JP3793031B2 - Moisture curable composition - Google Patents
Moisture curable composition Download PDFInfo
- Publication number
- JP3793031B2 JP3793031B2 JP2001048855A JP2001048855A JP3793031B2 JP 3793031 B2 JP3793031 B2 JP 3793031B2 JP 2001048855 A JP2001048855 A JP 2001048855A JP 2001048855 A JP2001048855 A JP 2001048855A JP 3793031 B2 JP3793031 B2 JP 3793031B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- group
- curable composition
- general formula
- different
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 31
- 150000003609 titanium compounds Chemical class 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- -1 diene compound Chemical class 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 229920000620 organic polymer Polymers 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 238000001723 curing Methods 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- JTQPTNQXCUMDRK-UHFFFAOYSA-N propan-2-olate;titanium(2+) Chemical compound CC(C)O[Ti]OC(C)C JTQPTNQXCUMDRK-UHFFFAOYSA-N 0.000 description 6
- 229920002379 silicone rubber Polymers 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000004945 silicone rubber Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 4
- 244000061458 Solanum melongena Species 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920006311 Urethane elastomer Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- LGSNSXWSNMARLH-UHFFFAOYSA-N butan-1-ol titanium Chemical compound C(CCC)O.[Ti].C(CCC)O LGSNSXWSNMARLH-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 231100000507 endocrine disrupting Toxicity 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 231100001231 less toxic Toxicity 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007665 sagging Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 125000005371 silicon functional group Chemical group 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-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
- YHFFINXFNYQPQA-UHFFFAOYSA-N 4-[diethoxy(methyl)silyl]butan-1-amine Chemical compound CCO[Si](C)(OCC)CCCCN YHFFINXFNYQPQA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- BPSLVNCMKDXZPC-UHFFFAOYSA-N benzyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC1=CC=CC=C1 BPSLVNCMKDXZPC-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- BQSLMFSQEBXZHN-UHFFFAOYSA-N bis(8-methylnonyl) butanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCC(=O)OCCCCCCCC(C)C BQSLMFSQEBXZHN-UHFFFAOYSA-N 0.000 description 1
- OAXZVLMNNOOMGN-UHFFFAOYSA-N bis(8-methylnonyl) decanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC(C)C OAXZVLMNNOOMGN-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 229940057995 liquid paraffin Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 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
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 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 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、速硬化性を有し、毒性、環境汚染性の少ない触媒系を有する湿気硬化型組成物に関する。
【０００２】
【従来の技術】
従来１液型の湿気硬化型ゴム組成物としては、シリコーンゴム系、ウレタンゴム系、ポリサルファイドゴム系等のものが知られている。１液型の湿気硬化型ゴム組成物は、一般に硬化が速く２液型のものに比べ、液の混合調整等の必要がない等、作業性の点で優れている。
【０００３】
【発明が解決しようとする課題】
しかし、シリコーンゴム系のものは、周囲への汚染の可能性、その表面への塗装性の点で問題があり、ウレタンゴム系のものは、貯蔵安定性、耐候性、耐発泡性、変色等の点で問題がある。さらに、ポリサルファイドゴム系についても、硬化性、周囲への汚染の可能性の点で問題がある。
【０００４】
変成シリコーンゴム系硬化型組成物は、ポリエーテルを主鎖とする架橋可能な加水分解性珪素官能基を有する重合体と硬化触媒とからなるものであり、密封下では長期間安定であるが、湿気にさらすと急速に硬化してゴム状物質に変わる１液型組成物である（特公昭６２−３５４２１号公報、特開昭６１−１４１７６１号公報、特開平１−５８２１９号公報）。この変成シリコーンゴム系硬化型組成物は、ポリウレタンゴム系に比べ貯蔵安定性、耐候性、耐発泡性、耐変色性が良好であり、ポリサルファイドゴム系に比べ、硬化性に優れ、周囲への汚染性が少なく、毒性がない。また、通常のシリコーンゴム系に比べ周囲への汚染性が少なく、表面への塗装性が良好である。この加水分解性珪素官能基を有する重合体の硬化触媒として、錫カルボン酸塩化合物、鉛カルボン酸塩化合物等が知られているが、有機鉛化合物は環境への負荷が大きく、有機錫化合物は内分泌撹乱物質として生体への影響が懸念されており、使用に際しては十分な注意が必要となることから、これらに代わる実用的な硬化速度を持つ触媒の開発が望まれていた。
【０００５】
【課題を解決するための手段】
そこで、本発明者らは、毒性、環境汚染性が少なく、しかも速硬化性を有する湿気硬化型組成物について検討し、本発明に至った。
【０００６】
すなわち本発明は、（１）分子末端または側鎖に加水分解性基と結合した珪素原子を１分子中に少なくとも１個有し、主鎖がアルキレンオキシド重合体、ポリエーテル、エーテル・エステルブロック共重合体、エチレン性不飽和化合物の重合体、ジエン系化合物の重合体のいずれかであるシリル基含有有機重合体（Ａ）１００重量部に対して、硬化触媒として、下記一般式（１）：
【０００７】
【化３】
（式中、Ｒ1およびＲ2はそれぞれ炭素原子数１〜１０の炭化水素基を示し、Ｒ1、Ｒ2は相互に同一であっても、異なっていてもよく、２個のＲ1は相互に同一であっても、異なっていてもよい）で表されるチタン化合物（Ｂ）および下記一般式（２）：
【０００９】
【化４】
（式中、Ｒ3は炭素原子数１〜１０の炭化水素基を示し、２個のＲ3は相互に同一であっても、異なっていてもよい）で表されるチタン化合物（Ｃ）よりなる群から選ばれる少なくとも１種を０．１〜２０重量部含有することを特徴とする湿気硬化型組成物を提供する。
【００１１】
また本発明は、（２）チタン化合物（Ｂ）が、一般式（１）においてＲ1およびＲ2がそれぞれ炭素原子数１〜４の炭化水素基（Ｒ1、Ｒ2は相互に同一であっても、異なっていてもよく、２個のＲ1は相互に同一であっても、異なっていてもよい）を示すものであり、チタン化合物（Ｃ）が、一般式（２）においてＲ3が炭素原子数１〜４の炭化水素基（２個のＲ3は相互に同一であっても、異なっていてもよい）を示すものである前記（１）項に記載の湿気硬化型組成物を提供する。
【００１２】
また本発明は、（３）チタン化合物（Ｂ）が、一般式（１）においてＲ1がイソプロピルまたはブチル、Ｒ2がメチルまたはエチルを示すものであり、チタン化合物（Ｃ）が、一般式（２）においてＲ3がイソプロピルまたはブチルを示すものである前記（１）項または（２）項に記載の湿気硬化型組成物を提供する。
【００１３】
【発明の実施の形態】
本発明においては、分子末端または側鎖に加水分解性基と結合した珪素原子を１分子中に少なくとも１個有するシリル基含有有機重合体に、硬化触媒として、前記特定のチタン化合物を配合することにより、毒性、環境汚染性が少なく、しかも速硬化性を有し、接着性、耐水接着性に優れた１液型の湿気硬化型組成物が得られることが見出された。
【００１４】
本発明に用いるシリル基含有有機重合体（Ａ）は、分子末端または側鎖に加水分解性基と結合した珪素原子（以下、加水分解性基と結合した珪素基という場合がある）を１分子中に少なくとも１個有する有機重合体であり、その主鎖としては、アルキレンオキシド重合体ないしポリエーテル、エーテル・エステルブロック共重合体が挙げられる。また、エチレン性不飽和化合物、ジエン系化合物の重合体が挙げられる。
【００１５】
前記アルキレンオキシド重合体ないしポリエーテルとしては、
［ＣＨ2ＣＨ2Ｏ］ｎ
［ＣＨ（ＣＨ3）ＣＨ2Ｏ］ｎ
［ＣＨ（Ｃ2Ｈ5）ＣＨ2Ｏ］ｎ
［ＣＨ2ＣＨ2ＣＨ2ＣＨ2Ｏ］ｎ
等の繰り返し単位を有するものが例示される。ここでｎは、２以上の整数である。
【００１６】
また、エチレン性不飽和化合物、ジエン系化合物の重合体としては、エチレン、プロピレン、アクリル酸エステル、メタクリル酸エステル、酢酸ビニル、アクリロニトリル、スチレン、イソブチレン、ブタジエン、イソプレン、クロロプレン等の単独重合体またはこれらの２種以上の共重合体が挙げられる。より具体的には、ポリブタジエン、スチレン−ブタジエン共重合体、アクリロニトリル−ブタジエン共重合体、エチレン−ブタジエン共重合体、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリル酸エステル共重合体、ポリイソプレン、スチレン−イソプレン共重合体、イソブチレン−イソプレン共重合体、ポリクロロプレン、スチレン−クロロプレン共重合体、アクリロニトリル−クロロプレン共重合体、ポリイソブチレン、ポリアクリル酸エステル、ポリメタクリル酸エステル等が挙げられる。
【００１７】
前記加水分解性基と結合した珪素基は、湿気や架橋剤の存在下、必要に応じて触媒等を使用することにより縮合反応を起こす基のことである。具体的には、ハロゲン化シリル基、アルコキシシリル基、アルケニルオキシシリル基、アシロキシシリル基、アミノシリル基、アミノオキシシリル基、オキシムシリル基、アミドシリル基等があげられる。ここで、１つの珪素原子に結合したこれら加水分解性基の数は１〜３の範囲から選択される。また１つの珪素原子に結合した加水分解性基は１種であってもよく、複数種であってもよい。さらに加水分解性基と非加水分解性基が１つの珪素原子に結合していてもよい。加水分解性基と結合した珪素基としては、取り扱いが容易である点で、とくにアルコキシシリル基（モノアルコキシシリル基、ジアルコキシシリル基、トリアルコキシシリル基を含む）が好ましい。加水分解性基と結合した珪素基は、重合体分子の末端に存在していても、側鎖に存在していてもよい。加水分解性基と結合した珪素基は、重合体の１分子当たり少なくとも１個あればよいが、硬化速度、硬化物性の点からは、１分子当たり平均して１．５個以上あるのが好ましい。加水分解性基と結合した珪素基を前記主鎖重合体に結合させる方法としては公知の方法が採用できる。
【００１８】
本発明で用いる有機重合体（Ａ）の分子量は、とくに制約はないが、過度に高分子量のものは高粘度であり、硬化型組成物とした場合に使用上困難となるから、数平均分子量として３００００以下が望ましい。このような有機重合体は、公知の方法によって製造することができるが、鐘淵化学工業（株）製のカネカＭＳポリマー等の市販品を使用してもよい。
【００１９】
本発明では、硬化触媒として、下記一般式（１）：
【００２０】
【化５】
（式中、Ｒ1およびＲ2はそれぞれ炭素原子数１〜１０の炭化水素基を示し、Ｒ1、Ｒ2は相互に同一であっても、異なっていてもよく、２個のＲ2は相互に同一であっても、異なっていてもよい）で表されるチタン化合物（Ｂ）および下記一般式（２）：
【００２２】
【化６】
（式中、Ｒ3は炭素原子数１〜１０の炭化水素基を示し、２個のＲ3は相互に同一であっても、異なっていてもよい）で表されるチタン化合物（Ｃ）よりなる群から選ばれる少なくとも１種を使用する。
【００２４】
一般式（１）、（２）において、Ｒ1、Ｒ2、Ｒ3で表される炭素原子数１〜１０の炭化水素基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチル、ペンチル、ヘキシル、オクチル、２−エチルヘキシル、デシルなどのアルキル基が好ましい。
【００２５】
好ましいチタン化合物（Ｂ）は、一般式（１）においてＲ1およびＲ2がそれぞれ炭素原子数１〜４の炭化水素基、とくにアルキル基（Ｒ1、Ｒ2は相互に同一であっても、異なっていてもよく、２個のＲ2は相互に同一であっても、異なっていてもよい）を示すものである。好ましいチタン化合物（Ｃ）は、一般式（２）においてＲ3が炭素原子数１〜４の炭化水素基、とくにアルキル基（２個のＲ3は相互に同一であっても、異なっていてもよい）を示すものである。とくに好ましいチタン化合物（Ｂ）は、一般式（１）においてＲ1がイソプロピルまたはブチル、Ｒ2がメチルまたはエチルを示すものである。とくに好ましいチタン化合物（Ｃ）は、一般式（２）においてＲ3がイソプロピルまたはブチルを示すものである。
【００２６】
チタン化合物（Ｂ）の具体例としては、たとえばジイソプロポキシチタンビス（アセト酢酸エチルエステル）、ジブトキシチタンビス（アセト酢酸エチルエステル）、ジイソプロポキシチタンビス（アセト酢酸メチルエステル）等が挙げられる。チタン化合物（Ｃ）の具体例としては、ジイソプロポキシチタンビス（アセトアセトネート）等が挙げられる。このような化合物は公知の方法によって製造することができる。
【００２７】
本発明の湿気硬化型組成物において、チタン化合物（Ｂ）およびチタン化合物（Ｃ）よりなる群から選ばれる少なくとも１種からなる硬化触媒の含有量は、シリル基含有有機重合体（Ａ）１００重量部に対して０．１〜２０重量部、特に０．５〜１０重量部が好ましい。硬化触媒の含有量が前記範囲未満では硬化速度などの硬化性能が不十分であり、一方前記範囲を超えると硬化後の硬化物の復元率、耐候性などの物性、貯蔵中の安定性が低下することがある。
【００２８】
本発明の湿気硬化性組成物には、硬化を促進し基材への密着性を良くするため、公知の種々のアミノ基置換アルコキシシラン化合物、またはその縮合物を使用することができる。具体的に例示すると、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、Ｎ−（トリメトキシシリルプロピル）エチレンジアミン、δ−アミノブチル（メチル）ジエトキシシラン、Ｎ，Ｎ’−ビス（トリメトキシシリルプロピル）エチレンジアミンおよびこれらの部分加水分解物等が挙げられる。また、基材への密着性の向上のために、ビニルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリイソプロポキシシラン等のビニルアルコキシシラン化合物を使用できる。
【００２９】
また本発明の湿気硬化型組成物には、さらに充填剤、着色剤、可塑剤、硬化促進剤、硬化遅延剤、タレ防止剤、老化防止剤、溶剤等の硬化型組成物に通常添加される添加剤を加えてもよい。例えば、充填剤としては、具体的には、炭酸カルシウム、カオリン、タルク、ヒュームドシリカ、沈降性シリカ、無水ケイ酸、含水ケイ酸、クレー、焼成クレー、ガラス、ベントナイト、有機ベントナイト、シラスバルーン、ガラス繊維、石綿、ガラスフィラメント、粉砕石英、珪藻土、ケイ酸アルミニウム、水酸化アルミニウム、酸化亜鉛、酸化マグネシウム、二酸化チタン等が挙げられる。着色剤としては、具体的には、酸化鉄、カーボンブラック、フタロシアニンブルー、フタロシアニングリーン等が使用される。可塑剤としては、具体的には、ジブチルフタレート、ジオクチルフタレート、ブチルベンジルフタレート等のフタル酸エステル類、アジピン酸ジオクチル、コハク酸ジオクチル、コハク酸ジイソデシル、セバシン酸ジイソデシル、オレイン酸ブチル等の脂肪族カルボン酸エステル類、ペンタエリスリトールエステル等のポリオール化合物のエステル類、リン酸トリオクチル、リン酸トリクレジル等のリン酸エステル類、エポキシ化大豆油、エポキシステアリン酸ベンジル等のエポキシ可塑剤、塩素化パラフィン等が使用される。タレ防止剤としては、具体的には、水添ヒマシ油、無水ケイ酸、有機ベントナイト、コロイド状シリカ等が使用される。また他の添加剤としては、フェノール樹脂、エポキシ樹脂等の接着付与剤、紫外線吸収剤、ラジカル連鎖禁止剤、過酸化物分解剤、各種の老化防止剤等が使用される。
【００３０】
【実施例】
以下に本発明を実施例を用いて具体的に説明するが、本発明の範囲はこれによってを限定されるものではない。
【００３１】
製造例１
窒素導入管を取り付けた５００ｍｌナス型フラスコに、テトライソプロポキシチタン１４２ｇ（０．５ｍｏｌ）、アセト酢酸エチルエステル１３０．１ｇ（１．０ｍｏｌ）を量り込み、マグネチックスターラーにて十分に混合した。発熱がおさまり、内温が室温付近になるまで攪拌を続けた後、イソプロピルアルコールを減圧留去し、黄色液体のチタン化合物Ａの２０８ｇ（９８％）を得た。この化合物のＦＴ−ＩＲ分析にて、アセト酢酸エチルエステルのカルボニル基の吸収（１７０６ｃｍ-1、１７３５ｃｍ-1）が低波数側（１６１４ｃｍ-1、１６３５ｃｍ-1）にシフトしたことを確認した。また、次の元素分析の結果より、ジイソプロポキシチタンビス（アセト酢酸エチルエステル）であることを確認した。
製造例２
窒素導入管を取り付けた５００ｍｌナス型フラスコに、テトラブトキシチタン１８９ｇ（０．５４ｍｏｌ）、アセト酢酸エチルエステル１４０ｇ（１．０８ｍｏｌ）を量り込み、マグネチックスターラーにて十分に混合した。発熱がおさまり、内温が室温付近になるまで攪拌を続けた後、ブチルアルコールを減圧留去し、黄色液体のチタン化合物Ｂの２３８ｇ（９５％）を得た。この化合物のＦＴ−ＩＲ分析にて、アセト酢酸エチルエステルのカルボニル基の吸収（１７０６ｃｍ-1、１７３５ｃｍ-1）が低波数側（１６１４ｃｍ-1、１６３５ｃｍ-1）にシフトしたことを確認した。また、次の元素分析の結果より、ジブトキシチタンビス（アセト酢酸エチルエステル）であることを確認した。
製造例３
窒素導入管を取り付けた５００ｍｌナス型フラスコに、テトライソプロポキシチタン１４２ｇ（０．５ｍｏｌ）、アセチルアセトン１００．１ｇ（１．０ｍｏｌ）を量り込み、マグネチックスターラーにて十分に混合した。発熱がおさまり、内温が室温付近になるまで攪拌を続けた後、イソプロピルアルコールを減圧留去し、黄色液体のチタン化合物Ｃの１７８ｇ（９８％）を得た。この化合物のＦＴ−ＩＲ分析にて、アセチルアセトンのカルボニル基の吸収（１７０６ｃｍ-1、１７３５ｃｍ-1）が低波数側（１６１４ｃｍ-1、１６３５ｃｍ-1）にシフトしたことを確認した。また、次の元素分析の結果より、ジイソプロポキシチタンビス（アセトアセトネート）であることを確認した。
製造例４
窒素導入管を取り付けた５００ｍｌナス型フラスコに、テトライソプロポキシチタン１４２ｇ（０．５ｍｏｌ）、アセト酢酸メチルエステル１１６．１ｇ（１．０ｍｏｌ）を量り込み、マグネチックスターラーにて十分に混合した。発熱がおさまり、内温が室温付近になるまで攪拌を続けた後、イソプロピルアルコールを減圧留去し、黄色液体のチタン化合物Ｄの１９６ｇ（９９％）を得た。この化合物のＦＴ−ＩＲ分析にて、アセト酢酸メチルエステルのカルボニル基の吸収（１７０６ｃｍ-1、１７３５ｃｍ-1）が低波数側（１６１４ｃｍ-1、１６３５ｃｍ-1）にシフトしたことを確認した。また、次の元素分析の結果より、ジイソプロポキシチタンビス（アセト酢酸メチルエステル）であることを確認した。
実施例１〜４
シリル基含有有機重合体（鐘淵化学工業（株）製ＭＳポリマーＳ３０３）１００重量部に対して、製造例１、２、３および４で得られたチタン化合物Ａ、Ｂ、ＣまたはＤ、および表１に示される各種添加剤を表１に示される重量部数配合し、混練して硬化型組成物を調製した。
【００３６】
得られた硬化型組成物について、下記の硬化性試験および引張接着性試験を行った。結果を表１に示す。なお、混練から硬化までの操作は、室温２５℃、湿度６０％ＲＨの恒温室にて行った。
【００３７】
＜硬化性試験＞
硬化型組成物について、スナップタイム（半ゲル化し流動性のなくなるまでの時間）およびタックフリータイム（表面タックのなくなるまでの時間）を測定した。
【００３８】
＜引張接着性試験＞
硬化型組成物について、ＪＩＳ Ａ ５７５８に準拠し、引張接着性を試験した。被着体は、アルミニウム板を使用した。破断状況は、以下の略号で示した。
ＣＦ：材料破断
ＴＣＦ：材料薄層破断
ＡＦ：被着体―材料界面剥離
【００３９】
比較例１〜２
シリル基含有有機重合体（鐘淵化学工業（株）製ＭＳポリマーＳ３０３）１００重量部に対して、変成シリコーンゴム系硬化型組成物の硬化剤として用いられている従来の錫化合物としてジブチル錫ジラウレートまたはジブチル錫ジアセテートおよび表１に示される各種添加剤を表１に示される重量部数配合し、実施例１〜４と同じ条件下に混練して硬化型組成物を得、実施例１〜４と同様にしてスナップタイム、タックフリータイムおよび引張接着性を測定した。結果を表１に示す。
【００４０】
表１に示す材料の詳細はつぎのとおりである。
【００４１】
ノクラックＮＳ−６：老化防止剤（大内新興化学工業株式会社製）
Ａ−１７１：ビニルアルコキシシラン化合物（日本ユニカー株式会社製）
Ａ−１１００：アミノ基置換アルコキシシラン化合物（日本ユニカー株式会社製）
スモイルＰ−３５０：流動パラフィン（村松石油（株）製）
ネオスタンＵ−２００：ジブチル錫ジアセテート（日東化成株式会社製）
ネオスタンＵ−１００：ジブチル錫ジラウレート（日東化成株式会社製）
【００４２】
【表１】
【発明の効果】
表１から明らかなように、本発明の湿気硬化型組成物を用いると、従来の湿気硬化型組成物に比べ早く硬化し、接着性、耐水接着性も優れている。また、本発明の湿気硬化型組成物は錫化合物を硬化触媒として使用しないため内分泌撹乱物質による生体への影響、環境への影響の心配のない硬化型組成物である。このような湿気硬化型組成物は、シーリング剤、コーティング剤、弾性接着剤として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a moisture curable composition having a catalyst system that has fast curing properties and is less toxic and less polluting to the environment.
[0002]
[Prior art]
Conventionally, as a one-pack type moisture curable rubber composition, silicone rubber, urethane rubber, polysulfide rubber, and the like are known. One-component moisture-curing rubber compositions are generally superior in terms of workability, such as quick curing and no need for liquid mixing adjustment, as compared with two-component ones.
[0003]
[Problems to be solved by the invention]
However, silicone rubber-based materials have problems in terms of possible contamination to the surroundings and paintability on the surface. Urethane rubber-based materials have storage stability, weather resistance, foam resistance, discoloration, etc. There is a problem in terms of. Furthermore, polysulfide rubber systems also have problems in terms of curability and the possibility of contamination to the surroundings.
[0004]
The modified silicone rubber-based curable composition comprises a polymer having a crosslinkable hydrolyzable silicon functional group having a polyether as a main chain and a curing catalyst, and is stable for a long time under sealing, It is a one-component composition that quickly cures to a rubbery substance when exposed to moisture (Japanese Patent Publication No. 62-35421, Japanese Patent Publication No. 61-141761 and Japanese Patent Publication No. 1-58219). This modified silicone rubber-based curable composition has better storage stability, weather resistance, foam resistance, and discoloration resistance than polyurethane rubber, and has excellent curability and contamination to the surroundings compared to polysulfide rubber. Less toxic and non-toxic. In addition, it is less contaminated to the surroundings than normal silicone rubbers and has good paintability on the surface. As a curing catalyst for a polymer having a hydrolyzable silicon functional group, a tin carboxylate compound, a lead carboxylate compound, and the like are known. However, an organic lead compound has a large environmental load, and an organic tin compound is As an endocrine disrupting substance, there is a concern about the influence on the living body, and sufficient caution is required for its use. Therefore, development of a catalyst having a practical curing rate instead of these has been desired.
[0005]
[Means for Solving the Problems]
Accordingly, the present inventors have studied a moisture curable composition having little toxicity and environmental pollution and having fast curability, and have reached the present invention.
[0006]
That is, the present invention provides (1) molecular terminal or the bound silicon atom and a hydrolyzable group in the side chain at least one organic in one molecule, the main chain is an alkylene oxide polymers, polyethers, polyether-ester block copolymer polymers, polymer of an ethylenically unsaturated compound, for either der Ru silyl group-containing organic polymer (a) 100 parts by weight of the polymer of diene compound, as a curing catalyst, the following general formula (1) :
[0007]
[Chemical 3]
(Wherein, R 1 and R 2 each represent a hydrocarbon group having 1 to 10 carbon atoms, also R 1, R 2 are identical to each other or different, two R 1 is And may be the same or different from each other) and a titanium compound (B) represented by the following general formula (2):
[0009]
[Formula 4]
(Wherein R 3 represents a hydrocarbon group having 1 to 10 carbon atoms, and two R 3 s may be the same or different from each other) Provided is a moisture curable composition containing 0.1 to 20 parts by weight of at least one selected from the group consisting of:
[0011]
The present invention, (2) a titanium compound (B), the hydrocarbon group (R 1, R 2 R 1 and R 2 are each 1 to 4 carbon atoms in the general formula (1) was identical to each other Or two R 1 may be the same or different from each other), and the titanium compound (C) is represented by R 3 in the general formula (2). Is a moisture curable composition as described in the above item (1), which represents a hydrocarbon group having 1 to 4 carbon atoms (two R 3 s may be the same or different from each other). I will provide a.
[0012]
In the present invention, (3) the titanium compound (B) is one in which R 1 is isopropyl or butyl and R 2 is methyl or ethyl in the general formula (1), and the titanium compound (C) is represented by the general formula ( The moisture-curable composition according to (1) or (2), wherein R 3 represents isopropyl or butyl in 2).
[0013]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the specific titanium compound is added as a curing catalyst to a silyl group-containing organic polymer having at least one silicon atom bonded to a hydrolyzable group at the molecular terminal or side chain in one molecule. Thus, it has been found that a one-component moisture-curing composition with low toxicity and environmental pollution, fast curability, and excellent adhesion and water-resistant adhesion can be obtained.
[0014]
The silyl group-containing organic polymer (A) used in the present invention contains one molecule of silicon atom bonded to a hydrolyzable group at the molecular end or side chain (hereinafter sometimes referred to as a silicon group bonded to a hydrolyzable group). an organic polymer having at least one in the, as its main chain, alkylene oxide polymers or polyethers, ether-ester block copolymer and the like. Moreover, the polymer of an ethylenically unsaturated compound and a diene type compound is mentioned.
[0015]
As the alkylene oxide polymer or polyether,
[CH 2 CH 2 O] n
[CH (CH 3 ) CH 2 O] n
[CH (C 2 H 5 ) CH 2 O] n
[CH 2 CH 2 CH 2 CH 2 O] n
Those having a repeating unit such as Here, n is an integer of 2 or more.
[0016]
In addition, as polymers of ethylenically unsaturated compounds and diene compounds, homopolymers such as ethylene, propylene, acrylic acid ester, methacrylic acid ester, vinyl acetate, acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene or the like 2 or more types of copolymers are mentioned. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acryl. Acid ester copolymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylic ester, polymethacrylic acid Acid ester etc. are mentioned.
[0017]
The silicon group bonded to the hydrolyzable group is a group that causes a condensation reaction by using a catalyst or the like as necessary in the presence of moisture or a crosslinking agent. Specific examples include a halogenated silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group, and the like. Here, the number of these hydrolyzable groups bonded to one silicon atom is selected from the range of 1 to 3. Further, the hydrolyzable group bonded to one silicon atom may be one kind or plural kinds. Further, the hydrolyzable group and the non-hydrolyzable group may be bonded to one silicon atom. As the silicon group bonded to the hydrolyzable group, an alkoxysilyl group (including a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group) is particularly preferable in terms of easy handling. The silicon group bonded to the hydrolyzable group may be present at the terminal of the polymer molecule or may be present in the side chain. The number of silicon groups bonded to the hydrolyzable group may be at least one per molecule of the polymer, but from the viewpoint of curing speed and cured physical properties, it is preferable that the average number is 1.5 or more per molecule. . As a method for bonding a silicon group bonded to a hydrolyzable group to the main chain polymer, a known method can be adopted.
[0018]
The molecular weight of the organic polymer (A) used in the present invention is not particularly limited. However, an excessively high molecular weight polymer has a high viscosity and is difficult to use when a curable composition is used. 30000 or less is desirable. Such an organic polymer can be produced by a known method, but commercially available products such as Kaneka MS polymer manufactured by Kaneka Chemical Industry Co., Ltd. may be used.
[0019]
In the present invention, as the curing catalyst, the following general formula (1):
[0020]
[Chemical formula 5]
(Wherein R 1 and R 2 each represent a hydrocarbon group having 1 to 10 carbon atoms, R 1 and R 2 may be the same or different from each other, and two R 2 are And may be the same or different from each other) and a titanium compound (B) represented by the following general formula (2):
[0022]
[Chemical 6]
(Wherein R 3 represents a hydrocarbon group having 1 to 10 carbon atoms, and two R 3 s may be the same or different from each other) At least one selected from the group consisting of
[0024]
In the general formulas (1) and (2), examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R 1 , R 2 and R 3 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s- Alkyl groups such as butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl and decyl are preferred.
[0025]
The preferred titanium compound (B) has the general formula (1) in which R 1 and R 2 are each a hydrocarbon group having 1 to 4 carbon atoms, particularly an alkyl group (R 1, R 2 may be the same to each other, They may be different, and the two R 2 may be the same or different from each other. The preferred titanium compound (C), general formula (2) in R 3 is a hydrocarbon group having 1 to 4 carbon atoms, even particularly alkyl groups (two R 3 mutually identical, be different Is good). Particularly preferred titanium compounds (B) are those in which R 1 is isopropyl or butyl and R 2 is methyl or ethyl in the general formula (1). Particularly preferred titanium compounds (C) are those in which R 3 represents isopropyl or butyl in the general formula (2).
[0026]
Specific examples of the titanium compound (B) include diisopropoxy titanium bis (acetoacetic acid ethyl ester), dibutoxy titanium bis (acetoacetic acid ethyl ester), diisopropoxy titanium bis (acetoacetic acid methyl ester), and the like. Specific examples of the titanium compound (C) include diisopropoxy titanium bis (acetoacetonate). Such a compound can be produced by a known method.
[0027]
In the moisture curable composition of the present invention, the content of the curing catalyst composed of at least one selected from the group consisting of the titanium compound (B) and the titanium compound (C) is 100 weights of the silyl group-containing organic polymer (A). 0.1 to 20 parts by weight, particularly 0.5 to 10 parts by weight is preferred with respect to parts. If the content of the curing catalyst is less than the above range, the curing performance such as the curing rate is insufficient. There are things to do.
[0028]
In the moisture curable composition of the present invention, various known amino group-substituted alkoxysilane compounds or condensates thereof can be used in order to accelerate curing and improve adhesion to a substrate. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, δ-aminobutyl (methyl) diethoxysilane, N, N′-bis ( And trimethoxysilylpropyl) ethylenediamine and partial hydrolysates thereof. In addition, vinyl alkoxysilane compounds such as vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltriisopropoxysilane can be used to improve adhesion to the substrate.
[0029]
Further, the moisture curable composition of the present invention is usually added to a curable composition such as a filler, a colorant, a plasticizer, a curing accelerator, a curing retarder, an anti-sagging agent, an anti-aging agent, and a solvent. Additives may be added. For example, as the filler, specifically, calcium carbonate, kaolin, talc, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, shirasu balloon, Examples thereof include glass fiber, asbestos, glass filament, pulverized quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, and titanium dioxide. Specifically, iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, and the like are used as the colorant. Specific examples of the plasticizer include phthalates such as dibutyl phthalate, dioctyl phthalate, and butyl benzyl phthalate, dioctyl adipate, dioctyl succinate, diisodecyl succinate, diisodecyl sebacate, and butyl oleate. Uses esters of polyol compounds such as acid esters, pentaerythritol esters, phosphate esters such as trioctyl phosphate, tricresyl phosphate, epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate, chlorinated paraffin, etc. Is done. As the sagging inhibitor, specifically, hydrogenated castor oil, silicic anhydride, organic bentonite, colloidal silica, or the like is used. As other additives, adhesion imparting agents such as phenol resins and epoxy resins, ultraviolet absorbers, radical chain inhibitors, peroxide decomposing agents, various anti-aging agents and the like are used.
[0030]
【Example】
Hereinafter, the present invention will be specifically described using examples, but the scope of the present invention is not limited thereto.
[0031]
Production Example 1
142 g (0.5 mol) of tetraisopropoxytitanium and 130.1 g (1.0 mol) of acetoacetic acid ethyl ester were weighed into a 500 ml eggplant type flask equipped with a nitrogen introduction tube, and thoroughly mixed with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then isopropyl alcohol was distilled off under reduced pressure to obtain 208 g (98%) of titanium compound A as a yellow liquid. FT-IR analysis of this compound confirmed that the absorption of carbonyl groups (1706 cm −1 , 1735 cm −1 ) of acetoacetic acid ethyl ester was shifted to the lower wavenumber side (1614 cm −1 , 1635 cm −1 ). Moreover, it confirmed that it was diisopropoxy titanium bis (acetoacetic acid ethyl ester) from the result of the following elemental analysis.
Production Example 2
189 g (0.54 mol) of tetrabutoxytitanium and 140 g (1.08 mol) of acetoacetic acid ethyl ester were weighed into a 500 ml eggplant type flask equipped with a nitrogen introduction tube, and thoroughly mixed with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then butyl alcohol was distilled off under reduced pressure to obtain 238 g (95%) of titanium compound B as a yellow liquid. FT-IR analysis of this compound confirmed that the absorption of carbonyl groups (1706 cm −1 , 1735 cm −1 ) of acetoacetic acid ethyl ester was shifted to the lower wavenumber side (1614 cm −1 , 1635 cm −1 ). Moreover, it confirmed that it was dibutoxy titanium bis (acetoacetic acid ethyl ester) from the result of the following elemental analysis.
Production Example 3
142 g (0.5 mol) of tetraisopropoxytitanium and 100.1 g (1.0 mol) of acetylacetone were weighed into a 500 ml eggplant type flask equipped with a nitrogen introduction tube, and thoroughly mixed with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature was close to room temperature, and then isopropyl alcohol was distilled off under reduced pressure to obtain 178 g (98%) of titanium compound C as a yellow liquid. FT-IR analysis of this compound confirmed that the absorption of carbonyl groups (1706 cm −1 , 1735 cm −1 ) of acetylacetone was shifted to the low wavenumber side (1614 cm −1 , 1635 cm −1 ). Moreover, it confirmed that it was diisopropoxy titanium bis (acetoacetonate) from the result of the following elemental analysis.
Production Example 4
In a 500 ml eggplant type flask equipped with a nitrogen introduction tube, 142 g (0.5 mol) of tetraisopropoxytitanium and 116.1 g (1.0 mol) of acetoacetic acid methyl ester were weighed and mixed thoroughly with a magnetic stirrer. Stirring was continued until the exotherm subsided and the internal temperature reached about room temperature, and then isopropyl alcohol was distilled off under reduced pressure to obtain 196 g (99%) of titanium compound D as a yellow liquid. FT-IR analysis of this compound confirmed that the absorption of carbonyl groups (1706 cm −1 , 1735 cm −1 ) of acetoacetic acid methyl ester was shifted to the low wavenumber side (1614 cm −1 , 1635 cm −1 ). Moreover, it confirmed that it was diisopropoxy titanium bis (acetoacetic acid methyl ester) from the result of the following elemental analysis.
Examples 1-4
Titanium compound A, B, C or D obtained in Production Examples 1, 2, 3 and 4 with respect to 100 parts by weight of a silyl group-containing organic polymer (MS polymer S303 manufactured by Kaneka Chemical Co., Ltd.), and Various additives shown in Table 1 were blended in the number of parts by weight shown in Table 1, and kneaded to prepare a curable composition.
[0036]
The obtained curable composition was subjected to the following curable test and tensile adhesion test. The results are shown in Table 1. The operation from kneading to curing was performed in a thermostatic chamber at room temperature of 25 ° C. and humidity of 60% RH.
[0037]
<Curing test>
The curable composition was measured for snap time (time until semi-gelling and loss of fluidity) and tack-free time (time until surface tack disappears).
[0038]
<Tensile adhesion test>
The curable composition was tested for tensile adhesion in accordance with JIS A 5758. An aluminum plate was used as the adherend. The breaking situation is indicated by the following abbreviations.
CF: material break TCF: material thin layer break AF: adherend-material interface peeling
Comparative Examples 1-2
Dibutyltin dilaurate as a conventional tin compound used as a curing agent for a modified silicone rubber-based curable composition with respect to 100 parts by weight of a silyl group-containing organic polymer (MS polymer S303 manufactured by Kaneka Chemical Co., Ltd.) Alternatively, dibutyltin diacetate and various additives shown in Table 1 are blended in parts by weight shown in Table 1, and kneaded under the same conditions as in Examples 1 to 4 to obtain a curable composition, Examples 1 to 4 The snap time, tack free time and tensile adhesion were measured in the same manner as above. The results are shown in Table 1.
[0040]
Details of the materials shown in Table 1 are as follows.
[0041]
NOCRACK NS-6: Anti-aging agent (Ouchi Shinsei Chemical Co., Ltd.)
A-171: Vinyl alkoxysilane compound (manufactured by Nippon Unicar Co., Ltd.)
A-1100: Amino group-substituted alkoxysilane compound (Nihon Unicar Co., Ltd.)
Sumoyle P-350: Liquid paraffin (Muramatsu Oil Co., Ltd.)
Neostan U-200: Dibutyltin diacetate (Nitto Kasei Co., Ltd.)
Neostan U-100: Dibutyltin dilaurate (manufactured by Nitto Kasei Corporation)
[0042]
[Table 1]
【The invention's effect】
As is apparent from Table 1, when the moisture curable composition of the present invention is used, it cures faster than conventional moisture curable compositions, and has excellent adhesion and water-resistant adhesion. In addition, the moisture curable composition of the present invention does not use a tin compound as a curing catalyst, and is a curable composition that does not have a concern about the influence on the living body and the environment due to the endocrine disrupting substance. Such a moisture curable composition is useful as a sealing agent, a coating agent, and an elastic adhesive.
Claims (3)
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| JP2001048855A JP3793031B2 (en) | 2001-02-23 | 2001-02-23 | Moisture curable composition |
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| EP1749858B1 (en) * | 2004-05-07 | 2019-04-03 | Kaneka Corporation | Curable composition |
| JP4480457B2 (en) * | 2004-05-17 | 2010-06-16 | 株式会社カネカ | Curable composition |
| JP5161578B2 (en) * | 2005-09-30 | 2013-03-13 | 株式会社カネカ | One-component curable composition |
| JP7048138B2 (en) * | 2019-11-29 | 2022-04-05 | 日東化成株式会社 | Moisture-curable composition, manufacturing method of cured product |
| WO2021106942A1 (en) * | 2019-11-29 | 2021-06-03 | 日東化成株式会社 | Curing catalyst used for curing of polymer, moisture curable composition, and method for producing cured product |
| US20230257487A1 (en) * | 2020-06-29 | 2023-08-17 | Nitto Kasei Co., Ltd. | Curing catalyst used for curing of polymer, production method for said curing catalyst, mositure-curable composition, and production method for cured product |
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