane, an alkoxysilane, and an organic titanium compound, and an alkoxysilyl group-terminated polyorganosiloxane, an alkoxysilane, and an alkoxytitanium compound. A composition comprising a linear polyorganosiloxane terminal-capped with an alkoxysilyl group via a silethylene group, an alkoxysilane, and an alkoxytitanium, further comprising a silanol-terminated polyorganosiloxane or Examples include compositions containing an alkoxysilyl end-capped polyorganosiloxane and an alkoxy-α-silyl ester compound (Patent Documents 1 to 4).
The room-temperature-curable organopolysiloxanes described in these patent documents have a certain degree of storage stability, water resistance, and humidity resistance, but do not yet satisfy all of these required properties. Furthermore, the fast curing properties were still insufficient.
これらの特許文献に記載された室温硬化性オルガノポリシロキサンは、ある程度の保存安定性、耐水性、耐湿性が得られているが、これらの要求特性を全て満足するには至っていない。さらに、速硬化性に関しては、まだ不十分であった。 Typical examples of dealcoholization-type room-temperature-curable organopolysiloxanes include compositions containing a silanol group-terminated polyorganosiloxane, an alkoxysilane, and an organic titanium compound, and an alkoxysilyl group-terminated polyorganosiloxane, an alkoxysilane, and an alkoxytitanium compound. A composition comprising a linear polyorganosiloxane terminal-capped with an alkoxysilyl group via a silethylene group, an alkoxysilane, and an alkoxytitanium, further comprising a silanol-terminated polyorganosiloxane or Examples include compositions containing an alkoxysilyl end-capped polyorganosiloxane and an alkoxy-α-silyl ester compound (Patent Documents 1 to 4).
The room-temperature-curable organopolysiloxanes described in these patent documents have a certain degree of storage stability, water resistance, and humidity resistance, but do not yet satisfy all of these required properties. Furthermore, the fast curing properties were still insufficient.
特許文献５には、脱アルコールタイプの室温硬化性オルガノシロキサン組成物であって、加水分解性シリル－ビニレン基を有するオルガノシラン化合物を架橋剤として用い、二成分型で速硬化性に優れる二成分型室温速硬化性オルガノシロキサン組成物の記載がある。速硬化性については議論されているが、硬化したゴムに対する耐久性については議論されていない。
Patent Document 5 discloses a dealcoholization-type room-temperature-curable organosiloxane composition, which uses an organosilane compound having a hydrolyzable silyl-vinylene group as a crosslinking agent, and is a two-component type with excellent fast curing properties. There is a description of an organosiloxane composition that cures quickly at mold room temperature. Although there is discussion about quick curing properties, there is no discussion about durability to cured rubber.
本発明の目的は、従来の室温硬化性オルガノポリシロキサン組成物において常用されていた環境負荷の大きな金属系縮合触媒を添加することなしに、速硬化性、接着性に優れると共に、良好な耐久性（耐熱性、耐湿性）を有する硬化物を与えることのできる二成分型室温硬化性オルガノポリシロキサン組成物、接着剤、シール剤及びコーティング剤を提供することにある。
The purpose of the present invention is to provide excellent fast curing and adhesive properties as well as good durability without adding metal condensation catalysts that have a large environmental impact and are commonly used in conventional room temperature curable organopolysiloxane compositions. An object of the present invention is to provide a two-component room-temperature-curable organopolysiloxane composition, an adhesive, a sealing agent, and a coating agent that can provide a cured product having (heat resistance, moisture resistance).
本発明者は、上記目的を達成するため、鋭意研究の結果、分子鎖両末端がシルアルキレン基を介して又は介さずに加水分解性シリル基で封鎖されたオルガノポリシロキサンを主剤（ベースポリマー）とし、同一ケイ素原子上に加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物を架橋剤（硬化剤）とした第一剤と、分子鎖両末端がヒドロキシル基で封鎖されたオルガノポリシロキサンを主剤（ベースポリマー）とし、特定のアミノ官能性基含有加水分解性オルガノシラン化合物を縮合触媒として配合し、ケトン基を有する有機化合物をさらに配合した第二剤とを、特定の配合比で混合して得られる室温硬化性（ＲＴＶ）シリコーンゴム組成物及びその硬化物が、上記目的を達成することができることを見出し、本発明をなすに至った。
In order to achieve the above-mentioned object, the present inventors have conducted intensive research and found that the main material (base polymer) is an organopolysiloxane in which both ends of the molecular chain are capped with hydrolyzable silyl groups with or without sylalkylene groups. The first agent is a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom as a crosslinking agent (curing agent), and the organosilane compound has two hydrolyzable silyl-vinylene groups on the same silicon atom. Polysiloxane is used as the main agent (base polymer), a specific amino-functional group-containing hydrolyzable organosilane compound is blended as a condensation catalyst, and a second component is further blended with an organic compound having a ketone group in a specific compounding ratio. It has been discovered that a room temperature curable (RTV) silicone rubber composition obtained by mixing and a cured product thereof can achieve the above object, and the present invention has been completed.
即ち、本発明は下記の二成分型室温硬化性オルガノポリシロキサン組成物、接着剤、シール剤及びコーティング剤を提供するものである。
That is, the present invention provides the following two-component room temperature curable organopolysiloxane composition, adhesive, sealant, and coating agent.
［１］
（Ａ）下記一般式（１）で示されるオルガノポリシロキサン１００質量部、
（式中、Ｒ1は独立に炭素数１～１０の非置換又はハロゲン置換１価炭化水素基であり、ｎは１０以上の数であり、Ｘは独立に酸素原子又は炭素数１～４のアルキレン基であり、Ｒ2は独立に炭素数１～６の置換又は非置換１価炭化水素基であり、ａは結合するケイ素原子毎に独立に０又は１である。）
及び
（Ｂ）下記一般式（２）で示される同一ケイ素原子上に加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物０．１～１０質量部、
（式中、Ｒ3は独立に炭素数１～２０の非置換又は置換１価炭化水素基であり、Ｒ4は独立に炭素数１～２０の非置換若しくは置換アルキル基又は炭素数３～２０の非置換若しくは置換シクロアルキル基である。ｂは０～２の整数である。）
を含有する第一剤と
（Ｃ）下記一般式（３）で示されるオルガノポリシロキサン１００質量部、
（式中、Ｒ1は独立に炭素数１～１０の非置換又はハロゲン置換１価炭化水素基であり、ｎは１０以上の数である。）
（Ｄ）１分子中に窒素原子を３個以上有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物０．１～５質量部、
及び
（Ｅ）ケトン基を有する有機化合物０．１～５質量部、
を含有する第二剤と
からなる二成分型室温硬化性オルガノポリシロキサン組成物。
［２］
（Ｄ）成分が、下記一般式（４）又は（４）’で表されるアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物である［１］に記載の二成分型室温硬化性オルガノポリシロキサン組成物。
（各式中、Ｙは、その構造中に窒素原子を２個以上含有する炭素数１～１５の１価又は２価炭化水素基を示し、Ｚは、ヘテロ原子を含んでもよい炭素数１～１０の非置換又は置換の２価炭化水素基を示す。Ｒは、炭素数１～６の加水分解性基及び炭素数１～６の１価炭化水素基から選ばれる１種又は２種以上の１価の基であり、ケイ素原子に結合する３個のＲのうち、少なくとも２個のＲは加水分解性基である。
［３］
有機金属化合物を含有しないものである［１］又は［２］に記載の二成分型室温硬化性オルガノポリシロキサン組成物。
［４］
第一剤と第二剤の混合割合が体積比で第一剤：第二剤＝１：１～１０：１である［１］～［３］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物。
［５］
第一剤と第二剤を混合して成型されたオルガノポリシロキサン組成物を８５℃／８５％ＲＨ環境下に１，０００時間放置した時の物性変化率が、放置前の物性と比較して５０％以内である硬化物を与えるものである［１］～［４］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物
［６］
［１］～［４］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有する接着剤。
［７］
［１］～［４］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有するシール剤。
［８］
［１］～［４］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有するコーティング剤。 [1]
(A) 100 parts by mass of organopolysiloxane represented by the following general formula (1),
(In the formula, R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, n is a number of 10 or more, and X is independently an oxygen atom or a halogen-substituted monovalent hydrocarbon group having 1 to 4 carbon atoms. It is an alkylene group, R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and a is independently 0 or 1 for each bonded silicon atom.)
and (B) 0.1 to 10 parts by mass of a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom represented by the following general formula (2),
(In the formula, R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 is independently an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted alkyl group having 3 to 20 carbon atoms. is an unsubstituted or substituted cycloalkyl group. b is an integer from 0 to 2.)
A first agent containing
(C) 100 parts by mass of organopolysiloxane represented by the following general formula (3),
(In the formula, R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is a number of 10 or more.)
(D) 0.1 to 5 parts by mass of an amino-functional group-containing hydrolyzable organosilane compound and/or a partially hydrolyzed condensate thereof having three or more nitrogen atoms in one molecule;
and (E) 0.1 to 5 parts by mass of an organic compound having a ketone group,
A two-component room temperature curable organopolysiloxane composition comprising a second agent containing:
[2]
The compound according to [1], wherein the component (D) is an amino-functional group-containing hydrolyzable organosilane compound represented by the following general formula (4) or (4)' and/or a partially hydrolyzed condensate thereof. Component-type room temperature curable organopolysiloxane composition.
(In each formula, Y represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms containing two or more nitrogen atoms in its structure, and Z represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms that may contain a hetero atom. 10 unsubstituted or substituted divalent hydrocarbon groups.R is one or more selected from a hydrolyzable group having 1 to 6 carbon atoms and a monovalent hydrocarbon group having 1 to 6 carbon atoms. It is a monovalent group, and among the three R's bonded to the silicon atom, at least two R's are hydrolyzable groups.
[3]
The two-component room temperature curable organopolysiloxane composition according to [1] or [2], which does not contain an organometallic compound.
[4]
Two-component room temperature curable according to any one of [1] to [3], wherein the mixing ratio of the first part and the second part is 1:1 to 10:1 by volume. Organopolysiloxane composition.
[5]
The rate of change in physical properties when an organopolysiloxane composition formed by mixing the first part and the second part was left in an 85°C/85% RH environment for 1,000 hours was compared to the physical properties before being left. The two-component room-temperature-curable organopolysiloxane composition according to any one of [1] to [4], which provides a cured product with a hardness of 50% or less.
[6]
An adhesive containing the two-component room temperature curable organopolysiloxane composition according to any one of [1] to [4].
[7]
A sealant containing the two-component room-temperature-curable organopolysiloxane composition according to any one of [1] to [4].
[8]
A coating agent containing the two-component room temperature curable organopolysiloxane composition according to any one of [1] to [4].
（Ａ）下記一般式（１）で示されるオルガノポリシロキサン１００質量部、
及び
（Ｂ）下記一般式（２）で示される同一ケイ素原子上に加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物０．１～１０質量部、
を含有する第一剤と
（Ｃ）下記一般式（３）で示されるオルガノポリシロキサン１００質量部、
（Ｄ）１分子中に窒素原子を３個以上有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物０．１～５質量部、
及び
（Ｅ）ケトン基を有する有機化合物０．１～５質量部、
を含有する第二剤と
からなる二成分型室温硬化性オルガノポリシロキサン組成物。
［２］
（Ｄ）成分が、下記一般式（４）又は（４）’で表されるアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物である［１］に記載の二成分型室温硬化性オルガノポリシロキサン組成物。
［３］
有機金属化合物を含有しないものである［１］又は［２］に記載の二成分型室温硬化性オルガノポリシロキサン組成物。
［４］
第一剤と第二剤の混合割合が体積比で第一剤：第二剤＝１：１～１０：１である［１］～［３］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物。
［５］
第一剤と第二剤を混合して成型されたオルガノポリシロキサン組成物を８５℃／８５％ＲＨ環境下に１，０００時間放置した時の物性変化率が、放置前の物性と比較して５０％以内である硬化物を与えるものである［１］～［４］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物
［６］
［１］～［４］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有する接着剤。
［７］
［１］～［４］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有するシール剤。
［８］
［１］～［４］のいずれかに記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有するコーティング剤。 [1]
(A) 100 parts by mass of organopolysiloxane represented by the following general formula (1),
and (B) 0.1 to 10 parts by mass of a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom represented by the following general formula (2),
A first agent containing
(C) 100 parts by mass of organopolysiloxane represented by the following general formula (3),
(D) 0.1 to 5 parts by mass of an amino-functional group-containing hydrolyzable organosilane compound and/or a partially hydrolyzed condensate thereof having three or more nitrogen atoms in one molecule;
and (E) 0.1 to 5 parts by mass of an organic compound having a ketone group,
A two-component room temperature curable organopolysiloxane composition comprising a second agent containing:
[2]
The compound according to [1], wherein the component (D) is an amino-functional group-containing hydrolyzable organosilane compound represented by the following general formula (4) or (4)' and/or a partially hydrolyzed condensate thereof. Component-type room temperature curable organopolysiloxane composition.
[3]
The two-component room temperature curable organopolysiloxane composition according to [1] or [2], which does not contain an organometallic compound.
[4]
Two-component room temperature curable according to any one of [1] to [3], wherein the mixing ratio of the first part and the second part is 1:1 to 10:1 by volume. Organopolysiloxane composition.
[5]
The rate of change in physical properties when an organopolysiloxane composition formed by mixing the first part and the second part was left in an 85°C/85% RH environment for 1,000 hours was compared to the physical properties before being left. The two-component room-temperature-curable organopolysiloxane composition according to any one of [1] to [4], which provides a cured product with a hardness of 50% or less.
[6]
An adhesive containing the two-component room temperature curable organopolysiloxane composition according to any one of [1] to [4].
[7]
A sealant containing the two-component room-temperature-curable organopolysiloxane composition according to any one of [1] to [4].
[8]
A coating agent containing the two-component room temperature curable organopolysiloxane composition according to any one of [1] to [4].
本発明は、従来の室温硬化性オルガノポリシロキサン組成物において常用されていた環境負荷の大きな金属系縮合触媒を添加することなしに、耐久性（耐熱性、耐湿性）を有する硬化物を与えることのできる速硬化性、接着性に優れた二成分型室温硬化性（ＲＴＶ）シリコーンゴム組成物を提供することができる。したがって、本発明の組成物は、接着剤、シール剤及びコーティング剤として有用である。
The present invention aims to provide a cured product with durability (heat resistance, moisture resistance) without adding a metal condensation catalyst that has a large environmental impact and is commonly used in conventional room temperature curable organopolysiloxane compositions. It is possible to provide a two-component room temperature curable (RTV) silicone rubber composition with excellent fast curing properties and adhesive properties. Accordingly, the compositions of the present invention are useful as adhesives, sealants, and coatings.
以下、本発明について詳しく説明する。
Hereinafter, the present invention will be explained in detail.
［（Ａ）成分］
本発明のオルガノポリシロキサン組成物の（Ａ）成分は、本発明の組成物において主剤（ベースポリマー）として作用するものであって、下記一般式（１）で示される、分子鎖両末端がシルアルキレン基を介して（Ｘがアルキレン基の場合）又は介さずに（Ｘが酸素原子の場合）、それぞれ２個又は３個のケイ素原子に結合したオルガノオキシ基を加水分解性基として有する加水分解性シリル基で封鎖された直鎖状のオルガノポリシロキサンである。 [(A) Component]
Component (A) of the organopolysiloxane composition of the present invention acts as a main agent (base polymer) in the composition of the present invention, and is represented by the following general formula (1), and has both ends of the molecular chain silyl. Hydrolysis that has an organooxy group bonded to two or three silicon atoms as a hydrolyzable group through an alkylene group (when X is an alkylene group) or without (when X is an oxygen atom) It is a linear organopolysiloxane blocked with silyl groups.
本発明のオルガノポリシロキサン組成物の（Ａ）成分は、本発明の組成物において主剤（ベースポリマー）として作用するものであって、下記一般式（１）で示される、分子鎖両末端がシルアルキレン基を介して（Ｘがアルキレン基の場合）又は介さずに（Ｘが酸素原子の場合）、それぞれ２個又は３個のケイ素原子に結合したオルガノオキシ基を加水分解性基として有する加水分解性シリル基で封鎖された直鎖状のオルガノポリシロキサンである。 [(A) Component]
Component (A) of the organopolysiloxane composition of the present invention acts as a main agent (base polymer) in the composition of the present invention, and is represented by the following general formula (1), and has both ends of the molecular chain silyl. Hydrolysis that has an organooxy group bonded to two or three silicon atoms as a hydrolyzable group through an alkylene group (when X is an alkylene group) or without (when X is an oxygen atom) It is a linear organopolysiloxane blocked with silyl groups.
上記式（１）中、Ｒ1は炭素数１～１０、好ましくは炭素数１～６の非置換又はハロゲン置換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、ネオペンチル基、ヘキシル基、へプチル基、オクチル基、２－エチルヘキシル基、ノニル基、デシル基などのアルキル基；シクロペンチル基、シクロヘキシル基などのシクロアルキル基；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、ペンテニル基、ヘキセニル基、シクロヘキセニル基などのアルケニル基；フェニル基、トリル基、キシリル基、α－，β－ナフチル基などのアリール基；ベンジル基、２－フェニルエチル基、３－フェニルプロピル基等のアラルキル基、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等である。これらの中では、特にメチル基が好ましい。また、複数のＲ1は同一の基であっても異種の基であってもよい。
In the above formula (1), R 1 is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group. , alkyl groups such as butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group; cyclopentyl group , cycloalkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group; phenyl group, tolyl group, xylyl group, α- , β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms, such as 3 , 3,3-trifluoropropyl group, etc. Among these, methyl group is particularly preferred. Furthermore, the plurality of R 1 may be the same group or different groups.
上記式（１）中のｎは１０以上の数であり、１０～２，０００の数が好ましく、２０～１，５００の数がより好ましく、３０～１，０００の数が更に好ましく、５０～８００の数が特に好ましい。また、このｎの値は、特に（Ａ）成分のジオルガノポリシロキサンの２３℃における粘度が２５～５００，０００ｍＰａ・ｓの範囲、好ましくは５００～１００，０００ｍＰａ・ｓの範囲となる数であることが好ましい。
n in the above formula (1) is a number of 10 or more, preferably a number of 10 to 2,000, more preferably a number of 20 to 1,500, even more preferably a number of 30 to 1,000, and a number of 50 to 1,000. A number of 800 is particularly preferred. In addition, the value of n is a number such that the viscosity of the diorganopolysiloxane of component (A) at 23°C is in the range of 25 to 500,000 mPa·s, preferably in the range of 500 to 100,000 mPa·s. It is preferable.
なお、本発明において、（Ａ）成分のジオルガノポリシロキサンの主鎖を構成する（（Ｒ1）2ＳｉＯ2/2）で示される２官能性のジオルガノシロキサン単位の繰り返し数であるｎ（又は重合度）は、通常、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。また、粘度は通常、２３℃において回転粘度計（例えば、ＢＬ型、ＢＨ型、ＢＳ型、コーンプレート型、レオメータ等）により測定することができる。
In addition, in the present invention, n(, which is the repeating number of bifunctional diorganosiloxane units represented by ((R 1 ) 2 SiO 2/2 ) constituting the main chain of the diorganopolysiloxane of component (A) The degree of polymerization (or degree of polymerization) can usually be determined as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene or the like as a developing solvent. Further, the viscosity can usually be measured at 23° C. using a rotational viscometer (eg, BL type, BH type, BS type, cone plate type, rheometer, etc.).
上記式（１）中、Ｘは独立に酸素原子又は炭素数１～４のアルキレン基であり、炭素数１～４のアルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基などの直鎖アルキレン基、及びこれらの異性体、例えば、プロピレン基（メチルエチレン基）、２－メチル－トリメチレン基などの分岐アルキレン基等が該当する。Ｘとしては、特に、エチレン基が好ましい。エチレン基の場合、α、ω－ジビニル末端オルガノポリシロキサンに対し、対応するヒドロシランを金属触媒存在化でヒドロシリル化付加反応させることにより容易に製造できることから、非常に汎用性がある。
In the above formula (1), X is independently an oxygen atom or an alkylene group having 1 to 4 carbon atoms, and examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group. Straight-chain alkylene groups such as, and isomers thereof, such as branched alkylene groups such as propylene group (methylethylene group) and 2-methyl-trimethylene group, etc. are applicable. As X, an ethylene group is particularly preferable. In the case of an ethylene group, it is very versatile because it can be easily produced by subjecting an α,ω-divinyl-terminated organopolysiloxane to a hydrosilylation addition reaction of the corresponding hydrosilane in the presence of a metal catalyst.
また上記式（１）中、Ｒ2は独立に炭素数１～６の置換又は非置換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、ヘキシル基などのアルキル基；メトキシメチル基、メトキシエチル基、メトキシエチル基、エトキシエチル基などのアルコキシ置換アルキル基；シクロヘキシル基などのシクロアルキル基；ビニル基、アリル基、プロペニル基などのアルケニル基；フェニル基等が挙げられるが、特にメチル基、エチル基が好ましい。
In the above formula (1), R 2 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group. , sec-butyl group, tert-butyl group, pentyl group, hexyl group and other alkyl groups; methoxymethyl group, methoxyethyl group, methoxyethyl group, ethoxyethyl group and other alkoxy-substituted alkyl groups; cyclohexyl group and other cycloalkyl groups ; Alkenyl groups such as vinyl, allyl, propenyl, and phenyl; methyl and ethyl groups are particularly preferred.
上記式（１）中、ａは、結合するケイ素原子毎に独立に０又は１であり、好ましくは０である。
なお、（Ａ）成分の分子鎖両末端加水分解性シリル基封鎖直鎖状オルガノポリシロキサンは、１種を単独で使用しても、２種以上を併用してもよい。 In the above formula (1), a is independently 0 or 1 for each bonded silicon atom, preferably 0.
In addition, the linear organopolysiloxane having hydrolyzable silyl groups endblocked at both molecular chain ends of component (A) may be used alone or in combination of two or more.
なお、（Ａ）成分の分子鎖両末端加水分解性シリル基封鎖直鎖状オルガノポリシロキサンは、１種を単独で使用しても、２種以上を併用してもよい。 In the above formula (1), a is independently 0 or 1 for each bonded silicon atom, preferably 0.
In addition, the linear organopolysiloxane having hydrolyzable silyl groups endblocked at both molecular chain ends of component (A) may be used alone or in combination of two or more.
［（Ｂ）成分］
本発明のオルガノポリシロキサン組成物の（Ｂ）成分は、下記一般式（２）で示される、同一ケイ素原子上に加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物（即ち、分子中に２個存在する加水分解性シリル基（－Ｓｉ（Ｒ3）b（ＯＲ4）3-b）のケイ素原子が、それぞれ分子中に１個存在するジオルガノシリレン基（－Ｓｉ（Ｒ3）2－）のケイ素原子とビニレン基（―ＣＨ＝ＣＨ―）で連結された、加水分解性オルガノトリシラン化合物）であって、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。 [(B) Component]
Component (B) of the organopolysiloxane composition of the present invention is a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom (i.e., Two silicon atoms of the hydrolyzable silyl group (-Si(R 3 ) b (OR 4 ) 3-b ) exist in the molecule, and the silicon atoms of the diorganosilylene group (-Si(R 3 ) A hydrolyzable organotrisilane compound in which the silicon atom of 2- ) is linked with a vinylene group (-CH=CH-), which acts as a crosslinking agent (curing agent) in the composition of the present invention. It is something.
本発明のオルガノポリシロキサン組成物の（Ｂ）成分は、下記一般式（２）で示される、同一ケイ素原子上に加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物（即ち、分子中に２個存在する加水分解性シリル基（－Ｓｉ（Ｒ3）b（ＯＲ4）3-b）のケイ素原子が、それぞれ分子中に１個存在するジオルガノシリレン基（－Ｓｉ（Ｒ3）2－）のケイ素原子とビニレン基（―ＣＨ＝ＣＨ―）で連結された、加水分解性オルガノトリシラン化合物）であって、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。 [(B) Component]
Component (B) of the organopolysiloxane composition of the present invention is a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom (i.e., Two silicon atoms of the hydrolyzable silyl group (-Si(R 3 ) b (OR 4 ) 3-b ) exist in the molecule, and the silicon atoms of the diorganosilylene group (-Si(R 3 ) A hydrolyzable organotrisilane compound in which the silicon atom of 2- ) is linked with a vinylene group (-CH=CH-), which acts as a crosslinking agent (curing agent) in the composition of the present invention. It is something.
ここで、上記一般式（２）中、Ｒ3の置換又は非置換の１価炭化水素基は、炭素数が１～２０、好ましくは１～１０、より好ましくは１～８程度であり、同一または異なっていてもよく、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、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、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、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；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、ペンテニル基、ヘキセニル基、シクロヘキセ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、α－，β－ナフチル基等のアリール基；ベンジル基、２－フェニルエチル基、３－フェニルプロピル基等のアラルキル基；また、これらの基の水素原子の一部又は全部が、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子やシアノ基等で置換された基、例えば、３－クロロプロピル基、３，３，３－トリフルオロプロピル基、２－シアノエチル基等を例示することができる。これらの中でも、メチル基、エチル基、フェニル基が好ましく、入手の容易さ、生産性、コストの面からメチル基、フェニル基が特に好ましい。
Here, in the above general formula (2), the substituted or unsubstituted monovalent hydrocarbon group of R 3 has about 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and is the same. or may be different, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group Alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group; cyclopentyl group, Cycloalkyl groups such as cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, and cyclohexenyl; phenyl, tolyl, xylyl, α-, Aryl groups such as β-naphthyl; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; and some or all of the hydrogen atoms of these groups are F, Cl, Br, etc. Examples include groups substituted with halogen atoms, cyano groups, etc., such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group. Among these, methyl group, ethyl group, and phenyl group are preferable, and methyl group and phenyl group are particularly preferable from the viewpoint of availability, productivity, and cost.
上記一般式（２）中、Ｒ4の非置換又は置換アルキル基は、炭素数が１～２０、好ましくは１～６、より好ましくは１～４程度であり、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、ネオペンチル基、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、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基等が挙げられる。非置換又は置換シクロアルキル基は、炭素数が３～２０、好ましくは４～８、より好ましくは５～６程度であり、例えば、シクロペンチル基、シクロヘキシル基等が挙げられる。また、これらのアルキル基やシクロアルキル基の水素原子の一部又は全部が、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子やシアノ基等で置換されていてもよく、これには、例えば、３－クロロプロピル基、３，３，３－トリフルオロプロピル基、２－シアノエチル基等が挙げられる。Ｒ4としては、これらの中でも、加水分解性などの点から、メチル基、エチル基が好ましく、メチル基が特に好ましい。
In the above general formula (2), the unsubstituted or substituted alkyl group of R 4 has about 1 to 20 carbon atoms, preferably about 1 to 6 carbon atoms, more preferably about 1 to 4 carbon atoms, and is, for example, a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group , dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and the like. The unsubstituted or substituted cycloalkyl group has about 3 to 20 carbon atoms, preferably about 4 to 8 carbon atoms, more preferably about 5 to 6 carbon atoms, and includes, for example, a cyclopentyl group and a cyclohexyl group. Further, some or all of the hydrogen atoms of these alkyl groups and cycloalkyl groups may be substituted with halogen atoms such as F, Cl, Br, etc., cyano groups, etc. Examples include propyl group, 3,3,3-trifluoropropyl group, and 2-cyanoethyl group. Among these, from the viewpoint of hydrolyzability, R 4 is preferably a methyl group or an ethyl group, and a methyl group is particularly preferable.
上記一般式（２）のｂは、それぞれ独立に、０～２の整数であるが、０又は１であることが硬化性の点から好ましい。
In the above general formula (2), b is each independently an integer of 0 to 2, but preferably 0 or 1 from the viewpoint of curability.
ここで（Ｂ）成分の製造例を以下に示す。
Here, a manufacturing example of component (B) is shown below.
＜同一ケイ素原子上に加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物の製造方法＞
（Ｂ）成分の同一ケイ素原子上に加水分解性シリル－ビニレンを２個有する加水分解性オルガノシラン化合物は、例えば、同一ケイ素原子上にエチニル基を２個有するシランと、２倍モルのアルコキシヒドロシラン等の加水分解性基含有ヒドロシランをヒドロシリル化反応による、付加反応で容易に製造することができる。この反応式は、例えば下記式［１］で表される。 <Method for producing a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom>
The hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom as component (B) is, for example, a silane having two ethynyl groups on the same silicon atom, and twice the mole of alkoxyhydrosilane. Hydrolyzable group-containing hydrosilanes such as the following can be easily produced by an addition reaction using a hydrosilylation reaction. This reaction formula is expressed, for example, by the following formula [1].
（Ｂ）成分の同一ケイ素原子上に加水分解性シリル－ビニレンを２個有する加水分解性オルガノシラン化合物は、例えば、同一ケイ素原子上にエチニル基を２個有するシランと、２倍モルのアルコキシヒドロシラン等の加水分解性基含有ヒドロシランをヒドロシリル化反応による、付加反応で容易に製造することができる。この反応式は、例えば下記式［１］で表される。 <Method for producing a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom>
The hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom as component (B) is, for example, a silane having two ethynyl groups on the same silicon atom, and twice the mole of alkoxyhydrosilane. Hydrolyzable group-containing hydrosilanes such as the following can be easily produced by an addition reaction using a hydrosilylation reaction. This reaction formula is expressed, for example, by the following formula [1].
アルコキシヒドロシランを付加する際に用いる付加反応触媒としては、白金族金属系触媒、例えば白金系、パラジウム系、ロジウム系、ルテニウム系のものがあるが、白金系のものが特に好適である。この白金系のものとしては、白金黒あるいはアルミナ、シリカ等の担体に固体白金を担持させたもの、塩化白金酸、アルコール変性塩化白金酸、塩化白金酸とオレフィンとの錯体あるいは白金とビニルシロキサンとの錯体等を例示することができる。これらの白金の使用量は、所謂触媒量でよく、例えばアルコキシヒドロシラン類に対して、白金族金属換算で０．１～１，０００ｐｐｍ、特に０．５～１００ｐｐｍの質量で使用できる。
The addition reaction catalyst used in adding the alkoxyhydrosilane includes platinum group metal catalysts, such as platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, with platinum-based catalysts being particularly preferred. Examples of platinum-based materials include platinum black, solid platinum supported on a carrier such as alumina or silica, chloroplatinic acid, alcohol-modified chloroplatinic acid, a complex of chloroplatinic acid and an olefin, or a complex of platinum and vinylsiloxane. Examples include complexes of. The amount of platinum to be used may be a so-called catalytic amount, and for example, it can be used in a mass of 0.1 to 1,000 ppm, particularly 0.5 to 100 ppm in terms of platinum group metal, relative to the alkoxyhydrosilane.
この反応は、一般に５０～１２０℃、特に６０～１００℃の温度で、０．５～１２時間、特に１～６時間行うことが望ましく、また溶媒を使用せずに行うことができるが、上記付加反応等に悪影響を与えない限りにおいて、必要によりトルエン、キシレン等の適当な溶剤を使用することができる。
This reaction is generally carried out at a temperature of 50 to 120°C, particularly 60 to 100°C, for 0.5 to 12 hours, particularly 1 to 6 hours, and can be carried out without using a solvent, but as mentioned above. An appropriate solvent such as toluene or xylene may be used as necessary, as long as it does not adversely affect the addition reaction.
アルコキシヒドロシラン等の加水分解性基含有ヒドロシランのアセチレニル基（エチニル基）に対する付加反応では、幾何異性体が生成される。Ｅ体（ｔｒａｎｓ体）の生成が高選択的であるが、本発明で使用する（Ｂ）成分は、Ｚ体（ｃｉｓ体）も、その特性に悪影響を与えないことから、これらを分離することなく使用することができる。
In the addition reaction of a hydrolyzable group-containing hydrosilane such as alkoxyhydrosilane to an acetylenyl group (ethynyl group), geometric isomers are generated. Although the production of E-form (trans-form) is highly selective, component (B) used in the present invention also has Z-form (cis-form), which does not adversely affect its properties, so these can be separated. It can be used without.
前記一般式（２）の同一ケイ素原子上にアルコキシシリル－ビニレン基等の加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物の具体例としては、例えば、下記構造式で表されるものが挙げられ、（Ｂ）成分としては、これら１種を単独で又は２種以上を併用して使用することができる。
Specific examples of hydrolyzable organosilane compounds having two hydrolyzable silyl-vinylene groups such as alkoxysilyl-vinylene groups on the same silicon atom in the general formula (2) are, for example, those represented by the following structural formula: As component (B), one type of these can be used alone or two or more types can be used in combination.
上記（Ｂ）成分の加水分解性オルガノシラン化合物は、（Ａ）成分のオルガノポリシロキサン１００質量部に対して、０．１～１０質量部、好ましくは１～１０質量部の範囲で使用されるものであり、０．１質量部未満では十分な架橋が得られず、目的とする速硬化性を有する組成物とならず、１０質量部を超えると得られるゴム物性の機械特性も低下し、経済的に不利となるという問題が発生する場合がある。
なお、（Ｂ）成分の加水分解性オルガノシラン化合物は、１種を単独で使用しても、２種以上を併用してもよい。
第一剤中の（Ａ）成分及び（Ｂ）成分の合計量は１００質量％であってもよいが、２０～９５質量％であることが好ましく、３０～９０質量％であることがより好ましい。 The hydrolyzable organosilane compound as component (B) is used in an amount of 0.1 to 10 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of organopolysiloxane as component (A). If it is less than 0.1 parts by mass, sufficient crosslinking will not be obtained and the composition will not have the desired fast-curing properties, and if it exceeds 10 parts by mass, the mechanical properties of the resulting rubber will deteriorate, Problems such as being economically disadvantaged may occur.
Note that the hydrolyzable organosilane compound as the component (B) may be used alone or in combination of two or more.
The total amount of component (A) and component (B) in the first agent may be 100% by mass, but is preferably 20 to 95% by mass, more preferably 30 to 90% by mass. .
なお、（Ｂ）成分の加水分解性オルガノシラン化合物は、１種を単独で使用しても、２種以上を併用してもよい。
第一剤中の（Ａ）成分及び（Ｂ）成分の合計量は１００質量％であってもよいが、２０～９５質量％であることが好ましく、３０～９０質量％であることがより好ましい。 The hydrolyzable organosilane compound as component (B) is used in an amount of 0.1 to 10 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of organopolysiloxane as component (A). If it is less than 0.1 parts by mass, sufficient crosslinking will not be obtained and the composition will not have the desired fast-curing properties, and if it exceeds 10 parts by mass, the mechanical properties of the resulting rubber will deteriorate, Problems such as being economically disadvantaged may occur.
Note that the hydrolyzable organosilane compound as the component (B) may be used alone or in combination of two or more.
The total amount of component (A) and component (B) in the first agent may be 100% by mass, but is preferably 20 to 95% by mass, more preferably 30 to 90% by mass. .
［（Ｃ）成分］
（Ｃ）成分は、分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖された直鎖状のジオルガノポリシロキサンであり、本発明組成物の第二剤の主剤（ベースポリマー）として作用するものである。 [(C) Component]
Component (C) is a linear diorganopolysiloxane whose molecular chain ends are blocked with silanol groups (hydroxyl groups bonded to silicon atoms), and is the main component (base polymer) of the second component of the composition of the present invention. It acts as a.
（Ｃ）成分は、分子鎖両末端がシラノール基（ケイ素原子に結合した水酸基）で封鎖された直鎖状のジオルガノポリシロキサンであり、本発明組成物の第二剤の主剤（ベースポリマー）として作用するものである。 [(C) Component]
Component (C) is a linear diorganopolysiloxane whose molecular chain ends are blocked with silanol groups (hydroxyl groups bonded to silicon atoms), and is the main component (base polymer) of the second component of the composition of the present invention. It acts as a.
式中、Ｒ1は独立に炭素数１～１０の非置換又はハロゲン置換１価炭化水素基であり、具体的なものは（Ａ）成分の一般式（１）中のＲ1で例示したものと同様である。ｎは１０以上の数、好ましくは１０～２，０００の数、より好ましくは５０～１，５００の数、更に好ましくは１００～１，０００の数であり、特に該ジオルガノポリシロキサンの２３℃における粘度が２５～５００，０００ｍＰａ・ｓ、好ましくは５０～１００，０００ｍＰａ・ｓ、より好ましくは１００～５０，０００ｍＰａ・ｓとなる数である。なお、本発明において、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）等による２３℃での測定値であり、ジオルガノポリシロキサン中の主鎖を構成する繰り返し単位（（Ｒ1）2ＳｉＯ2/2）の繰り返し数ｎの値（又は重合度）は、例えば、トルエン等を展開溶媒としたゲルパーミエーションクロマトグラフィ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）等として求めた値である。（Ｃ）成分は１種単独でも又は２種以上を併用してもよい。
In the formula, R 1 is independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and specific examples are those exemplified for R 1 in general formula (1) of component (A). It is similar to n is a number of 10 or more, preferably a number of 10 to 2,000, more preferably a number of 50 to 1,500, and still more preferably a number of 100 to 1,000, particularly when the diorganopolysiloxane is heated at 23°C. The viscosity is 25 to 500,000 mPa·s, preferably 50 to 100,000 mPa·s, more preferably 100 to 50,000 mPa·s. In the present invention, the viscosity is a value measured at 23°C using a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer), etc. The value of the repeating number n (or degree of polymerization) of the repeating unit ((R 1 ) 2 SiO 2/2 or number average molecular weight). Component (C) may be used alone or in combination of two or more.
［（Ｄ）成分］
（Ｄ）成分は、本室温硬化性オルガノポリシロキサン組成物において、縮合触媒として働く重要な化合物であり、具体的には、１分子中に窒素原子を３個以上、好ましくは３～６個、より好ましくは３～５個有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物であり、特に、下記一般式（４）又は（４）’で表される、触媒機能を発現する１価又は２価の塩基性部位（Ｙ）を有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物が好ましいものとして挙げられる。 [(D) Component]
Component (D) is an important compound that acts as a condensation catalyst in the present room temperature curable organopolysiloxane composition, and specifically contains 3 or more nitrogen atoms, preferably 3 to 6 nitrogen atoms in one molecule, More preferably a hydrolyzable organosilane compound containing 3 to 5 amino functional groups and/or a partially hydrolyzed condensate thereof, particularly a catalyst represented by the following general formula (4) or (4)'. Hydrolyzable organosilane compounds containing an amino functional group and/or partially hydrolyzed condensates thereof having a monovalent or divalent basic moiety (Y) that exhibits a function are preferred.
（Ｄ）成分は、本室温硬化性オルガノポリシロキサン組成物において、縮合触媒として働く重要な化合物であり、具体的には、１分子中に窒素原子を３個以上、好ましくは３～６個、より好ましくは３～５個有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物であり、特に、下記一般式（４）又は（４）’で表される、触媒機能を発現する１価又は２価の塩基性部位（Ｙ）を有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物が好ましいものとして挙げられる。 [(D) Component]
Component (D) is an important compound that acts as a condensation catalyst in the present room temperature curable organopolysiloxane composition, and specifically contains 3 or more nitrogen atoms, preferably 3 to 6 nitrogen atoms in one molecule, More preferably a hydrolyzable organosilane compound containing 3 to 5 amino functional groups and/or a partially hydrolyzed condensate thereof, particularly a catalyst represented by the following general formula (4) or (4)'. Hydrolyzable organosilane compounds containing an amino functional group and/or partially hydrolyzed condensates thereof having a monovalent or divalent basic moiety (Y) that exhibits a function are preferred.
式（４）又は（４）’中、Ｙは、その構造中に窒素原子を２個以上含有する炭素数１～１５の１価又は２価炭化水素基を示し、Ｚは、ヘテロ原子を含んでもよい炭素数１～１０の非置換又は置換の２価炭化水素基を示す。Ｒは、炭素数１～６の加水分解性基及び炭素数１～６の１価炭化水素基から選ばれる１種又は２種以上の１価の基であり、ケイ素原子に結合する３個のＲのうち、少なくとも２個のＲは加水分解性基である。
In formula (4) or (4)', Y represents a monovalent or divalent hydrocarbon group having 1 to 15 carbon atoms containing two or more nitrogen atoms in its structure, and Z does not contain a heteroatom. represents an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, which may be substituted or unsubstituted. R is one or more monovalent groups selected from a hydrolyzable group having 1 to 6 carbon atoms and a monovalent hydrocarbon group having 1 to 6 carbon atoms; At least two of R are hydrolyzable groups.
一般式（４）又は（４）’において、触媒機能を発現する１価又は２価の塩基性部位（Ｙ）は、その構造中に窒素原子を２個以上、好ましくは２～５個、より好ましくは２～４個有する炭素数１～１５の１価又は２価炭化水素基を示し、塩基性部位（Ｙ）のうち、１価の基としては、例えば、下記式（５）で示される１，５，７－トリアザビシクロ［４．４．０］デカ－５－エンから誘導される基など、２価の基としては、例えば、下記式（６）で示されるＮ－置換又は非置換のグアニジル基等が挙げられる。なお、下記式（５）及び（６）において、波線部は、式（４）又は式（４）’の窒素原子との結合部位を示す。
In general formula (4) or (4)', the monovalent or divalent basic moiety (Y) that exhibits a catalytic function has 2 or more nitrogen atoms, preferably 2 to 5, or more, in its structure. It preferably represents a monovalent or divalent hydrocarbon group having 2 to 4 carbon atoms and having 1 to 15 carbon atoms, and among the basic moieties (Y), the monovalent group is, for example, represented by the following formula (5). Examples of divalent groups such as groups derived from 1,5,7-triazabicyclo[4.4.0]dec-5-ene include N-substituted or non-substituted groups represented by the following formula (6). Examples include substituted guanidyl groups. Note that in the following formulas (5) and (6), the wavy line portion indicates a bonding site with the nitrogen atom of formula (4) or formula (4)'.
式（６）中のＲ5～Ｒ8はそれぞれ独立に、水素原子又は炭素数１～１０の直鎖状、分岐状もしくは環状のアルキル基、アルケニル基、アリール基を示し、例えば、メチル基、エチル基、プロピ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、アリル基等のアルケニル基；フェニル基、トリル基等のアリール基などが挙げられる。これらの中では、メチル基、エチル基、フェニル基が好ましく、特にメチル基が好ましい。また、Ｒ5～Ｒ8は同じであっても、異なっていてもよい。
In formula (6), R 5 to R 8 each independently represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an aryl group, such as a methyl group, Examples include alkyl groups such as ethyl group and propyl group; cyclic alkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group and allyl group; and aryl groups such as phenyl group and tolyl group. Among these, methyl group, ethyl group, and phenyl group are preferred, and methyl group is particularly preferred. Further, R 5 to R 8 may be the same or different.
また、上記式（４）又は（４）’において、Ｒは、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｔｅｒｔ－ブトキシ基等のアルコキシ基、ビニロキシ基、アリロキシ基、プロペノキシ基、イソプロペノキシ基等のアルケニルオキシ基、ジメチルケトオキシム基、ジエチルケトオキシム基、メチルエチルケトオキシム基等のケトオキシム基、アセトキシ基等のアシルオキシ基などの炭素数１～６、好ましくは炭素数１～４の加水分解性基（即ち、ケイ素原子に結合してＳｉ－Ｏ－Ｃ結合を形成し得る基）、及び、メチル基、エチル基等のアルキル基、ビニル基等のアルケニル基、フェニル基等のアリール基などの炭素数１～６、好ましくは炭素数１～４の１価炭化水素基から選ばれる１種又は２種以上の１価の基であり、ケイ素原子に結合する３個のＲのうち、少なくとも２個、好ましくは３個のＲは加水分解性基である。
In the above formula (4) or (4)', R is an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a vinyloxy group, an allyloxy group. , an alkenyloxy group such as a propenoxy group, an isopropenoxy group, a ketoxime group such as a dimethylketoxime group, a diethylketoxime group, a methylethylketoxime group, an acyloxy group such as an acetoxy group, etc. having 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms. 4 hydrolyzable groups (that is, groups that can bond to silicon atoms to form Si-O-C bonds), alkyl groups such as methyl groups and ethyl groups, alkenyl groups such as vinyl groups, phenyl groups, etc. One or more monovalent groups selected from monovalent hydrocarbon groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as an aryl group, and three R bonded to a silicon atom. Among them, at least two, preferably three R's are hydrolyzable groups.
また、上記式（４）又は（４）’において、加水分解性シリル基（－ＳｉＲ3）としては、例えば、トリメトキシシリル基、メチルジメトキシシリル基、ビニルジメトキシシリル基、フェニルジメトキシシリル基、トリエトキシシリル基等のアルコキシシリル基；トリイソプロペノキシシリル基、メチルジイソプロペノキシシリル基、エチルジイソプロペノキシシリル基、ビニルジイソプロペノキシシリル基、フェニルジイソプロペノキシシリル基等のイソプロペノキシシリル基；トリス（ジメチルケトオキシム）シリル基、トリス（ジエチルケトオキシム）シリル基、トリス（エチルメチルケトオキシム）シリル基等のケトオキシムシリル基などが挙げられる。
In the above formula (4) or (4)', the hydrolyzable silyl group (-SiR 3 ) is, for example, trimethoxysilyl group, methyldimethoxysilyl group, vinyldimethoxysilyl group, phenyldimethoxysilyl group, trimethoxysilyl group, Alkoxysilyl group such as ethoxysilyl group; Penoxysilyl group: Ketoxime silyl groups such as tris(dimethylketoxime)silyl group, tris(diethylketoxime)silyl group, tris(ethylmethylketoxime)silyl group, and the like.
上記式（４）又は（４）’において、Ｚは、酸素原子、窒素原子等のヘテロ原子を含んでもよい、炭素数１～１０、特には炭素数３～６の、直鎖状、分岐状もしくは環状のアルキレン基、アルケニレン基、アリーレン基等又はこれらが組み合わされた基などの非置換又は置換の２価炭化水素基を示す。Ｚとしては、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ヘキサメチレン基、オクタメチレン基、デカメチレン基、２－メチルプロピレン基等のアルキレン基；フェニレン基等のアリーレン基、これらアルキレン基とアリーレン基が結合した基、ケトン、エステル、アミド等が介在した上記アルキレン基などが挙げられるが、好ましくはメチレン基、エチレン基、トリメチレン基、プロピレン基、アミド結合を介したプロピレン基等であり、特に好ましくはトリメチレン基である。
In the above formula (4) or (4)', Z is a straight chain, branched, carbon atom having 1 to 10 carbon atoms, particularly 3 to 6 carbon atoms, which may contain a hetero atom such as an oxygen atom or a nitrogen atom. Alternatively, it represents an unsubstituted or substituted divalent hydrocarbon group such as a cyclic alkylene group, alkenylene group, arylene group, or a combination thereof. Examples of Z include alkylene groups such as methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, and 2-methylpropylene group; arylene groups such as phenylene group; Examples include groups in which these alkylene groups and arylene groups are bonded, and the above-mentioned alkylene groups with intervening ketones, esters, amide, etc., but preferred are methylene groups, ethylene groups, trimethylene groups, propylene groups, and propylene groups via amide bonds. etc., and trimethylene group is particularly preferred.
一般式（４）又は一般式（４）’で示されるアミノ官能性基含有加水分解性オルガノシランの具体例としては、下記一般式（７）～（１２）に示されるもの等を挙げることができる。なお、Ｍｅ、Ｅｔ、Ｐｈはそれぞれ、メチル基、エチル基、フェニル基を示す。
Specific examples of the amino-functional group-containing hydrolyzable organosilane represented by general formula (4) or general formula (4)' include those shown by general formulas (7) to (12) below. can. Note that Me, Et, and Ph represent a methyl group, an ethyl group, and a phenyl group, respectively.
上記一般式（７）～（１２）のうち、式（７）、式（８）又は式（９）で示される、特には、式（９）で示される、Ｎ－メチル置換のグアニジル基含有トリメトキシシラン（例えば、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン）等の、Ｎ－メチル置換グアニジル基含有トリアルコキシシランが好ましい。
Among the above general formulas (7) to (12), it is represented by formula (7), formula (8), or formula (9), and in particular, it is represented by formula (9), and contains an N-methyl substituted guanidyl group. Preferred are trialkoxysilanes containing N-methyl substituted guanidyl groups, such as trimethoxysilane (eg, γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane).
（Ｄ）成分の配合量は、（Ｃ）成分１００質量部に対して、０．１～１０質量部であり、０．１～５質量部が好ましく、０．５～５質量部がより好ましい。０．１質量部未満では、目的とする硬化触媒としての機能を果たさない場合がある。１０質量部を超えると、コスト的に不利となり硬化性も低下するため好ましくない。
The blending amount of component (D) is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (C). . If it is less than 0.1 part by mass, it may not function as the intended curing catalyst. If it exceeds 10 parts by mass, it is not preferable because it is disadvantageous in terms of cost and curability decreases.
［（Ｅ）成分］
（Ｅ）成分は、ケトン基を有する有機化合物（ケトン類）であり、具体例としてはアセトン、２－ブタノン、３－ペンタノン、２－ヘプタノンなどの直鎖状ケトン化合物；メチルイソブチルケトン、４－メチルヘキサン－２－オン、４－メチルヘプタン－３－オン、６－メチルヘプタン－３－オンなどの分岐状ケトン化合物；シクロペンタノン、シクロヘキサノン、シクロヘプタノン、３－メチルシクロペンタン－１－オン、３，３－ジメチルシクロペンタン－１－オン、２－エチルシクロペンタン－１－オン、３－メチルシクロヘキサン－１－オン、４－メチルシクロヘキサン－１－オン、２，５－ジメチルシクロヘキサン－１－オンなどの環状ケトン化合物；シクロペンタン－１，３－ジオン、シクロペンタン－１，２－ジオン、３－メチルシクロペンタン－１，２－ジオン、シクロヘキサン－１，２－ジオン、３－メチルシクロヘキサン－１，２－ジオンなどのジケトン類；アセト酢酸メチル、アセト酢酸エチル、アセト酢酸プロピル、アセト酢酸イソプロピル、アセト酢酸ブチル、アセト酢酸イソブチル、プロピオニル酢酸メチル、プロピオニル酢酸エチル等のβ－ケトエステル類などが挙げられる。 [(E) component]
Component (E) is an organic compound (ketones) having a ketone group, and specific examples include linear ketone compounds such as acetone, 2-butanone, 3-pentanone, and 2-heptanone; methyl isobutyl ketone, 4- Branched ketone compounds such as methylhexan-2-one, 4-methylheptan-3-one, 6-methylheptan-3-one; cyclopentanone, cyclohexanone, cycloheptanone, 3-methylcyclopentan-1-one , 3,3-dimethylcyclopentan-1-one, 2-ethylcyclopentan-1-one, 3-methylcyclohexan-1-one, 4-methylcyclohexan-1-one, 2,5-dimethylcyclohexan-1-one Cyclic ketone compounds such as cyclopentane-1,3-dione, cyclopentane-1,2-dione, 3-methylcyclopentane-1,2-dione, cyclohexane-1,2-dione, 3-methylcyclohexane- Diketones such as 1,2-dione; β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isopropyl acetoacetate, butyl acetoacetate, isobutyl acetoacetate, methyl propionyl acetate, ethyl propionyl acetate, etc. It will be done.
（Ｅ）成分は、ケトン基を有する有機化合物（ケトン類）であり、具体例としてはアセトン、２－ブタノン、３－ペンタノン、２－ヘプタノンなどの直鎖状ケトン化合物；メチルイソブチルケトン、４－メチルヘキサン－２－オン、４－メチルヘプタン－３－オン、６－メチルヘプタン－３－オンなどの分岐状ケトン化合物；シクロペンタノン、シクロヘキサノン、シクロヘプタノン、３－メチルシクロペンタン－１－オン、３，３－ジメチルシクロペンタン－１－オン、２－エチルシクロペンタン－１－オン、３－メチルシクロヘキサン－１－オン、４－メチルシクロヘキサン－１－オン、２，５－ジメチルシクロヘキサン－１－オンなどの環状ケトン化合物；シクロペンタン－１，３－ジオン、シクロペンタン－１，２－ジオン、３－メチルシクロペンタン－１，２－ジオン、シクロヘキサン－１，２－ジオン、３－メチルシクロヘキサン－１，２－ジオンなどのジケトン類；アセト酢酸メチル、アセト酢酸エチル、アセト酢酸プロピル、アセト酢酸イソプロピル、アセト酢酸ブチル、アセト酢酸イソブチル、プロピオニル酢酸メチル、プロピオニル酢酸エチル等のβ－ケトエステル類などが挙げられる。 [(E) component]
Component (E) is an organic compound (ketones) having a ketone group, and specific examples include linear ketone compounds such as acetone, 2-butanone, 3-pentanone, and 2-heptanone; methyl isobutyl ketone, 4- Branched ketone compounds such as methylhexan-2-one, 4-methylheptan-3-one, 6-methylheptan-3-one; cyclopentanone, cyclohexanone, cycloheptanone, 3-methylcyclopentan-1-one , 3,3-dimethylcyclopentan-1-one, 2-ethylcyclopentan-1-one, 3-methylcyclohexan-1-one, 4-methylcyclohexan-1-one, 2,5-dimethylcyclohexan-1-one Cyclic ketone compounds such as cyclopentane-1,3-dione, cyclopentane-1,2-dione, 3-methylcyclopentane-1,2-dione, cyclohexane-1,2-dione, 3-methylcyclohexane- Diketones such as 1,2-dione; β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isopropyl acetoacetate, butyl acetoacetate, isobutyl acetoacetate, methyl propionyl acetate, ethyl propionyl acetate, etc. It will be done.
（Ｅ）成分の配合量は、（Ｃ）成分１００質量部に対して、０．１～５質量部であり、０．１～３質量部が好ましく、０．５～２質量部がより好ましい。０．１質量部未満では、目的とする硬化性が発現しない場合がある。５質量部を超えると、コスト的に不利となるばかりか、硬化したゴムからのブリードや臭気が強くなるため好ましくない。
第二剤中の（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分の合計量は１００質量％であってもよいが、２０～９５質量％であることが好ましく、３０～９０質量％であることがより好ましい。 The blending amount of component (E) is 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.5 to 2 parts by mass, per 100 parts by mass of component (C). . If the amount is less than 0.1 part by mass, the desired curability may not be achieved. If it exceeds 5 parts by mass, it is not preferable because it is not only disadvantageous in terms of cost, but also causes strong bleeding and odor from the cured rubber.
The total amount of component (C), component (D), and component (E) in the second agent may be 100% by mass, but preferably 20 to 95% by mass, and 30 to 90% by mass. It is more preferable that there be.
第二剤中の（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分の合計量は１００質量％であってもよいが、２０～９５質量％であることが好ましく、３０～９０質量％であることがより好ましい。 The blending amount of component (E) is 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, and more preferably 0.5 to 2 parts by mass, per 100 parts by mass of component (C). . If the amount is less than 0.1 part by mass, the desired curability may not be achieved. If it exceeds 5 parts by mass, it is not preferable because it is not only disadvantageous in terms of cost, but also causes strong bleeding and odor from the cured rubber.
The total amount of component (C), component (D), and component (E) in the second agent may be 100% by mass, but preferably 20 to 95% by mass, and 30 to 90% by mass. It is more preferable that there be.
［その他の成分］
本発明の組成物の硬化物の各種被着体への接着性をさらに向上させるために、必要に応じて配合できる任意成分として、シランカップリング剤（１分子中に、窒素、硫黄及び酸素から選ばれるヘテロ原子を含有する官能性基（但し、グアニジル基を除く）を有する１価炭化水素基を有するアルコキシシラン等の加水分解性シラン化合物、又はいわゆるカーボンファンクショナルシラン化合物）を接着性付与剤として組成物に配合してもよい。シランカップリング剤としては、加水分解性基として、アルコキシシリル基又はアルケノキシシリル基を有するシラン化合物が挙げられ、ビニルトリス（β－メトキシエトキシ）シラン、γ－メタクリロキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、Ｎ－β－（アミノエチル）γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、３－（Ｎ－アミノメチルベンジルアミノ）プロピルトリメトキシシラン、Ｎ，Ｎ’－ビス［３－（トリメトキシシリル）プロピル］エチレンジアミン、Ｎ，Ｎ－ビス［３－（トリメトキシシリル）プロピル］アミン、γ－メルカプトプロピルトリメトキシシラン、γ－グリシドキシプロピルトリイソプロペノキシシラン、（メタ）アクリルシランとアミノシランの反応物、エポキシシランとアミノシランの反応物等、アミノシランとハロゲン化アルキル基含有シランとの反応物などが例示される。特にはアミノ基を１分子内に少なくとも１つ有するシランカップリング剤の使用が好ましい。 [Other ingredients]
In order to further improve the adhesion of the cured product of the composition of the present invention to various adherends, a silane coupling agent (from nitrogen, sulfur, and oxygen in one molecule) can be added as an optional component. A hydrolyzable silane compound such as an alkoxysilane having a monovalent hydrocarbon group having a functional group containing a selected heteroatom (however, excluding a guanidyl group), or a so-called carbon functional silane compound) is used as an adhesion imparting agent. It may be added to the composition as Examples of the silane coupling agent include silane compounds having an alkoxysilyl group or an alkenoxysilyl group as a hydrolyzable group, such as vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-(N-aminomethylbenzylamino)propyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N-bis[3-( Trimethoxysilyl)propyl]amine, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltriisopropenoxysilane, reaction products of (meth)acrylic silane and aminosilane, reaction products of epoxysilane and aminosilane, etc., aminosilane and Examples include reactants with halogenated alkyl group-containing silanes. In particular, it is preferable to use a silane coupling agent having at least one amino group in one molecule.
本発明の組成物の硬化物の各種被着体への接着性をさらに向上させるために、必要に応じて配合できる任意成分として、シランカップリング剤（１分子中に、窒素、硫黄及び酸素から選ばれるヘテロ原子を含有する官能性基（但し、グアニジル基を除く）を有する１価炭化水素基を有するアルコキシシラン等の加水分解性シラン化合物、又はいわゆるカーボンファンクショナルシラン化合物）を接着性付与剤として組成物に配合してもよい。シランカップリング剤としては、加水分解性基として、アルコキシシリル基又はアルケノキシシリル基を有するシラン化合物が挙げられ、ビニルトリス（β－メトキシエトキシ）シラン、γ－メタクリロキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、Ｎ－β－（アミノエチル）γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、３－（Ｎ－アミノメチルベンジルアミノ）プロピルトリメトキシシラン、Ｎ，Ｎ’－ビス［３－（トリメトキシシリル）プロピル］エチレンジアミン、Ｎ，Ｎ－ビス［３－（トリメトキシシリル）プロピル］アミン、γ－メルカプトプロピルトリメトキシシラン、γ－グリシドキシプロピルトリイソプロペノキシシラン、（メタ）アクリルシランとアミノシランの反応物、エポキシシランとアミノシランの反応物等、アミノシランとハロゲン化アルキル基含有シランとの反応物などが例示される。特にはアミノ基を１分子内に少なくとも１つ有するシランカップリング剤の使用が好ましい。 [Other ingredients]
In order to further improve the adhesion of the cured product of the composition of the present invention to various adherends, a silane coupling agent (from nitrogen, sulfur, and oxygen in one molecule) can be added as an optional component. A hydrolyzable silane compound such as an alkoxysilane having a monovalent hydrocarbon group having a functional group containing a selected heteroatom (however, excluding a guanidyl group), or a so-called carbon functional silane compound) is used as an adhesion imparting agent. It may be added to the composition as Examples of the silane coupling agent include silane compounds having an alkoxysilyl group or an alkenoxysilyl group as a hydrolyzable group, such as vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-(N-aminomethylbenzylamino)propyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N-bis[3-( Trimethoxysilyl)propyl]amine, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltriisopropenoxysilane, reaction products of (meth)acrylic silane and aminosilane, reaction products of epoxysilane and aminosilane, etc., aminosilane and Examples include reactants with halogenated alkyl group-containing silanes. In particular, it is preferable to use a silane coupling agent having at least one amino group in one molecule.
シランカップリング剤を配合する場合、第一剤及び第二剤のいずれに配合してもよいが、第一剤に配合することが好ましく、その配合量は、（Ａ）成分１００質量部当たり、通常、０．１～２０質量部、好ましくは０．１～１５質量部、特に好ましくは０．１～１０質量部である。０．１質量部未満では十分な接着性が得られない場合があり、２０質量部を超えると良好な機械特性が得られなかったり、また価格的に不利となる場合がある。
When blending a silane coupling agent, it may be blended in either the first part or the second part, but it is preferably blended in the first part, and the blending amount is per 100 parts by mass of component (A). It is usually 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, particularly preferably 0.1 to 10 parts by weight. If it is less than 0.1 parts by mass, sufficient adhesiveness may not be obtained, and if it exceeds 20 parts by mass, good mechanical properties may not be obtained or it may be disadvantageous in terms of price.
また、本発明の組成物を硬化して得られるシリコーンゴム硬化物の機械的強度等の物性を向上させるため、任意成分として無機充填剤を組成物に配合してもよい。例えば、粉砕シリカ、煙霧質シリカ（ヒュームドシリカ）、湿式シリカ、結晶性シリカ、水酸化アルミニウム、アルミナ、ベーマイト、水酸化マグネシウム、酸化マグネシウム、水酸化カルシウム、炭酸カルシウム、炭酸亜鉛、塩基性炭酸亜鉛、酸化亜鉛、酸化チタン、カーボンブラック、ガラスビーズ、ガラスバルーンなどが挙げられ、単独で使用してもよく、また２種類以上を組み合わせてもよい。これらの無機充填剤は、表面処理されていなくても、公知の処理剤で表面処理されていてもよい。公知の処理剤としては例えば、特開２０００－２５６５５８号公報に記載の加水分解性基含有ポリシロキサンが好ましいが、これに限定されるものではない。これらの中では、粉砕シリカ、煙霧質シリカ、湿式シリカ、結晶性シリカ等のシリカ系充填剤、あるいは炭酸カルシウムが好ましい。
Furthermore, in order to improve physical properties such as mechanical strength of the silicone rubber cured product obtained by curing the composition of the present invention, an inorganic filler may be added to the composition as an optional component. For example, ground silica, fumed silica, wet silica, crystalline silica, aluminum hydroxide, alumina, boehmite, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium carbonate, zinc carbonate, basic zinc carbonate. , zinc oxide, titanium oxide, carbon black, glass beads, glass balloons, etc., and may be used alone or in combination of two or more. These inorganic fillers may not be surface-treated or may be surface-treated with a known treatment agent. As a known treatment agent, for example, a hydrolyzable group-containing polysiloxane described in JP-A No. 2000-256558 is preferred, but the treatment agent is not limited thereto. Among these, silica-based fillers such as ground silica, fumed silica, wet silica, and crystalline silica, or calcium carbonate are preferred.
無機充填剤を配合する場合、第一剤及び第二剤のいずれに配合してもよく、その配合量は、（Ａ）成分ないし（Ｃ）成分の配合量１００質量部に対して１～４００質量部が好ましく、より好ましくは１～３５０質量部、特に好ましくは１～３００質量部である。１質量部未満では、目的とするゴム強度やゴム弾性を有する硬化物が得難い場合がある。また４００質量部を超えると、前記（Ａ）成分ないし（Ｃ）成分との混練が困難となり、良好な室温硬化性オルガノポリシロキサン組成物を調製するのが難しい場合がある。
When blending an inorganic filler, it may be blended in either the first part or the second part, and the blending amount is 1 to 400 parts by mass per 100 parts by mass of components (A) to (C). Parts by weight are preferred, more preferably 1 to 350 parts by weight, particularly preferably 1 to 300 parts by weight. If the amount is less than 1 part by mass, it may be difficult to obtain a cured product having the desired rubber strength and rubber elasticity. If the amount exceeds 400 parts by mass, it becomes difficult to knead with the components (A) to (C), and it may be difficult to prepare a good room-temperature-curable organopolysiloxane composition.
また、本発明の二成分型室温硬化性オルガノポリシロキサン組成物は上記成分以外に、各種の添加剤を任意成分として配合してもよい。添加剤としては、公知の添加剤を本発明の目的を損なわない範囲で添加してもよい。例えば、ウェッターやチキソトロピー向上剤としてのポリエーテル化合物、可塑剤としての非反応性ジメチルシリコーンオイル（分子鎖両末端トリアルキルシリル基封鎖ジメチルポリシロキサン）、イソパラフィン、架橋密度向上剤としてのトリメチルシロキシ単位〔（ＣＨ3）3ＳｉＯ1/2単位〕とＳｉＯ2単位とからなる三次元網状構造のオルガノポリシロキサンレジン等が挙げられる。
In addition to the above-mentioned components, the two-component room-temperature-curable organopolysiloxane composition of the present invention may contain various additives as optional components. As additives, known additives may be added within a range that does not impair the purpose of the present invention. For example, polyether compounds as wetters and thixotropy improvers, non-reactive dimethyl silicone oil (dimethyl polysiloxane blocked with trialkylsilyl groups at both ends of the molecular chain) as plasticizers, isoparaffins, trimethylsiloxy units as crosslinking density improvers [ (CH 3 ) 3 SiO 1/2 units] and an organopolysiloxane resin having a three-dimensional network structure consisting of SiO 2 units.
更に、必要に応じて、顔料、染料、蛍光増白剤等の着色剤；防かび剤；抗菌剤；非反応性フェニルシリコーンオイル（分子鎖両末端トリアルキルシリル基封鎖メチルフェニルポリシロキサン）、フルオロシリコーンオイル（分子鎖両末端トリアルキルシリル基封鎖メチル（３，３，３－トリフルオロプロピル）ポリシロキサン）等のブリードオイル；シリコーンと非相溶性である有機液体等の表面改質剤；及びトルエン、キシレン、溶剤揮発油、シクロヘキサン、メチルシクロヘキサン、低沸点イソパラフィン等の溶剤も添加してよい。
Furthermore, if necessary, colorants such as pigments, dyes, and optical brighteners; fungicides; antibacterial agents; non-reactive phenyl silicone oil (methylphenyl polysiloxane blocked with trialkylsilyl groups at both molecular chain ends), Bleed oil such as silicone oil (methyl (3,3,3-trifluoropropyl)polysiloxane blocked with trialkylsilyl groups at both ends of the molecular chain); Surface modifier such as organic liquid that is incompatible with silicone; and toluene Solvents such as , xylene, solvent volatile oils, cyclohexane, methylcyclohexane, and low boiling isoparaffins may also be added.
組成物の製造方法
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、（Ａ）成分及び（Ｂ）成分を含有する第一剤と、（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分を含有する第二剤とからなるものである。第一剤、第二剤ともに各成分を常法に従い混合することによって調製でき、混合方法は、従来の方法でよく、各成分は減圧下で混合されてもよい。
本発明の二成分型室温硬化性オルガノポリシロキサン組成物は、第一剤及び第二剤を、湿分を避けた雰囲気下で保存することができ、第一剤と第二剤を任意の配合比で混合し、これを室温（２３℃±１５℃）で空気雰囲気下に放置すると、従来の室温硬化性オルガノポリシロキサン組成物において常用されていた環境負荷の大きな金属系縮合触媒を添加せずとも、空気中の水分（湿気）により通常５分～３日で硬化する。
第一剤と第二剤の混合比は、体積比で好ましくは第一剤：第二剤＝１：１～１０：１、特に好ましくは第一剤：第二剤＝１：１～５：１となるように配合することが作業性や第一剤と第二剤を混合する際の均一性（混ざり易さ）の点から好ましい。また、任意成分は第一剤と第二剤のどちらに配合してもよく、どちらか一方に配合しても両方に配合してもよい。 Method for producing composition The two-component room-temperature fast-curing organopolysiloxane composition of the present invention comprises a first part containing component (A) and component (B), component (C), component (D) and ( and a second agent containing component E). Both the first part and the second part can be prepared by mixing the respective components according to a conventional method.The mixing method may be a conventional method, and the respective components may be mixed under reduced pressure.
The two-component room-temperature-curable organopolysiloxane composition of the present invention allows the first and second parts to be stored in an atmosphere that avoids moisture, and the first and second parts can be mixed in any desired combination. When mixed at the same ratio and left in an air atmosphere at room temperature (23°C ± 15°C), a metal-based condensation catalyst that has a large environmental impact, which is commonly used in conventional room-temperature curable organopolysiloxane compositions, is not added. Both types usually harden in 5 minutes to 3 days due to moisture in the air.
The mixing ratio of the first part and the second part is preferably first part: second part = 1:1 to 10:1, particularly preferably first part: second part = 1:1 to 5: 1 from the viewpoint of workability and uniformity (easiness of mixing) when mixing the first and second agents. Further, the optional component may be blended in either the first part or the second part, or may be blended in either one or both.
本発明の二成分型室温速硬化性オルガノポリシロキサン組成物は、（Ａ）成分及び（Ｂ）成分を含有する第一剤と、（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分を含有する第二剤とからなるものである。第一剤、第二剤ともに各成分を常法に従い混合することによって調製でき、混合方法は、従来の方法でよく、各成分は減圧下で混合されてもよい。
本発明の二成分型室温硬化性オルガノポリシロキサン組成物は、第一剤及び第二剤を、湿分を避けた雰囲気下で保存することができ、第一剤と第二剤を任意の配合比で混合し、これを室温（２３℃±１５℃）で空気雰囲気下に放置すると、従来の室温硬化性オルガノポリシロキサン組成物において常用されていた環境負荷の大きな金属系縮合触媒を添加せずとも、空気中の水分（湿気）により通常５分～３日で硬化する。
第一剤と第二剤の混合比は、体積比で好ましくは第一剤：第二剤＝１：１～１０：１、特に好ましくは第一剤：第二剤＝１：１～５：１となるように配合することが作業性や第一剤と第二剤を混合する際の均一性（混ざり易さ）の点から好ましい。また、任意成分は第一剤と第二剤のどちらに配合してもよく、どちらか一方に配合しても両方に配合してもよい。 Method for producing composition The two-component room-temperature fast-curing organopolysiloxane composition of the present invention comprises a first part containing component (A) and component (B), component (C), component (D) and ( and a second agent containing component E). Both the first part and the second part can be prepared by mixing the respective components according to a conventional method.The mixing method may be a conventional method, and the respective components may be mixed under reduced pressure.
The two-component room-temperature-curable organopolysiloxane composition of the present invention allows the first and second parts to be stored in an atmosphere that avoids moisture, and the first and second parts can be mixed in any desired combination. When mixed at the same ratio and left in an air atmosphere at room temperature (23°C ± 15°C), a metal-based condensation catalyst that has a large environmental impact, which is commonly used in conventional room-temperature curable organopolysiloxane compositions, is not added. Both types usually harden in 5 minutes to 3 days due to moisture in the air.
The mixing ratio of the first part and the second part is preferably first part: second part = 1:1 to 10:1, particularly preferably first part: second part = 1:1 to 5: 1 from the viewpoint of workability and uniformity (easiness of mixing) when mixing the first and second agents. Further, the optional component may be blended in either the first part or the second part, or may be blended in either one or both.
以下、本発明を具体的に説明する実施例及び比較例を示すが、本発明は下記の実施例に制限されるものではない。なお、実施例において、粘度は２３℃における回転粘度計による測定値であり、重合度は、トルエンを展開溶媒としたゲルパーミエーションクロマトグラフィ分析におけるポリスチレン換算の数平均重合度を示す。
Examples and comparative examples specifically illustrating the present invention will be shown below, but the present invention is not limited to the following examples. In the examples, the viscosity is a value measured by a rotational viscometer at 23° C., and the degree of polymerization indicates the number average degree of polymerization in terms of polystyrene in gel permeation chromatography analysis using toluene as a developing solvent.
＜第一剤の調製＞
１．第一剤Ａ－１
分子鎖両末端がトリメトキシシロキシ基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（１）において、Ｘ＝酸素原子、Ｒ1＝Ｒ2＝メチル基、ａ＝０、ｎ＝約６２０に該当する、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン）５０質量部と分子鎖両末端がトリメトキシシロキシ基で封鎖され、粘度が９００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（１）において、Ｘ＝酸素原子、Ｒ1＝Ｒ2＝メチル基、ａ＝０、ｎ＝約２７０に該当する、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン）５０質量部、ＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ８質量部及び炭酸カルシウム８０質量部を減圧条件下で３０分間均一に混合した。その後、ビス（ジメトキシメチルシリル－ビニレン）ジメチルシラン（即ち、前記式（２）において、Ｒ3＝Ｒ4＝メチル基、ｂ＝１に該当する。以下、同様）２．５質量部、γ－アミノプロピルトリエトキシシラン１．０質量部を加え、減圧条件下１５分間均一に混合して第一剤Ａ－１を調製した。 <Preparation of first agent>
1. First agent A-1
Dimethylpolysiloxane with both molecular chain ends blocked with trimethoxysiloxy groups and a viscosity of 20,000 mPa·s (i.e., in the above formula (1), X = oxygen atom, R 1 = R 2 = methyl group, a = 50 parts by mass of dimethylpolysiloxane (dimethylpolysiloxane with trimethoxysiloxy groups blocked at both ends of the molecular chain, corresponding to n = about 620) and dimethylpolysiloxane (with trimethoxysiloxy groups blocked at both ends of the molecular chain and a viscosity of 900 mPa・s) That is, in the above formula (1), X = oxygen atom, R 1 = R 2 = methyl group, a = 0, n = about 270, dimethylpolysiloxane (trimethoxysiloxy group-blocked dimethylpolysiloxane at both molecular chain ends) 50 mass 8 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g and 80 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 2.5 parts by mass of bis(dimethoxymethylsilyl-vinylene)dimethylsilane (that is, in the above formula (2), R 3 =R 4 =methyl group, b=1; the same applies hereinafter), γ- 1.0 parts by mass of aminopropyltriethoxysilane was added and mixed uniformly for 15 minutes under reduced pressure to prepare a first agent A-1.
１．第一剤Ａ－１
分子鎖両末端がトリメトキシシロキシ基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（１）において、Ｘ＝酸素原子、Ｒ1＝Ｒ2＝メチル基、ａ＝０、ｎ＝約６２０に該当する、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン）５０質量部と分子鎖両末端がトリメトキシシロキシ基で封鎖され、粘度が９００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（１）において、Ｘ＝酸素原子、Ｒ1＝Ｒ2＝メチル基、ａ＝０、ｎ＝約２７０に該当する、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン）５０質量部、ＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ８質量部及び炭酸カルシウム８０質量部を減圧条件下で３０分間均一に混合した。その後、ビス（ジメトキシメチルシリル－ビニレン）ジメチルシラン（即ち、前記式（２）において、Ｒ3＝Ｒ4＝メチル基、ｂ＝１に該当する。以下、同様）２．５質量部、γ－アミノプロピルトリエトキシシラン１．０質量部を加え、減圧条件下１５分間均一に混合して第一剤Ａ－１を調製した。 <Preparation of first agent>
1. First agent A-1
Dimethylpolysiloxane with both molecular chain ends blocked with trimethoxysiloxy groups and a viscosity of 20,000 mPa·s (i.e., in the above formula (1), X = oxygen atom, R 1 = R 2 = methyl group, a = 50 parts by mass of dimethylpolysiloxane (dimethylpolysiloxane with trimethoxysiloxy groups blocked at both ends of the molecular chain, corresponding to n = about 620) and dimethylpolysiloxane (with trimethoxysiloxy groups blocked at both ends of the molecular chain and a viscosity of 900 mPa・s) That is, in the above formula (1), X = oxygen atom, R 1 = R 2 = methyl group, a = 0, n = about 270, dimethylpolysiloxane (trimethoxysiloxy group-blocked dimethylpolysiloxane at both molecular chain ends) 50 mass 8 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g and 80 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 2.5 parts by mass of bis(dimethoxymethylsilyl-vinylene)dimethylsilane (that is, in the above formula (2), R 3 =R 4 =methyl group, b=1; the same applies hereinafter), γ- 1.0 parts by mass of aminopropyltriethoxysilane was added and mixed uniformly for 15 minutes under reduced pressure to prepare a first agent A-1.
２．第一剤Ａ－２
分子鎖両末端がトリメトキシシロキシ基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（１）において、Ｘ＝酸素原子、Ｒ1＝Ｒ2＝メチル基、ａ＝０、ｎ＝約６２０に該当する、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン）５０質量部と分子鎖両末端がトリメトキシシロキシ基で封鎖され、粘度が９００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（１）において、Ｘ＝酸素原子、Ｒ1＝Ｒ2＝メチル基、ａ＝０、ｎ＝約２７０に該当する、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン）５０質量部、ＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ８質量部及び炭酸カルシウム８０質量部を減圧条件下で３０分間均一に混合した。その後、ビス（ジメトキシメチルシリル－ビニレン）ジメチルシラン（即ち、前記式（２）において、Ｒ3＝Ｒ4＝メチル基、ｂ＝１に該当する。以下、同様）２．５質量部、Ｎ－β－（アミノエチル）γ－アミノプロピルトリメトキシシラン１．０質量部を加え、減圧条件下１５分間均一に混合して第一剤Ａ－２を調製した。 2. First agent A-2
Dimethylpolysiloxane with both molecular chain ends blocked with trimethoxysiloxy groups and a viscosity of 20,000 mPa·s (i.e., in the above formula (1), X = oxygen atom, R 1 = R 2 = methyl group, a = 50 parts by mass of dimethylpolysiloxane (dimethylpolysiloxane with trimethoxysiloxy groups blocked at both ends of the molecular chain, corresponding to n = about 620) and dimethylpolysiloxane (with trimethoxysiloxy groups blocked at both ends of the molecular chain and a viscosity of 900 mPa・s) That is, in the above formula (1), X = oxygen atom, R 1 = R 2 = methyl group, a = 0, n = about 270, dimethylpolysiloxane (trimethoxysiloxy group-blocked dimethylpolysiloxane at both molecular chain ends) 50 mass 8 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g and 80 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 2.5 parts by mass of bis(dimethoxymethylsilyl-vinylene)dimethylsilane (that is, in the above formula (2), R 3 = R 4 = methyl group, b = 1. The same applies hereinafter), N- 1.0 parts by mass of β-(aminoethyl)γ-aminopropyltrimethoxysilane was added and mixed uniformly for 15 minutes under reduced pressure to prepare a first agent A-2.
分子鎖両末端がトリメトキシシロキシ基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（１）において、Ｘ＝酸素原子、Ｒ1＝Ｒ2＝メチル基、ａ＝０、ｎ＝約６２０に該当する、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン）５０質量部と分子鎖両末端がトリメトキシシロキシ基で封鎖され、粘度が９００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（１）において、Ｘ＝酸素原子、Ｒ1＝Ｒ2＝メチル基、ａ＝０、ｎ＝約２７０に該当する、分子鎖両末端トリメトキシシロキシ基封鎖ジメチルポリシロキサン）５０質量部、ＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ８質量部及び炭酸カルシウム８０質量部を減圧条件下で３０分間均一に混合した。その後、ビス（ジメトキシメチルシリル－ビニレン）ジメチルシラン（即ち、前記式（２）において、Ｒ3＝Ｒ4＝メチル基、ｂ＝１に該当する。以下、同様）２．５質量部、Ｎ－β－（アミノエチル）γ－アミノプロピルトリメトキシシラン１．０質量部を加え、減圧条件下１５分間均一に混合して第一剤Ａ－２を調製した。 2. First agent A-2
Dimethylpolysiloxane with both molecular chain ends blocked with trimethoxysiloxy groups and a viscosity of 20,000 mPa·s (i.e., in the above formula (1), X = oxygen atom, R 1 = R 2 = methyl group, a = 50 parts by mass of dimethylpolysiloxane (dimethylpolysiloxane with trimethoxysiloxy groups blocked at both ends of the molecular chain, corresponding to n = about 620) and dimethylpolysiloxane (with trimethoxysiloxy groups blocked at both ends of the molecular chain and a viscosity of 900 mPa・s) That is, in the above formula (1), X = oxygen atom, R 1 = R 2 = methyl group, a = 0, n = about 270, dimethylpolysiloxane (trimethoxysiloxy group-blocked dimethylpolysiloxane at both molecular chain ends) 50 mass 8 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g and 80 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 2.5 parts by mass of bis(dimethoxymethylsilyl-vinylene)dimethylsilane (that is, in the above formula (2), R 3 = R 4 = methyl group, b = 1. The same applies hereinafter), N- 1.0 parts by mass of β-(aminoethyl)γ-aminopropyltrimethoxysilane was added and mixed uniformly for 15 minutes under reduced pressure to prepare a first agent A-2.
＜第二剤の調製＞
１．第二剤Ｂ－１
分子鎖両末端がシラノール基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（３）において、Ｒ1＝メチル基、ｎ＝約６２０に該当する、分子鎖両末端シラノール基封鎖ジメチルポリシロキサン）１００質量部とＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ４質量部及び炭酸カルシウム９０質量部を減圧条件下で３０分間均一に混合した。その後、シクロヘキサノン１質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン３質量部を加え、減圧条件下１５分間均一に混合して第二剤Ｂ－１を調製した。 <Preparation of second agent>
1. Second agent B-1
Dimethylpolysiloxane whose molecular chain ends are blocked with silanol groups and whose viscosity is 20,000 mPa·s (i.e., in the above formula (3), R 1 = methyl group, n = approximately 620, both molecular chain ends) 100 parts by mass of silanol group-blocked dimethylpolysiloxane), 4 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g, and 90 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 1 part by mass of cyclohexanone and 3 parts by mass of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane were added and mixed uniformly for 15 minutes under reduced pressure to prepare a second agent B-1.
１．第二剤Ｂ－１
分子鎖両末端がシラノール基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（３）において、Ｒ1＝メチル基、ｎ＝約６２０に該当する、分子鎖両末端シラノール基封鎖ジメチルポリシロキサン）１００質量部とＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ４質量部及び炭酸カルシウム９０質量部を減圧条件下で３０分間均一に混合した。その後、シクロヘキサノン１質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン３質量部を加え、減圧条件下１５分間均一に混合して第二剤Ｂ－１を調製した。 <Preparation of second agent>
1. Second agent B-1
Dimethylpolysiloxane whose molecular chain ends are blocked with silanol groups and whose viscosity is 20,000 mPa·s (i.e., in the above formula (3), R 1 = methyl group, n = approximately 620, both molecular chain ends) 100 parts by mass of silanol group-blocked dimethylpolysiloxane), 4 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g, and 90 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 1 part by mass of cyclohexanone and 3 parts by mass of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane were added and mixed uniformly for 15 minutes under reduced pressure to prepare a second agent B-1.
２．第二剤Ｂ－２
分子鎖両末端がシラノール基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（３）において、Ｒ1＝メチル基、ｎ＝約６２０に該当する、分子鎖両末端シラノール基封鎖ジメチルポリシロキサン）１００質量部とＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ４質量部及び炭酸カルシウム９０質量部を減圧条件下で３０分間均一に混合した。その後、シクロヘキサノン１質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン５質量部を加え、減圧条件下１５分間均一に混合して第二剤Ｂ－２を調製した。 2. Second agent B-2
Dimethylpolysiloxane whose molecular chain ends are blocked with silanol groups and whose viscosity is 20,000 mPa·s (i.e., in the above formula (3), R 1 = methyl group, n = approximately 620, both molecular chain ends) 100 parts by mass of silanol group-blocked dimethylpolysiloxane), 4 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g, and 90 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 1 part by mass of cyclohexanone and 5 parts by mass of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane were added and mixed uniformly for 15 minutes under reduced pressure to prepare a second agent B-2.
分子鎖両末端がシラノール基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（３）において、Ｒ1＝メチル基、ｎ＝約６２０に該当する、分子鎖両末端シラノール基封鎖ジメチルポリシロキサン）１００質量部とＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ４質量部及び炭酸カルシウム９０質量部を減圧条件下で３０分間均一に混合した。その後、シクロヘキサノン１質量部、γ－（Ｎ，Ｎ’－ジメチルグアニジル）プロピルトリメトキシシラン５質量部を加え、減圧条件下１５分間均一に混合して第二剤Ｂ－２を調製した。 2. Second agent B-2
Dimethylpolysiloxane whose molecular chain ends are blocked with silanol groups and whose viscosity is 20,000 mPa·s (i.e., in the above formula (3), R 1 = methyl group, n = approximately 620, both molecular chain ends) 100 parts by mass of silanol group-blocked dimethylpolysiloxane), 4 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g, and 90 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 1 part by mass of cyclohexanone and 5 parts by mass of γ-(N,N'-dimethylguanidyl)propyltrimethoxysilane were added and mixed uniformly for 15 minutes under reduced pressure to prepare a second agent B-2.
３．第二剤Ｂ－３
分子鎖両末端がシラノール基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（３）において、Ｒ1＝メチル基、ｎ＝約６２０に該当する、分子鎖両末端シラノール基封鎖ジメチルポリシロキサン）１００質量部とＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ４質量部及び炭酸カルシウム９０質量部を減圧条件下で３０分間均一に混合した。その後、シクロヘキサノン１質量部、ジオクチル錫ジネオデカノエート０．４質量部を加え、減圧条件下１５分間均一に混合して第二剤Ｂ－３を調製した。 3. Second agent B-3
Dimethylpolysiloxane whose molecular chain ends are blocked with silanol groups and whose viscosity is 20,000 mPa·s (i.e., in the above formula (3), R 1 = methyl group, n = approximately 620, both molecular chain ends) 100 parts by mass of silanol group-blocked dimethylpolysiloxane), 4 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g, and 90 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 1 part by mass of cyclohexanone and 0.4 parts by mass of dioctyltin dineodecanoate were added and mixed uniformly for 15 minutes under reduced pressure to prepare a second agent B-3.
分子鎖両末端がシラノール基で封鎖され、粘度が２０，０００ｍＰａ・ｓのジメチルポリシロキサン（即ち、前記式（３）において、Ｒ1＝メチル基、ｎ＝約６２０に該当する、分子鎖両末端シラノール基封鎖ジメチルポリシロキサン）１００質量部とＢＥＴ比表面積１３０ｍ2／ｇの煙霧質シリカ４質量部及び炭酸カルシウム９０質量部を減圧条件下で３０分間均一に混合した。その後、シクロヘキサノン１質量部、ジオクチル錫ジネオデカノエート０．４質量部を加え、減圧条件下１５分間均一に混合して第二剤Ｂ－３を調製した。 3. Second agent B-3
Dimethylpolysiloxane whose molecular chain ends are blocked with silanol groups and whose viscosity is 20,000 mPa·s (i.e., in the above formula (3), R 1 = methyl group, n = approximately 620, both molecular chain ends) 100 parts by mass of silanol group-blocked dimethylpolysiloxane), 4 parts by mass of fumed silica having a BET specific surface area of 130 m 2 /g, and 90 parts by mass of calcium carbonate were uniformly mixed for 30 minutes under reduced pressure conditions. Thereafter, 1 part by mass of cyclohexanone and 0.4 parts by mass of dioctyltin dineodecanoate were added and mixed uniformly for 15 minutes under reduced pressure to prepare a second agent B-3.
＜第一剤と第二剤の混合＞
下記表１の組み合わせで、上記第一剤と第二剤を混合比（体積比）１：１で均一に混合し組成物１～６を調製した。混合する方法は、Ｍｉｘｐａｃ製の２５０ｍｌ×２５０ｍｌのカートリッジを使用した。 <Mixing of the first part and the second part>
Compositions 1 to 6 were prepared by uniformly mixing the first agent and the second agent at a mixing ratio (volume ratio) of 1:1 using the combinations shown in Table 1 below. The mixing method used a 250 ml x 250 ml cartridge manufactured by Mixpac.
下記表１の組み合わせで、上記第一剤と第二剤を混合比（体積比）１：１で均一に混合し組成物１～６を調製した。混合する方法は、Ｍｉｘｐａｃ製の２５０ｍｌ×２５０ｍｌのカートリッジを使用した。 <Mixing of the first part and the second part>
Compositions 1 to 6 were prepared by uniformly mixing the first agent and the second agent at a mixing ratio (volume ratio) of 1:1 using the combinations shown in Table 1 below. The mixing method used a 250 ml x 250 ml cartridge manufactured by Mixpac.
調製した組成物１～６を用いて、以下の特性を測定した。
The following properties were measured using the prepared compositions 1 to 6.
・硬化性、接着性
調製した組成物１～６のそれぞれを、２３℃／５０％ＲＨ環境下にて厚さが３ｍｍになるように３日放置し硬化させてシリコーンゴム硬化物（厚さ３ｍｍ）の測定用サンプルを作製し、ＪＩＳ Ｋ ６２４９に従い２号ダンベル試験片を作製し、硬さ、切断時伸び、引張り強度を測定した。なお、硬さはデュロメーターＡの値とした。接着性に関しては、トルエンで洗浄したアルミニウム基板（Ａ１０５０Ｐ、ｔ＝０．３ｍｍ）を用い、組成物１～６がそれぞれ接着面積２５ｍｍ×１０ｍｍで厚み２ｍｍになるようにそれぞれ２枚の上記アルミニウム基板で挟み込み２３℃／５０％ＲＨ環境下にて３日放置し、上記組成物を硬化させた。その後、５００ｍｍ／ｍｉｎのスピードでそれぞれ２枚のアルミニウム基板をせん断方向に引張り、せん断接着強度を求めた。結果を表２に示す。 ・Curing properties, adhesive properties Each of the prepared compositions 1 to 6 was left to cure in a 23°C/50% RH environment for 3 days to a thickness of 3 mm to form a silicone rubber cured product (3 mm thick). ) was prepared, and a No. 2 dumbbell test piece was prepared according to JIS K 6249, and the hardness, elongation at cutting, and tensile strength were measured. In addition, the hardness was taken as the value of durometer A. Regarding adhesion, using toluene-cleaned aluminum substrates (A1050P, t = 0.3 mm), compositions 1 to 6 were each attached to two of the above aluminum substrates so that the adhesion area was 25 mm x 10 mm and the thickness was 2 mm. The composition was sandwiched and left in an environment of 23° C./50% RH for 3 days to cure the composition. Thereafter, each of the two aluminum substrates was pulled in the shear direction at a speed of 500 mm/min to determine the shear adhesive strength. The results are shown in Table 2.
調製した組成物１～６のそれぞれを、２３℃／５０％ＲＨ環境下にて厚さが３ｍｍになるように３日放置し硬化させてシリコーンゴム硬化物（厚さ３ｍｍ）の測定用サンプルを作製し、ＪＩＳ Ｋ ６２４９に従い２号ダンベル試験片を作製し、硬さ、切断時伸び、引張り強度を測定した。なお、硬さはデュロメーターＡの値とした。接着性に関しては、トルエンで洗浄したアルミニウム基板（Ａ１０５０Ｐ、ｔ＝０．３ｍｍ）を用い、組成物１～６がそれぞれ接着面積２５ｍｍ×１０ｍｍで厚み２ｍｍになるようにそれぞれ２枚の上記アルミニウム基板で挟み込み２３℃／５０％ＲＨ環境下にて３日放置し、上記組成物を硬化させた。その後、５００ｍｍ／ｍｉｎのスピードでそれぞれ２枚のアルミニウム基板をせん断方向に引張り、せん断接着強度を求めた。結果を表２に示す。 ・Curing properties, adhesive properties Each of the prepared compositions 1 to 6 was left to cure in a 23°C/50% RH environment for 3 days to a thickness of 3 mm to form a silicone rubber cured product (3 mm thick). ) was prepared, and a No. 2 dumbbell test piece was prepared according to JIS K 6249, and the hardness, elongation at cutting, and tensile strength were measured. In addition, the hardness was taken as the value of durometer A. Regarding adhesion, using toluene-cleaned aluminum substrates (A1050P, t = 0.3 mm), compositions 1 to 6 were each attached to two of the above aluminum substrates so that the adhesion area was 25 mm x 10 mm and the thickness was 2 mm. The composition was sandwiched and left in an environment of 23° C./50% RH for 3 days to cure the composition. Thereafter, each of the two aluminum substrates was pulled in the shear direction at a speed of 500 mm/min to determine the shear adhesive strength. The results are shown in Table 2.
組成物１～４は、いずれも良好な接着性を示した。一方組成物５と組成物６においては、組成物１～４と比べて硬さ、引張り強度が高い数値を示したが、せん断接着強度が低く接着性は悪い結果であった。
Compositions 1 to 4 all showed good adhesion. On the other hand, compositions 5 and 6 showed higher values for hardness and tensile strength than compositions 1 to 4, but had low shear adhesive strength and poor adhesion.
・短時間硬化性の評価
上記組成物１～６のそれぞれを、２３℃／５０％ＲＨ環境下にて厚さが３ｍｍになるように１日又は２日放置し硬化させてシリコーンゴム硬化物（厚さ３ｍｍ）の測定用サンプルを作製し、ＪＩＳ Ｋ ６２４９に従い２号ダンベル試験片を作製し、硬さ、切断時伸び、引張り強度を測定した。３日放置して硬化させた結果（表２）と比較した。得られた結果を表３に示す。 ・Evaluation of short-time curability Each of the above compositions 1 to 6 was left to cure for 1 or 2 days in an environment of 23°C/50% RH to a thickness of 3 mm, resulting in a silicone rubber cured product ( A measurement sample with a thickness of 3 mm) was prepared, and a No. 2 dumbbell test piece was prepared according to JIS K 6249, and hardness, elongation at cutting, and tensile strength were measured. Comparison was made with the results obtained by leaving it for 3 days to harden (Table 2). The results obtained are shown in Table 3.
上記組成物１～６のそれぞれを、２３℃／５０％ＲＨ環境下にて厚さが３ｍｍになるように１日又は２日放置し硬化させてシリコーンゴム硬化物（厚さ３ｍｍ）の測定用サンプルを作製し、ＪＩＳ Ｋ ６２４９に従い２号ダンベル試験片を作製し、硬さ、切断時伸び、引張り強度を測定した。３日放置して硬化させた結果（表２）と比較した。得られた結果を表３に示す。 ・Evaluation of short-time curability Each of the above compositions 1 to 6 was left to cure for 1 or 2 days in an environment of 23°C/50% RH to a thickness of 3 mm, resulting in a silicone rubber cured product ( A measurement sample with a thickness of 3 mm) was prepared, and a No. 2 dumbbell test piece was prepared according to JIS K 6249, and hardness, elongation at cutting, and tensile strength were measured. Comparison was made with the results obtained by leaving it for 3 days to harden (Table 2). The results obtained are shown in Table 3.
いずれの組成物も２３℃／５０％ＲＨ環境下 ２日放置で硬化が完了していることが分かった。組成物１～４においては、従来の有機スズを配合した組成物５と組成物６と比較しても硬化性は同等である結果であった。
It was found that all compositions were completely cured after being left for 2 days in an environment of 23° C./50% RH. Compositions 1 to 4 had similar curability when compared with Compositions 5 and 6, both of which contained conventional organic tin.
・耐湿性の評価
上記組成物１～６のそれぞれを、２３℃／５０％ＲＨ環境下にて厚さが３ｍｍになるように３日放置し硬化させてシリコーンゴム硬化物（厚さ３ｍｍ）の測定用サンプルを作製し、ＪＩＳ Ｋ ６２４９に従い、２号ダンベル試験片を作製した。それを８５℃／８５％ＲＨのチャンバーにそれぞれ５００時間又は１，０００時間放置し、硬さ、切断時伸び、引張り強度の変化を測定した。得られた結果を表４に示す。なお、各チャンバーで５００時間又は１，０００時間放置する前のもので測定した値を初期値とした。 ・Evaluation of moisture resistance Each of the above compositions 1 to 6 was left to harden in an environment of 23° C./50% RH for 3 days to a thickness of 3 mm to form a cured silicone rubber product (3 mm thick). A measurement sample was prepared, and a No. 2 dumbbell test piece was prepared according to JIS K 6249. It was left in a chamber at 85° C./85% RH for 500 hours or 1,000 hours, respectively, and changes in hardness, elongation at break, and tensile strength were measured. The results obtained are shown in Table 4. Note that the initial value was the value measured before leaving each chamber for 500 hours or 1,000 hours.
上記組成物１～６のそれぞれを、２３℃／５０％ＲＨ環境下にて厚さが３ｍｍになるように３日放置し硬化させてシリコーンゴム硬化物（厚さ３ｍｍ）の測定用サンプルを作製し、ＪＩＳ Ｋ ６２４９に従い、２号ダンベル試験片を作製した。それを８５℃／８５％ＲＨのチャンバーにそれぞれ５００時間又は１，０００時間放置し、硬さ、切断時伸び、引張り強度の変化を測定した。得られた結果を表４に示す。なお、各チャンバーで５００時間又は１，０００時間放置する前のもので測定した値を初期値とした。 ・Evaluation of moisture resistance Each of the above compositions 1 to 6 was left to harden in an environment of 23° C./50% RH for 3 days to a thickness of 3 mm to form a cured silicone rubber product (3 mm thick). A measurement sample was prepared, and a No. 2 dumbbell test piece was prepared according to JIS K 6249. It was left in a chamber at 85° C./85% RH for 500 hours or 1,000 hours, respectively, and changes in hardness, elongation at break, and tensile strength were measured. The results obtained are shown in Table 4. Note that the initial value was the value measured before leaving each chamber for 500 hours or 1,000 hours.
８５℃／８５％ＲＨのチャンバーで５００時間又は１，０００時間放置後の結果を初期値と比較すると、組成物１～４では、硬さが若干低下する傾向にあるが、切断時伸び及び引張り強度の大きな変化は無く、耐湿性良好と判断できる。いずれの項目においても物性変化率は５０％以内であった。
一方、有機スズを配合した組成物５と組成物６においては、組成物１～４と比較して硬さの変化は小さいものの、切断時伸び並びに引張り強度が大きく低下する結果となり、変化率は５０％以上となった。 Comparing the results after being left in a chamber at 85°C/85% RH for 500 hours or 1,000 hours with the initial values, compositions 1 to 4 tend to have a slight decrease in hardness, but the elongation and tensile strength at cutting tend to decrease slightly. There was no major change in strength, and it can be judged that the moisture resistance is good. The rate of change in physical properties was within 50% in all items.
On the other hand, in compositions 5 and 6 containing organic tin, although the change in hardness was small compared to compositions 1 to 4, the elongation at break and tensile strength decreased significantly, and the rate of change was It became more than 50%.
一方、有機スズを配合した組成物５と組成物６においては、組成物１～４と比較して硬さの変化は小さいものの、切断時伸び並びに引張り強度が大きく低下する結果となり、変化率は５０％以上となった。 Comparing the results after being left in a chamber at 85°C/85% RH for 500 hours or 1,000 hours with the initial values, compositions 1 to 4 tend to have a slight decrease in hardness, but the elongation and tensile strength at cutting tend to decrease slightly. There was no major change in strength, and it can be judged that the moisture resistance is good. The rate of change in physical properties was within 50% in all items.
On the other hand, in compositions 5 and 6 containing organic tin, although the change in hardness was small compared to compositions 1 to 4, the elongation at break and tensile strength decreased significantly, and the rate of change was It became more than 50%.
Claims (8)
- （Ａ）下記一般式（１）で示されるオルガノポリシロキサン１００質量部、
及び
（Ｂ）下記一般式（２）で示される同一ケイ素原子上に加水分解性シリル－ビニレン基を２個有する加水分解性オルガノシラン化合物０．１～１０質量部、
を含有する第一剤と
（Ｃ）下記一般式（３）で示されるオルガノポリシロキサン１００質量部、
（Ｄ）１分子中に窒素原子を３個以上有するアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物０．１～１０質量部、
及び
（Ｅ）ケトン基を有する有機化合物０．１～５質量部、
を含有する第二剤と
からなる二成分型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 organopolysiloxane represented by the following general formula (1),
and (B) 0.1 to 10 parts by mass of a hydrolyzable organosilane compound having two hydrolyzable silyl-vinylene groups on the same silicon atom represented by the following general formula (2),
A first agent containing
(C) 100 parts by mass of organopolysiloxane represented by the following general formula (3),
(D) 0.1 to 10 parts by mass of an amino-functional group-containing hydrolysable organosilane compound having three or more nitrogen atoms in one molecule and/or a partially hydrolyzed condensate thereof;
and (E) 0.1 to 5 parts by mass of an organic compound having a ketone group,
A two-component room temperature curable organopolysiloxane composition comprising a second agent containing: - （Ｄ）成分が、下記一般式（４）又は（４）’で表されるアミノ官能性基含有加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物である請求項１に記載の二成分型室温硬化性オルガノポリシロキサン組成物。
- 有機金属化合物を含有しないものである請求項１に記載の二成分型室温硬化性オルガノポリシロキサン組成物。 The two-component room temperature curable organopolysiloxane composition according to claim 1, which does not contain an organometallic compound.
- 第一剤と第二剤の混合割合が体積比で第一剤：第二剤＝１：１～１０：１である請求項１に記載の二成分型室温硬化性オルガノポリシロキサン組成物。 The two-component room temperature curable organopolysiloxane composition according to claim 1, wherein the mixing ratio of the first part and the second part is 1:1 to 10:1 by volume.
- 第一剤と第二剤を混合して成型されたオルガノポリシロキサン組成物を８５℃／８５％ＲＨ環境下に１，０００時間放置した時の物性変化率が、放置前の物性と比較して５０％以内である硬化物を与えるものである請求項１に記載の二成分型室温硬化性オルガノポリシロキサン組成物。 The rate of change in physical properties when an organopolysiloxane composition formed by mixing the first part and the second part was left in an 85°C/85% RH environment for 1,000 hours was compared to the physical properties before being left. 2. The two-component room temperature curable organopolysiloxane composition according to claim 1, which provides a cured product with a hardness of 50% or less.
- 請求項１～４のいずれか１項に記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有する接着剤。 An adhesive comprising the two-component room temperature curable organopolysiloxane composition according to any one of claims 1 to 4.
- 請求項１～４のいずれか１項に記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有するシール剤。 A sealant containing the two-component room temperature curable organopolysiloxane composition according to any one of claims 1 to 4.
- 請求項１～４のいずれか１項に記載の二成分型室温硬化性オルガノポリシロキサン組成物を含有するコーティング剤。 A coating agent containing the two-component room temperature curable organopolysiloxane composition according to any one of claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-087309 | 2022-05-30 | ||
| JP2022087309 | 2022-05-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023234084A1 true WO2023234084A1 (en) | 2023-12-07 |
Family
ID=89024752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/018853 WO2023234084A1 (en) | 2022-05-30 | 2023-05-22 | Two-pack type room temperature curable organopolysiloxane composition and various articles containing said composition |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2023234084A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649363A (en) * | 1992-08-04 | 1994-02-22 | Shin Etsu Chem Co Ltd | Room-temperature-curable organopolysiloxane composition |
| JP2000234057A (en) * | 1998-12-14 | 2000-08-29 | Shin Etsu Chem Co Ltd | Room-temperature quick-curing composition |
| JP2001107023A (en) * | 1999-07-30 | 2001-04-17 | Three Bond Co Ltd | Room temperature curing sealant composition for automobile |
| JP2002226708A (en) * | 2001-01-30 | 2002-08-14 | Three Bond Co Ltd | Room temperature-curable sealing material composition used for automobiles |
| WO2015093139A1 (en) * | 2013-12-17 | 2015-06-25 | 信越化学工業株式会社 | Multicomponent room temperature-curable organopolysiloxane composition, cured product of said composition, and molded product comprising said cured product |
| WO2022009759A1 (en) * | 2020-07-07 | 2022-01-13 | 信越化学工業株式会社 | Two-component type room temperature fast-curing organopolysiloxane composition, cured product thereof and article |
| WO2023068094A1 (en) * | 2021-10-19 | 2023-04-27 | 信越化学工業株式会社 | Room temperature-curable organopolysiloxane composition, adhesive, sealing agent, and coating agent |
-
2023
- 2023-05-22 WO PCT/JP2023/018853 patent/WO2023234084A1/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0649363A (en) * | 1992-08-04 | 1994-02-22 | Shin Etsu Chem Co Ltd | Room-temperature-curable organopolysiloxane composition |
| JP2000234057A (en) * | 1998-12-14 | 2000-08-29 | Shin Etsu Chem Co Ltd | Room-temperature quick-curing composition |
| JP2001107023A (en) * | 1999-07-30 | 2001-04-17 | Three Bond Co Ltd | Room temperature curing sealant composition for automobile |
| JP2002226708A (en) * | 2001-01-30 | 2002-08-14 | Three Bond Co Ltd | Room temperature-curable sealing material composition used for automobiles |
| WO2015093139A1 (en) * | 2013-12-17 | 2015-06-25 | 信越化学工業株式会社 | Multicomponent room temperature-curable organopolysiloxane composition, cured product of said composition, and molded product comprising said cured product |
| WO2022009759A1 (en) * | 2020-07-07 | 2022-01-13 | 信越化学工業株式会社 | Two-component type room temperature fast-curing organopolysiloxane composition, cured product thereof and article |
| WO2023068094A1 (en) * | 2021-10-19 | 2023-04-27 | 信越化学工業株式会社 | Room temperature-curable organopolysiloxane composition, adhesive, sealing agent, and coating agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102326223B1 (en) | Room-temperature-curable organopolysiloxane composition, and moulded product comprising cured product of said room- temperature-curable organopolysiloxane composition | |
| JP5997778B2 (en) | Novel alkoxysilyl-ethylene group-terminated silicon-containing compound, room temperature curable organopolysiloxane composition, and molded product obtained by curing the composition | |
| JP2738235B2 (en) | Ultraviolet and moisture curable organopolysiloxane composition, cured product thereof and method for producing the same | |
| JP5960843B2 (en) | Process for producing alkoxysilyl-ethylene group-terminated organosiloxane polymer, room temperature curable composition and molded product which is cured product thereof | |
| JP6314993B2 (en) | Multi-component room temperature curable organopolysiloxane composition, cured product of the composition, and molded product comprising the cured product | |
| JP6747507B2 (en) | Room temperature curable composition, sealant and article | |
| CN107429061B (en) | Room temperature curable organopolysiloxane composition and molded article that is cured product of the composition | |
| KR101954055B1 (en) | Multi-component room-temperature-curable silicone elastomer composition | |
| EP1323782B1 (en) | Room temperature curable organopolysiloxane compositions | |
| WO2020209083A1 (en) | Room-temperature-curable organopolysiloxane composition for oil seal, and automotive part | |
| JPS62252456A (en) | Room temperature-curable organopolysiloxane composition | |
| JP6760223B2 (en) | Room temperature curable organopolysiloxane composition, and sealants, coating agents, adhesives, molded articles containing the same. | |
| WO2022009759A1 (en) | Two-component type room temperature fast-curing organopolysiloxane composition, cured product thereof and article | |
| WO2023068094A1 (en) | Room temperature-curable organopolysiloxane composition, adhesive, sealing agent, and coating agent | |
| JPH0457850A (en) | Room-temperature-curable composition | |
| JP2006131824A (en) | Room temperature curable organopolysiloxane composition | |
| WO2014185276A1 (en) | Aluminium chelate compound, and room-temperature-curable resin composition including same | |
| EP3967730B1 (en) | Room-temperature-vulcanizing organopolysiloxane composition, silicone rubber, and article | |
| WO2023234084A1 (en) | Two-pack type room temperature curable organopolysiloxane composition and various articles containing said composition | |
| JPH09241509A (en) | Room-temperature-curing polyorganosiloxane composition | |
| JP2005213487A (en) | Room temperature-curing polyorganosiloxane composition | |
| JPH11323132A (en) | Room-temperature-curable polyorganosiloxane composition | |
| JP6690737B2 (en) | Novel arylene group-containing organopolysiloxane and curable organopolysiloxane composition using the same | |
| JP2017095603A (en) | Room temperature curable polyorganosiloxane composition | |
| KR20240000527A (en) | Room temperature curable silicone coating compositions and articles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23815843 Country of ref document: EP Kind code of ref document: A1 |