JP4283586B2 - Curable composition - Google Patents
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- JP4283586B2 JP4283586B2 JP2003113329A JP2003113329A JP4283586B2 JP 4283586 B2 JP4283586 B2 JP 4283586B2 JP 2003113329 A JP2003113329 A JP 2003113329A JP 2003113329 A JP2003113329 A JP 2003113329A JP 4283586 B2 JP4283586 B2 JP 4283586B2
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- Japan
- Prior art keywords
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- weight
- curable composition
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- carbon atoms
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 41
- -1 tertiary amine compound Chemical class 0.000 claims description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 45
- 229920000642 polymer Polymers 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 35
- 239000003822 epoxy resin Substances 0.000 claims description 27
- 229920000647 polyepoxide Polymers 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 21
- 125000003700 epoxy group Chemical group 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 238000000034 method Methods 0.000 description 25
- 230000001070 adhesive effect Effects 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 150000004756 silanes Chemical class 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000004383 yellowing Methods 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000001309 chloro group Chemical group Cl* 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000005370 alkoxysilyl group Chemical group 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
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 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
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 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 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VEAZEPMQWHPHAG-UHFFFAOYSA-N n,n,n',n'-tetramethylbutane-1,4-diamine Chemical compound CN(C)CCCCN(C)C VEAZEPMQWHPHAG-UHFFFAOYSA-N 0.000 description 2
- PMHXGHYANBXRSZ-UHFFFAOYSA-N n,n-dimethyl-2-morpholin-4-ylethanamine Chemical compound CN(C)CCN1CCOCC1 PMHXGHYANBXRSZ-UHFFFAOYSA-N 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 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
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009864 tensile test Methods 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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 1
- XULIXFLCVXWHRF-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidine Chemical compound CN1C(C)(C)CCCC1(C)C XULIXFLCVXWHRF-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- DPMZXMBOYHBELT-UHFFFAOYSA-N 1,3,5-trimethyl-1,3,5-triazinane Chemical compound CN1CN(C)CN(C)C1 DPMZXMBOYHBELT-UHFFFAOYSA-N 0.000 description 1
- RHEIHVJNIMFDKB-UHFFFAOYSA-N 1-[4-[(dimethylamino)methyl]phenyl]-n,n-dimethylmethanamine Chemical compound CN(C)CC1=CC=C(CN(C)C)C=C1 RHEIHVJNIMFDKB-UHFFFAOYSA-N 0.000 description 1
- JWOTWWORMYMZCR-UHFFFAOYSA-N 1-methyl-4-[3-(1-methylpiperidin-4-yl)propyl]piperidine Chemical compound C1CN(C)CCC1CCCC1CCN(C)CC1 JWOTWWORMYMZCR-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- DVDGHRQOLYEZAE-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylcyclohexane-1,2-diamine Chemical compound CN(C)C1CCCCC1N(C)C DVDGHRQOLYEZAE-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine Chemical compound CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 description 1
- RNSVQNMGXFXULJ-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylcyclohexane-1,4-diamine Chemical compound CN(C)C1CCC(N(C)C)CC1 RNSVQNMGXFXULJ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical group CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical group CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 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 1
- VEBFUHQIQCLTJD-UHFFFAOYSA-N n,n,1,2,2,6,6-heptamethylpiperidin-4-amine Chemical compound CN(C)C1CC(C)(C)N(C)C(C)(C)C1 VEBFUHQIQCLTJD-UHFFFAOYSA-N 0.000 description 1
- CMWMUSYWBQEHEJ-UHFFFAOYSA-N n,n,2-trimethylcyclohexan-1-amine Chemical compound CC1CCCCC1N(C)C CMWMUSYWBQEHEJ-UHFFFAOYSA-N 0.000 description 1
- GDHRQDYGUDOEIZ-UHFFFAOYSA-N n,n,2-trimethylpropan-1-amine Chemical compound CC(C)CN(C)C GDHRQDYGUDOEIZ-UHFFFAOYSA-N 0.000 description 1
- OXQMIXBVXHWDPX-UHFFFAOYSA-N n,n,2-trimethylpropan-2-amine Chemical compound CN(C)C(C)(C)C OXQMIXBVXHWDPX-UHFFFAOYSA-N 0.000 description 1
- XIHHDIPVRCDUOT-UHFFFAOYSA-N n,n,4-trimethylcyclohexan-1-amine Chemical compound CC1CCC(N(C)C)CC1 XIHHDIPVRCDUOT-UHFFFAOYSA-N 0.000 description 1
- AIVGHALKDNEHNX-UHFFFAOYSA-N n,n,6-trimethylheptan-1-amine Chemical compound CC(C)CCCCCN(C)C AIVGHALKDNEHNX-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- USSPHSVODLAWSA-UHFFFAOYSA-N n,n-dimethylbutan-2-amine Chemical compound CCC(C)N(C)C USSPHSVODLAWSA-UHFFFAOYSA-N 0.000 description 1
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical group CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WOLFCKKMHUVEPN-UHFFFAOYSA-N n-ethyl-n-methylbutan-1-amine Chemical compound CCCCN(C)CC WOLFCKKMHUVEPN-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 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 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-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
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- WIJVUKXVPNVPAQ-UHFFFAOYSA-N silyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)O[SiH3] WIJVUKXVPNVPAQ-UHFFFAOYSA-N 0.000 description 1
- ACECBHHKGNTVPB-UHFFFAOYSA-N silylformic acid Chemical class OC([SiH3])=O ACECBHHKGNTVPB-UHFFFAOYSA-N 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 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
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- KRLHYNPADOCLAJ-UHFFFAOYSA-N undecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C(C)=C KRLHYNPADOCLAJ-UHFFFAOYSA-N 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- UMVAHUBFIVIZAX-UHFFFAOYSA-N zinc cobalt(2+) 1,2-dimethoxyethane tetracyanide Chemical compound C(OC)COC.[C-]#N.[Zn+2].[Co+2].[C-]#N.[C-]#N.[C-]#N UMVAHUBFIVIZAX-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
Description
【0001】
【発明の属する技術分野】
本発明は、硬化物の適度な強度と伸び、好適な接着強度を有し、黄変を抑制した湿気硬化性組成物に関するものである。本発明の組成物は、コーティング剤、シール剤、注入材、目地材、接着剤、粘着剤、コンクリート等の表面処理材、パテ材等の種々の分野において広く使用することができる。
【0002】
【従来の技術】
エポキシ樹脂は、注型材、積層板、封止材、接着剤、塗料、コンクリート補修材、各種複合材料等の幅広い用途に使用されているが、硬化物が硬くて脆い為、強靭さや衝撃強さに劣るという欠点があった。こうした硬化物の強靭さや衝撃強さの改善に対し、エポキシ樹脂へ反応性ケイ素基含有ポリオキシアルキレン系重合体等をブレンドした硬化性組成物が提案されている(例えば、特許文献1〜3参照)。
【0003】
このエポキシ樹脂と反応性ケイ素基含有ポリオキシアルキレン系重合体等とのブレンド系に使用されるエポキシ樹脂用硬化剤としては、重付加型のポリアミンや酸無水物、ポリフェノール、ポリメルカプタン等よりも、触媒型の3級アミン系化合物(2,4,6−トリス(ジメチルアミノメチル)フェノール、2−(ジメチルアミノメチル)フェノール)を用いた方が、より強度と伸びに優れた硬化物が得られることが分かっている。
【0004】
ところが、上記3級アミン系化合物は黄色に着色している為、エポキシ樹脂と反応性ケイ素基含有ポリオキシアルキレン系重合体等との反応硬化物も黄色くなる傾向にあり、硬化後の外観が重要となるコーティング用途や接着剤用途等においては使用できないという問題があった。
【0005】
【特許文献1】
特開昭61−268720号公報
【特許文献2】
特開昭63−273625号公報
【特許文献3】
特開平9−279047号公報
【0006】
【発明が解決しようとする課題】
本発明は、硬化物の適度な強度と伸び、好適な接着強度を有し、硬化後の黄変を抑制した硬化性組成物を得ることを目的とする。
【0007】
【課題を解決するための手段】
上記課題を解決する為に本発明者らが鋭意検討を行ったところ、エポキシ樹脂硬化剤として水酸基非含有3級アミン系化合物を使用することにより、硬化物の適度な強度と伸び、好適な接着強度を有し、黄変の抑制された硬化性組成物が得られることを見出し、本発明を完成するに到った。
【0008】
即ち、本発明は、(A)反応性ケイ素基含有ポリオキシアルキレン系重合体と(B)(メタ)アクリル酸アルキルエステル系共重合体、を重量比で100/0〜1/99の割合で混合した成分100重量部に対し、(C)エポキシ基含有化合物1〜150重量部、(D)水酸基非含有3級アミン系化合物0.1〜120重量部を含むことを特徴とする硬化性組成物に関する。
【0009】
好ましい実施態様としては、(A)反応性ケイ素基含有ポリオキシアルキレン系重合体と(B)(メタ)アクリル酸アルキルエステル系共重合体、を重量比で100/0〜1/99の割合で混合した成分100重量部に対し、(C)エポキシ基含有化合物1〜150重量部、(D)水酸基非含有3級アミン系化合物0.1〜120重量部、(E)縮合触媒0.1〜10重量部、(F)シランカップリング剤0.1〜20重量部を含むことを特徴とする硬化性組成物に関する。
【0010】
更にまた、好ましい実施態様としては、(A)成分であるポリオキシアルキレン系重合体の反応性ケイ素基が、一般式(1):
−Si(R1 3−c)Xc (1)
(式中、R1は炭素数1から20のアルキル基、炭素数6から20のアリール基または炭素数7から20のアラルキル基を示し、Xは水酸基または加水分解性基を示す。cは1、2または3を示す。)で表されることを特徴とする前記硬化性組成物に関する。
【0011】
更に好ましい実施態様としては、(A)成分であるポリオキシアルキレン系重合体の主鎖骨格が、ポリオキシプロピレンから成ることを特徴とする前記いずれかの硬化性組成物に関する。
【0012】
更にまた、好ましい実施態様としては、(B)成分が、分子鎖が実質的に(a)炭素数1〜8のアルキル基を有する(メタ)アクリル酸アルキルエステル単量体単位と(b)炭素数10以上のアルキル基を有する(メタ)アクリル酸アルキルエステル単量体単位とからなる共重合体であることを特徴とする前記いずれかの硬化性組成物に関する。
【0013】
更にまた、好ましい実施態様としては、(B)成分が、反応性ケイ素基を有する共重合体であることを特徴とする前記いずれかの硬化性組成物に関する。
【0014】
更にまた、好ましい実施態様としては、(C)成分が、エポキシ樹脂であることを特徴とする前記いずれかの硬化性組成物に関する。
更にまた、好ましい実施態様としては、(D)成分が、非複素環構造の水酸基非含有3級アミン系化合物であることを特徴とする前記いずれかの硬化性組成物に関する。
【0015】
【発明の実施の形態】
以下に、本発明を詳細に説明する。
本発明の硬化性組成物は、(A)反応性ケイ素基含有ポリオキシアルキレン系重合体と(B)(メタ)アクリル酸アルキルエステル系共重合体、を重量比で100/0〜1/99の割合で混合した成分100重量部に対し、(C)エポキシ基含有化合物1〜150重量部、(D)水酸基非含有3級アミン系化合物0.1〜120重量部を含むものである。
また、上記硬化性組成物に、さらに(E)縮合触媒0.1〜10重量部、(F)シランカップリング剤0.1〜20重量部を含有させたものも、本発明の硬化性組成物である。
【0016】
本発明に使用される(A)成分の反応性ケイ素基含有ポリオキシアルキレン系重合体における反応性ケイ素基としては、シロキサン結合を形成することによって架橋しうるケイ素含有基であれば特に限定されるものではないが、代表的なものを示すと、例えば一般式(i):
−[Si(R2 2−b)(Xb)O]mSi(R1 3−a)Xa (i)
(式中、R1、R2はそれぞれ炭素数1から20のアルキル基、炭素数6から20のアリール基または炭素数7から20のアラルキル基を示し、Xは水酸基または加水分解性基を示す。aは0、1、2または3、bは0、1または2、mは0以上の整数を示す。但し、a+Σbは1以上。)で表される基が挙げられる。
経済性等の点から、好ましい反応性ケイ素基は、一般式(1):
−Si(R1 3−c)Xc (1)
(式中、R1、Xは前記と同じ。cは1、2または3を示す。)で表される基が挙げられる。
【0017】
上記Xのうちの加水分解性基としては、特に限定されず、従来公知の加水分解性基であれば良い。具体的には、例えば水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基等が挙げられる。これらの内では、加水分解性が穏やかで取り扱い易いという点で、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基等のアルコキシ基が特に好ましい。
上記Xとしての水酸基や加水分解性基は、1個のケイ素原子に1〜3個結合することができ、反応性ケイ素基中に2個以上存在する場合には、それらは同一であっても異なっていてもよい。
【0018】
上記一般式(i)、(1)におけるR1、R2は、炭素数1から20のアルキル基、炭素数6から20のアリール基または炭素数7から20のアラルキル基である。
炭素数1から20のアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、デシル基、ステアリル基等が挙げられ、好ましくは炭素数1から10のアルキル基である。
炭素数6から20のアリール基としては、例えばフェニル基、ナフチル基等が挙げられ、好ましくは炭素数6から10のアリール基である。
炭素数7から20のアラルキル基としては、例えばベンジル基、フェニルエチル基等が挙げられ、好ましくは炭素数7から10のアラルキル基である。
R1としては、メチル基が特に好ましい。
なお、一般式(i)において、R1またはR2が、それぞれ2個以上存在する場合には、それらは同一であっても異なっていてもよい。また、一般式(1)において、R1が2個以上存在する場合には、それらは同一であっても異なっていてもよい。
【0019】
本発明に使用される(A)成分のポリオキシアルキレン系重合体の主鎖構造としては、−R−O−で示される構造を繰り返し単位とする重合体であればよく、このとき、Rは炭素数1から20の2価のアルキレン基であればよい。また、繰り返し単位の全てが同一である単独重合体であっても良く、2つ以上の種類の繰り返し単位を含む共重合体であっても良い。更に、主鎖中に分岐構造を有していても良い。
【0020】
Rとしては、炭素数1から20の2価のアルキレン基であれば特に限定されず、具体的には、−CH2CH2−、−CH(CH3)CH2−、−CH(C2H5)CH2−、−C(CH3)2CH2−、−CH2CH2CH2CH2−等が挙げられる。好ましくは炭素数1から10の2価のアルキレン基であり、特に−CH(CH3)CH2−が好ましい。
【0021】
(A)成分のポリオキシアルキレン系重合体の主鎖骨格は、例えば開始剤と触媒の存在下、モノエポキシドを開環重合することによって得られる。
開始剤の具体例としては、エチレングリコール、プロピレングリコール、ブタンジオール、ヘキサメチレングリコール、メタリルアルコール、ビスフェノールA、水添ビスフェノールA、ネオペンチルグリコール、ポリブタジエンジオール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリプロピレントリオール、ポリプロピレンテトラオール、ジプロピレングリコール、グリセリン、トリメチロールメタン、トリメチロールプロパン、ペンタエリスリトール等のアルコール、2価アルコール、多価アルコール、水酸基を有する各種のオリゴマー等が挙げられる。
【0022】
モノエポキシドの具体例としては、エチレンオキサイド、プロピレンオキサイド、α−ブチレンオキサイド、β−ブチレンオキサイド、ヘキセンオキサイド、シクロヘキセンオキサイド、スチレンオキサイド、α−メチルスチレンオキサイド等のアルキレンオキサイド類;メチルグリシジルエーテル、エチルグリシジルエーテル、イソプロピルグリシジルエーテル、ブチルグリシジルエーテル等のアルキルグリシジルエーテル類;アリルグリシジルエーテル類;アリールグリシジルエーテル類等が挙げられる。
【0023】
触媒としてはKOH、NaOH等のアルカリ触媒、トリフルオロボラン−エーテラート等の酸性触媒、アルミノポルフィリン金属錯体やシアン化コバルト亜鉛−グライム錯体触媒等の複合金属シアン化物錯体触媒等の公知のものが用いられる。特に、副反応が少ない複合金属シアン化物錯体触媒の使用が好ましいが、それ以外のものであってもよい。
【0024】
この他、ポリオキシアルキレン系重合体の主鎖骨格は、水酸基末端ポリオキシアルキレン重合体を、塩基性化合物、例えばKOH、NaOH、KOCH3、NaOCH3等の存在下、2官能以上のハロゲン化アルキル、例えばCH2Cl2、CH2Br2等による鎖延長等によっても得ることができる。また、2官能や3官能のイソシアネート化合物によって、水酸基末端ポリオキシアルキレン重合体を鎖延長する方法等も挙げられる。
【0025】
また、ポリオキシアルキレン系重合体の分子量には特に制限はないが、GPCにおけるポリスチレン換算での数平均分子量が、500から100,000であることが好ましい。更には1,000から70,000であることが、取り扱いの容易さ等の点から好ましい。
【0026】
反応性ケイ素基をポリオキシアルキレン系重合体中に導入する方法としては、特に限定されず、種々の方法を用いることができる。
特に、1分子中に一般式(2):
CH2=C(R4)−R3−O− (2)
(式中、R3は炭素数1から20の2価の有機基、R4は水素原子または炭素数1から10の炭化水素基)で示される不飽和基を末端に有するポリオキシアルキレン系重合体と、
一般式(3):
H−[Si(R2 2−b)(Xb)O]mSi(R1 3−a)Xa (3)
(式中、R1,R2,X,a,b,mは前記と同じ。)で示される反応性ケイ素基含有化合物とを、VIII族遷移金属触媒の存在下で反応させる方法が好ましい。
【0027】
なお、R1、R2またはXが、それぞれ2個以上存在する場合には、それらは同一であっても異なっていてもよい。
また、上記一般式(3)で示される化合物は、代表的にはm=0であり、その際、好ましいaは2または3である。
【0028】
R3の炭素数1から20の2価の有機基としては、好ましくは炭素数1から20のアルキレン基であり、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられ、好ましくは炭素数1から10のアルキレン基である。
R4の炭素数1から10の炭化水素基としては、好ましくは炭素数1から10のアルキル基であり、より好ましくはメチル基である。
【0029】
これ以外にも、水酸基末端ポリオキシアルキレン重合体と反応性ケイ素基含有イソシアネート化合物との反応、イソシアネート基末端ポリオキシアルキレン重合体と反応性ケイ素基含有アミン化合物との反応、イソシアネート基末端ポリオキシアルキレン重合体と反応性ケイ素基含有メルカプタン化合物との反応等によっても、反応性ケイ素基含有ポリオキシアルキレン系重合体を得ることができる。
【0030】
一般式(2)で示される不飽和基を末端に有するポリオキシアルキレン系重合体の製造法としては、従来公知の方法を用いればよく、例えば水酸基末端ポリオキシアルキレン系重合体に不飽和結合を有する化合物を反応させて、エーテル結合、エステル結合、ウレタン結合、カーボネート結合等により結合させる方法等が挙げられる。
【0031】
例えばエーテル結合により不飽和基を導入する場合は、ポリオキシアルキレン重合体の水酸基末端のメタルオキシ化により−OM(MはNaまたはK等)を生成した後、一般式(4):
CH2=C(R4)−R3−X2 (4)
(式中、R3,R4は前記に同じ。X2はハロゲン原子)で示される不飽和基含有化合物を反応させる方法が挙げられる。
【0032】
X2のハロゲン原子としては、塩素原子、臭素原子等が挙げられる。
一般式(4)で示される不飽和基含有化合物の具体例としては、CH2=CH−CH2−Cl、CH2=CH−CH2−Br、CH2=CH−C2H4−Cl、CH2=C(CH3)−CH2−Cl、CH2=C(CH3)−CH2−Br、CH2=C(CH2CH3)−CH2−Cl等が挙げられる。特に反応性の点から、CH2=CH−CH2−Cl、CH2=C(CH3)−CH2−Clが好ましい。
【0033】
不飽和基の導入方法としては、これ以外に、CH2=CH−CH2−基やCH2=C(CH3)−CH2−基等を有するイソシアネート化合物、カルボン酸、エポキシ化合物等を用いることもできる。
【0034】
VIII族遷移金属触媒としては、白金、ロジウム、コバルト、パラジウムおよびニッケル等のVIII族遷移金属元素から選ばれた金属錯体触媒等が有効に使用される。例えば、H2PtCl6・6H2O、白金−ビニルシロキサン錯体、白金−オレフィン錯体、Ptメタル、RhCl(PPh3)3、RhCl3、Rh/Al2O3、RuCl3、IrCl3、FeCl3、PdCl2・2H2O、NiCl2等のような化合物が使用できる。ヒドロシリル化の反応性の点から、H2PtCl6・6H2O、白金−ビニルシロキサン錯体、白金−オレフィン錯体のいずれかであることが特に好ましい。
【0035】
この様な反応性ケイ素基含有ポリオキシアルキレン系重合体の製造法は、例えば、特許第1396791号、特許第1727750号、特許第2135751号、特開平3−72527号等の各公報に記載されている。
【0036】
本発明の硬化性組成物では、必要に応じて下記の(B)成分を添加することができる。
本発明に用いる(B)成分である(メタ)アクリル酸アルキルエステル系共重合体(以下、重合体(B)という)の単量体単位としては、従来公知のものが広く使用でき、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸n−プロピル、アクリル酸n−ブチル、アクリル酸イソブチル、アクリル酸tert−ブチル、アクリル酸n−ヘキシル、アクリル酸2−エチルヘキシル、アクリル酸デシル、アクリル酸ウンデシル、アクリル酸ラウリル、アクリル酸トリデシル、アクリル酸ミリスチル、アクリル酸セチル、アクリル酸ステアリル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n−プロピル、メタクリル酸n−ブチル、メタクリル酸イソブチル、メタクリル酸tert−ブチル、メタクリル酸n−ヘキシル、メタクリル酸2−エチルヘキシル、メタクリル酸デシル、メタクリル酸ウンデシル、メタクリル酸ラウリル、メタクリル酸トリデシル、メタクリル酸ミリスチル、メタクリル酸セチル、メタクリル酸ステアリル等を挙げることができる。
【0037】
重合体(B)の分子鎖は、実質的に1種または2種以上の(メタ)アクリル酸アルキルエステル単量体単位からなる。ここでいう「実質的に上記の単量体単位からなる」とは、重合体(B)中に存在する(メタ)アクリル酸アルキルエステル単量体単位の総量の割合が50重量%を超えることを意味し、好ましくは70重量%以上である。
【0038】
また、これら単量体の組み合わせの中では、相溶性、安定性の点から、分子鎖が実質的に(a)炭素数1〜8のアルキル基を有する(メタ)アクリル酸アルキルエステル単量体単位と(b)炭素数10以上のアルキル基を有する(メタ)アクリル酸アルキルエステル単量体単位からなる共重合体(以下、共重合体(B)−aという)が好ましい。
【0039】
この共重合体における(a)炭素数1〜8のアルキル基を有する(メタ)アクリル酸アルキルエステル単量体は、一般式(5):
CH2=C(R5)COOR6 (5)
(式中、R5は水素原子またはメチル基、R6は炭素数1から8のアルキル基を示す。)で表される。
【0040】
前記一般式(5)におけるR6の炭素数1から8のアルキル基としては、例えばメチル基、エチル基、プロピル基、n−ブチル基、t−ブチル基、2−エチルヘキシル基等が挙げられ、好ましくは炭素数1〜4、より好ましくは炭素数1〜2のアルキル基を挙げることができる。
なお、一般式(5)で表される単量体は、1種類でも、2種以上用いてもよい。
【0041】
また、(b)炭素数10以上のアルキル基を有する(メタ)アクリル酸アルキルエステル単量体は、一般式(6):
CH2=C(R5)COOR7 (6)
(式中、R5は前記に同じ。R7は炭素数10以上のアルキル基を示す。)で表される。
【0042】
前記一般式(6)におけるR7の炭素数10以上のアルキル基としては、例えばラウリル基、トリデシル基、セチル基、ステアリル基、炭素数22のアルキル基等が挙げられ、好ましくは炭素数10〜30、より好ましくは10〜20の長鎖アルキル基が挙げられる。
なお、一般式(6)で示される単量体は、1種類でもよく、例えば炭素数12と13との混合物のように、2種以上混合した単量体であってもよい。
【0043】
共重合体(B)−aの「分子鎖が実質的に(a)および(b)の単量体単位からなる」とは、共重合体(B)−a中に存在する(a)および(b)の単量体単位の総量の割合が50重量%を超えることを意味し、好ましくは70重量%以上である。(a)および(b)の単量体単位の総量の割合が50重量%未満であると、ポリオキシアルキレン系重合体(A)と共重合体(B)−aの相溶性が低下し、白濁したり、接着特性が低下し易くなる傾向がある。
【0044】
また(a)の単量体単位と(b)の単量体単位の割合は、重量比で95:5〜40:60が好ましく、90:10〜60:40がより好ましい。前記割合が95:5より大きくなると相溶性が低下し易くなる傾向があり、40:60より小さくなるとコスト的に不利になりがちになる。
【0045】
重合体(B)には、(メタ)アクリル酸アルキルエステル単量体単位の他に、これらと共重合性を有する単量体単位が含有されていてもよい。例えばアクリル酸、メタクリル酸等のアクリル酸;アクリルアミド、メタクリルアミド、N−メチロールアクリルアミド、N−メチロールメタクリルアミド等のアミド基を含む単量体;グリシジルアクリレート、グリシジルメタクリレート等のエポキシ基を含む単量体;ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート、アミノエチルビニルエーテル等のアミノ基を含む単量体;その他アクリロニトリル、スチレン、α−メチルスチレン、アルキルビニルエーテル、塩化ビニル、酢酸ビニル、プロピオン酸ビニル、エチレン等に起因する単量体等が挙げられる。
【0046】
重合体(B)成分の分子量には特に制限はないが、GPCにおけるポリスチレン換算での数平均分子量が500から100,000であるものが好ましい。更には1,000〜20,000のものが取り扱いの容易さ等の点から好ましい。
【0047】
重合体(B)は、通常のビニル重合の方法によって得ることができる。例えば、ラジカル反応による溶液重合法や塊重合法等によって重合させることにより得ることができるが、特にこれらの方法に限定されるものではない。反応は、通常前記単量体およびラジカル開始剤や連鎖移動剤、溶剤等を加えて50〜150℃で反応させることにより行われる。
【0048】
前記ラジカル開始剤としては、例えばアゾビスイソブチロニトリル、ベンゾイルパーオキサイド等が挙げられる。連鎖移動剤としては、例えばn−ドデシルメルカプタン、t−ドデシルメルカプタン、ラウリルメルカプタン等のメルカプタン類や含ハロゲン化合物等が挙げられる。溶剤としては、例えばエーテル類、炭化水素類、エステル類等の非反応性の溶剤を使用するのが好ましい。
【0049】
重合体(B)には、最終接着強さの点から、反応性ケイ素基を有していることが好ましい。
重合体(B)に反応性ケイ素基を導入する方法には種々の方法があり、例えば、
(I)重合性不飽和結合と反応性ケイ素基を有する化合物を、1種または2種以上の(メタ)アクリル酸アルキルエステル単量体とともに共重合させる方法、
(II)重合性不飽和結合と反応性官能基(以下Y基という)を有する化合物(例えばアクリル酸)を、1種または2種以上の(メタ)アクリル酸アルキルエステル単量体とともに共重合させ、そののち生成した共重合体を反応性ケイ素基およびY基と反応しうる官能基(以下Y’基という)を有する化合物(例えばイソシアネート基と−Si(OCH3)3基を有する化合物)と反応させる方法、
(III)連鎖移動剤として反応性ケイ素基を含有するメルカプタンの存在下、1種または2種以上の(メタ)アクリル酸アルキルエステル単量体を共重合させる方法、
(IV)反応性ケイ素基を含有するアゾビスニトリル化合物やジスルフィド化合物を開始剤として、1種または2種以上の(メタ)アクリル酸アルキルエステル単量体を共重合させる方法、
(V)リビングラジカル重合法によって1種または2種以上の(メタ)アクリル酸アルキルエステル単量体を重合させ、分子末端に反応性ケイ素基を導入する方法、
等が挙げられるが、特にこれらに限定されるものではない。
【0050】
また、(I)〜(V)の方法を各々任意に組み合わせることも可能である。例えば、(I)と(III)の組み合わせとして、連鎖移動剤として反応性ケイ素基を含有するメルカプタンの存在下、重合性不飽和結合と反応性ケイ素基を有する化合物を、1種または2種以上の(メタ)アクリル酸アルキルエステル単量体と共重合させる方法をとることも可能である。
【0051】
(I)記載の重合性不飽和結合と反応性ケイ素基を有する化合物は、一般式(7):
CH2=C(R5)COOR8−[Si(R2 2−b)(Xb)O]mSi(R1 3−a)Xa (7)
(式中、R1,R2,R5,X,a,b,mは前記と同じ。R8は炭素数1〜6の2価のアルキレン基を示す。)、または、一般式(8):
CH2=C(R5)−[Si(R2 2−b)(Xb)O]mSi(R1 3−a)Xa (8)
(式中、R1,R2,R5,X,a,b,mは前記と同じ。)で表される。
【0052】
前記一般式(7)におけるR8の炭素数1〜6の2価のアルキレン基としては、例えばメチレン基、エチレン基、プロピレン基、ブチレン基等が挙げられ、好ましくは炭素数1〜4の2価のアルキレン基である。
なお、R1、R2またはXが、それぞれ2個以上存在する場合には、それらは同一であっても異なっていてもよい。
また、上記一般式(7)または(8)で示される化合物は、代表的にはm=0であり、その際、好ましいaは2または3である。
【0053】
一般式(7)または(8)で表される、重合性不飽和結合と反応性ケイ素基を有する化合物としては、例えば、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン等のγ−メタクリロキシプロピルアルキルポリアルコキシシラン;γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルメチルジメトキシシラン、γ−アクリロキシプロピルトリエトキシシラン等のγ−アクリロキシプロピルアルキルポリアルコキシシラン;ビニルトリメトキシシラン、ビニルメチルジメトキシシラン、ビニルトリエトキシシラン等のビニルアルキルポリアルコキシシラン等が挙げられる。これらの化合物は1種類でもよく、2種以上用いてもよい。
【0054】
(II)記載のY基およびY’基の例としては、種々の基の組み合わせがあるが、例えば、Y基としてアミノ基、水酸基、カルボン酸基を、Y’基としてイソシアネート基を挙げることができる。また別の一例として、特開昭54−36395号公報、特開平1−272654号公報、特開平2−214759号公報に記載されているように、Y基としてはアリル基、Y’基としては水素化ケイ素基(H−Si)を挙げることができる。この場合、VIII族遷移金属の存在下で、ヒドロシリル化反応によりY基とY’基は結合しうる。
【0055】
(III)記載の連鎖移動剤として使用する反応性ケイ素基を含有するメルカプタンとしては、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルトリエトキシシラン等を挙げることができる。
また、特開昭59−78222号公報に記載されているように、1種または2種以上の(メタ)アクリル酸アルキルエステル単量体を、2官能ラジカル重合性化合物および連鎖移動剤としてアルコキシシリル基を含有するメルカプタンの存在下で共重合させる方法も可能である。
【0056】
(IV)記載の、反応性ケイ素基を含有するアゾビスニトリル化合物やジスルフィド化合物としては、特開昭60−23405号公報、特開昭62−70405号公報等に記載されている、アルコキシシリル基を含有するアゾビスニトリル化合物やアルコキシシリル基を含有するジスルフィド化合物を例として挙げることができる。
【0057】
(V)記載の方法としては、特開平9−272714号公報等に記載されている方法を挙げることができる。
その他に、特開昭59−168014号公報、特開昭60−228516号公報等に記載されている、反応性ケイ素基をもつメルカプタンと反応性ケイ素基をもつラジカル重合開始剤を併用する方法も挙げることができる。
【0058】
重合体(B)が反応性ケイ素基を含有する場合、含有される反応性ケイ素基の数は、特に限定されるものではないが、接着力への効果、コストの点から、重合体(B)一分子中に平均0.1個以上3.0個以下、好ましくは平均0.5個以上2.5個以下がよい。
【0059】
(A)成分と(B)成分は重量比で100/0〜1/99の割合で混合されるが、(B)成分を混合することによる接着性の向上等の効果を発現させるためには、(A)成分/(B)成分の重量比が99/1〜10/90の範囲であることが好ましく、より好ましくは95/5〜40/60である。
【0060】
本発明の(C)成分であるエポキシ基含有化合物としては、従来公知のものを広く使用でき、例えばビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールAD型エポキシ樹脂、ビスフェノールS型エポキシ樹脂やこれらを水添したエポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、脂環式エポキシ樹脂、ノボラック型エポキシ樹脂、ウレタン結合を有するウレタン変性エポキシ樹脂、フッ素化エポキシ樹脂、ポリブタジエンあるいはNBRを含有するゴム変性エポキシ樹脂、テトラブロモビスフェノールAのグリシジルエーテル等の難燃型エポキシ樹脂、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メトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、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等のエポキシ基含有シラン類等が挙げられる。これらのエポキシ基含有化合物は、単独で用いてもよく2種以上併用してもよい。これらエポキシ基含有化合物の中では、作業性、硬化性、接着強度、被着体汎用性等の観点から、エポキシ樹脂が好ましく、更に耐水性、耐久性等からビスフェノールA型エポキシ樹脂が好ましい。
【0061】
斯かるエポキシ基含有化合物は、(A)成分と(B)成分の総量の100重量部に対し、通常1〜150重量部程度の範囲、好ましくは5〜120重量部の範囲で使用されるのが良い。1重量部未満では接着強度や耐水性が不十分となり、150重量部を超えると耐衝撃性の低下等が起こり好ましくない。
【0062】
本発明の(D)成分は、水酸基非含有3級アミン系化合物であり、以下の化合物を例示することができる。例えば、トリエチルアミン、トリブチルアミン、n−ブチルエチルメチルアミン、N,N−ジメチル−n−プロピルアミン、N,N−ジメチル−n−ブチルアミン、N,N−ジメチルイソブチルアミン、N,N−ジメチル−sec−ブチルアミン、N,N−ジメチル−tert−ブチルアミン、N,N−ジメチル−n−ヘキシルアミン、N,N−ジメチル−n−オクチルアミン、N,N−ジメチルイソオクチルアミン、N,N,N´,N´−テトラメチルジアミノメタン、N,N,N´,N´−テトラメチルエチレンジアミン、N,N,N´,N´−テトラメチル−1,3−ジアミノプロパン、N,N,N´,N´−テトラメチル−1,4−ジアミノブタン、N,N,N´,N´−テトラメチル−1,3−ブタンジアミン、N,N,N´,N´−テトラメチル−1,6−ジアミノヘキサン、N,N,N´,N´,N´´−ペンタメチルジエチレントリアミン等の脂肪族3級アミン類;N,N−ジメチルアニリン、N,N,N´,N´−テトラメチル−1,4−フェニレンジアミン、N,N−ジメチルベンジルアミン、α−メチルベンジルジメチルアミン、1,4−ビス(ジメチルアミノメチル)ベンゼン、1,3,5−トリス(ジメチルアミノメチル)ベンゼン等の芳香族系3級アミン類;N,N−ジメチルシクロヘキシルアミン、N,N−ジメチル−2−メチルシクロヘキシルアミン、N,N−ジメチル−4−メチルシクロヘキシルアミン、1,2−ビス(ジメチルアミノ)シクロヘキサン、1,4−ビス(ジメチルアミノ)シクロヘキサン、N,N,N´,N´−テトラメチルイソホロンジアミン、N,N,N´,N´−テトラメチルノルボルナンジアミン、ビス(4−ジメチルアミノシクロヘキシル)メタン、ビス(4−ジメチルアミノ−3−メチルシクロヘキシル)メタン等の脂環式3級アミン類;N−メチルピロリジン、N−メチルピペリジン、1,2,2,6,6−ペンタメチルピペリジン、4−(ジメチルアミノ)−1,2,2,6,6−ペンタメチルピペリジン、4,4´−トリメチレンビス(1−メチルピペリジン)、N,N’−ジメチルピペラジン、1,3,5−トリメチルヘキサヒドロ−1,3,5−トリアジン、N−メチルモルホリン、4−[2−(ジメチルアミノ)エチル]モルホリン、2−(ジメチルアミノ)ピリジン、1,8−ジアザビシクロ(5,4,0)−ウンデセン−7(DBU)、6−ジブチルアミノ−1,8−ジアザビシクロ(5,4,0)−ウンデセン−7、4−[2−(ジメチルアミノ)エチル]モルホリン、ビス(モルホリノエチル)エーテル、ビス(2,6−ジメチルモルホリノエチル)エーテル、ビス(3,5−ジメチルモルホリノエチル)エーテル等の複素環式3級アミン類等が挙げられる。これらの水酸基非含有3級アミン系化合物は、単独で用いてもよく2種以上併用してもよい。これら水酸基非含有3級アミン化合物の中では、硬化性、非黄変性、物性バランスといった点で、非複素環構造のものがより好ましい。
【0063】
斯かる水酸基非含有3級アミン系化合物は、(A)成分と(B)成分の総量100重量部に対し、通常0.1〜120重量部程度の範囲、好ましくは1〜100重量部程度の範囲で使用されるのが良い。0.1重量部未満ではエポキシ樹脂の硬化が不十分となり耐衝撃性が低下する。また、120重量部を超えると界面へのブリード等が起こって接着性が低下し好ましくない。
【0064】
本発明の(E)成分である縮合触媒としては、反応性ケイ素基含有重合体の縮合に用いられる従来公知のものを広く使用でき、例えば、ジブチルスズジラウレート、ビス(ジブチルスズラウレート)オキサイド、ジブチルスズマレート、ジブチルスズジアセテート、2−エチルヘキサン酸スズ、ナフテン酸スズ、バーサチック酸スズ、ジブチルスズオキサイドとフタル酸エステルとの反応物、ジブチルスズオキサイドとマレイン酸エステルとの反応物、ジブチルスズオキサイドとエチルシリケートとの反応物、ジブチルスズビスアセチルアセトナート等の有機スズ化合物類;テトラブチルチタネート、テトラプロピルチタネート等のチタン酸エステル類;アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、ジイソプロポキシアルミニウムエチルアセトアセテート等の有機アルミニウム化合物類;ジルコニウムテトラアセチルアセトナート、チタンテトラアセチルアセトナート等のキレート化合物類;ビスマストリス(2−エチルヘキサノエート);オクチル酸亜鉛;オクチルアミン、ラウリルアミン、2,4,6−トリス(ジメチルアミノメチル)フェノール等のアミン化合物、あるいはこれらのカルボン酸塩;酸性リン酸エステル;酸性リン酸エステルとアミンの反応物;飽和若しくは不飽和の多価カルボン酸またはその酸無水物;過剰のポリアミンと多塩基酸とから得られる低分子量ポリアミド樹脂;過剰のポリアミンとエポキシ化合物との反応生成物;γ−アミノプロピルトリメトキシシラン、N−(β−アミノエチル)アミノプロピルメチルジメトキシシラン等のアミノ基を有するシランカップリング剤;等のシラノール縮合触媒、更には他の酸性触媒、塩基性触媒等の公知のシラノール縮合触媒等が挙げられる。これらの触媒は単独で使用してもよく、2種類以上併用してもよい。これら縮合触媒の中では、硬化性や貯蔵安定性、物性バランスの点から、有機スズ化合物類が好ましい。特に硬化速度や貯蔵安定性の点より、4価のスズ触媒が好ましい。
【0065】
斯かる縮合触媒は、硬化性および接着性の観点から、(A)成分と(B)成分の総量の100重量部に対し、通常0.1〜10重量部程度の範囲、好ましくは0.2〜6重量部の範囲で使用されるのが良い。
【0066】
本発明の(F)成分であるシランカップリング剤としては、例えばγ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−(2−アミノエチル)アミノプロピルトリメトキシシラン、γ−(2−アミノエチル)アミノプロピルメチルジメトキシシラン、γ−(2−アミノエチル)アミノプロピルトリエトキシシラン、γ−ウレイドプロピルトリエトキシシラン、N−β−(N−ビニルベンジルアミノエチル)−γ−アミノプロピルトリメトキシシラン、γ−アニリノプロピルトリメトキシシラン等のアミノ基含有シラン類;γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン等のメルカプト基含有シラン類;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メトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、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等のエポキシ基含有シラン類;β−カルボキシルエチルフェニルビス(2−メトキシエトキシ)シラン、N−β−(N−カルボキシルメチルアミノエチル)−γ−アミノプロピルトリメトキシシラン等のカルボキシシラン類;アミノ基含有シラン類と各種ケトンとの脱水縮合により得られるケチミン化シラン類;アミノ基含有シラン類とエポキシ基含有シラン類との反応物;メルカプト基含有シラン類とエポキシ基含有シラン類との反応物;アミノ基含有シラン類とエポキシ樹脂との反応物;メルカプト基含有シラン類とエポキシ樹脂との反応物;テトラエトキシシラン、テトラエトキシシラン4量体、テトラエトキシシラン6量体等のエチルシリケート類;ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン等のビニルシラン類;3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン等のメタクリロキシシラン類等が挙げられる。これらのシランカップリング剤は、単独で用いてもよく2種以上併用してもよい。接着性の点から、好ましくはアミノ基含有シラン類、エポキシ基含有シラン類である。
【0067】
斯かるシランカップリング剤は、接着性、貯蔵安定性、硬化性の観点から、(A)成分および(B)成分の総量の100重量部に対し、通常0.1〜20重量部程度の範囲、好ましくは0.2〜10重量部程度の範囲で添加されるのが良い。
【0068】
本発明の硬化性組成物には、必要に応じ、水、充填剤、揺変剤、可塑剤、反応性希釈剤、安定剤、着色剤等を添加することができる。
充填剤の具体例としては、フュームシリカ、沈降性シリカ、無水ケイ酸およびカーボンブラック等の補強性充填剤;炭酸カルシウム、炭酸マグネシウム、ケイソウ土、焼成クレー、クレー、タルク、酸化チタン、ベントナイト、有機ベントナイト、カオリン、酸化第二鉄、酸化亜鉛、活性亜鉛華、水添ヒマシ油およびシラスバルーン等の充填剤;石綿、ガラス繊維およびフィラメント等の繊維状充填剤等が挙げられる。これら充填剤は1種類のみで使用してもよいし、2種類以上混合使用してもよい。
【0069】
本発明の硬化性組成物は、各種配合剤を使用直前に計量、混合して用いることもできるが、2成分型にして用いることもできる。その際、本硬化性組成物は被着体へビード状に塗布されても良いし、スプレーで塗布されても良く、場合によっては流し出したり、ハケ塗りされても良い。硬化性組成物は塗工後、加熱によって硬化させても良いし、室温下で放置し硬化させることもできる。
【0070】
本発明の硬化性組成物は、コーティング剤、シール剤、注入材、目地材、接着剤、粘着剤、コンクリート等の表面処理材、パテ材等の種々の分野において広く使用することができる。
【0071】
【実施例】
本発明をより一層明らかにする為に、以下具体的な実施例を挙げて説明するが、本発明はこれらに限定されるものではない。
【0072】
(合成例1)
ポリプロピレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキサイドの重合を行い、平均分子量10,000のポリオキシプロピレングリコールを得た。続いて、この水酸基末端ポリエーテルオリゴマーの水酸基に対して1.2倍当量のNaOMeのメタノール溶液を添加してメタノールを留去し、更に3−クロロ−1−プロペンを添加して末端の水酸基をアリル基に変換した。次に、得られた重合体500gに対し、ヘキサン10gを加えて90℃で共沸脱水を行い、ヘキサンを減圧下留去した後、窒素置換した。これに対して白金ジビニルジシロキサン錯体(白金換算で3重量%のキシレン溶液)30μlを加え、撹拌しながら、ジメトキシメチルシラン(DMS)9.0gをゆっくりと滴下した。その混合溶液を90℃で2時間反応させた後、未反応のDMSを減圧下留去し、反応性ケイ素基含有ポリオキシプロピレン重合体を得た。得られた重合体の1H−NMR分析より、末端への反応性ケイ素基導入率は82%であることを確認した(ポリマーA)。
【0073】
(合成例2)
110℃に加熱したトルエン43g中に、アクリル酸ブチル6.0g、メタクリル酸メチル66g、メタクリル酸ステアリル13g、γ−メタクリロキシプロピルメチルジメトキシシラン5.4g、γ−メルカプトプロピルメチルジメトキシシラン7.0gおよびトルエン23gの混合物に、重合開始剤としてアゾビスイソブチロニトリル2.6gを溶かした溶液を、4時間かけて滴下した後、2時間、後重合を行い、固形分濃度60%で、GPC(ポリスチレン換算)による数平均分子量(Mn)が2,200の共重合体を得た。
合成例1で得られたポリマーAと、この共重合体とを固形分比(重量比)60/40でブレンドし、エバポレーターを用い、減圧下、110℃加熱条件で脱揮を行い、固形分濃度99%以上の透明で粘稠な液体を得た(ポリマーB)。
【0074】
(実施例1〜6および比較例1〜5)
表1に示す組成で配合物を作製し、硬化物の外観、引張り物性および接着強度を評価した。なお、実施例1〜6および比較例2で用いた3級アミン化合物の添加量は、比較例1で用いた2,4,6−トリス(ジメチルアミノメチル)フェノールの3級窒素原子と同程度となる様設定した。また、比較例3〜5で用いた1級アミン化合物の添加量は、活性水素基がエポキシ樹脂のグリシジル基と同程度の量となる様設定した。
【0075】
硬化物の外観、引張り物性および接着強度の評価方法は以下のとおり。
(1)外観
配合物を23℃下で2日間静置した後、50℃で3日間加熱し、得られた硬化物表面の黄変の程度を目視により評価した。◎:殆ど黄変せず、○:僅かながら黄変しているが問題ないレベル、×:黄変あり。
【0076】
(2)ダンベル引張り物性
配合物を厚さ約3mmで上記条件(23℃×2日間、50℃×3日間)にて硬化させ、JIS K6251の3号形ダンベル試験片を打ち抜き、引張り速度200mm/分、温度23℃、湿度50%で引張り試験を実施した。なお、M50、M100はそれぞれ伸びが50%、100%の時の引張り強度を、TBは破断強度を、EBは破断時の伸びを示す。
【0077】
(3)接着強度
引張り剪断接着強さおよびT形剥離接着強さを評価した。
引張り剪断接着試験では、100×25×2mmのアルミニウム基材(A1050P)へ配合物を塗布した後、2枚の基材を重ね合わせて長さ12.5mmで貼り合わせ、上記条件(23℃×2日間、50℃×3日間)にて養生し、引張り速度50mm/分、温度23℃、湿度50%で引張り試験を実施した。
剥離接着試験では、200×25×0.1mmのアルミニウム基材(A1050P)へ配合物を塗布した後、2枚の基材を貼り合わせ、重さ3kgのローラーを2往復させ、上記条件(23℃×2日間、50℃×3日間)で養生後、引張り速度200mm/分、温度23℃、湿度50%でT形剥離試験を実施した。
配合組成および評価結果を表1に示す。
【0078】
【表1】
【0079】
水酸基非含有3級アミン化合物を用いた実施例1〜6では、いずれも着色は殆どなく、適度な強度と伸び、好適な接着強度が得られた。一方、水酸基含有3級アミンを用いた比較例1では、硬化物の黄変の程度が大きく、また、1級アミンを用いた比較例3〜5では、物性バランスが大幅に低下した。
【0080】
【発明の効果】
本発明の硬化性組成物の使用により、硬化物の適度な強度と伸び、好適な接着強度を有し、黄変を抑制することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a moisture curable composition having moderate strength and elongation of a cured product, suitable adhesive strength, and suppressed yellowing. The composition of the present invention can be widely used in various fields such as a coating agent, a sealant, an injection material, a joint material, an adhesive, a pressure-sensitive adhesive, a surface treatment material such as concrete, and a putty material.
[0002]
[Prior art]
Epoxy resins are used in a wide range of applications such as casting materials, laminates, sealing materials, adhesives, paints, concrete repair materials, and various composite materials. There was a disadvantage of being inferior. In order to improve the toughness and impact strength of the cured product, a curable composition in which a reactive silicon group-containing polyoxyalkylene polymer or the like is blended with an epoxy resin has been proposed (see, for example, Patent Documents 1 to 3). ).
[0003]
As a curing agent for epoxy resin used in a blend system of this epoxy resin and reactive silicon group-containing polyoxyalkylene polymer, than polyaddition type polyamine, acid anhydride, polyphenol, polymercaptan, etc. The use of a catalyst type tertiary amine compound (2,4,6-tris (dimethylaminomethyl) phenol, 2- (dimethylaminomethyl) phenol) provides a cured product with better strength and elongation. I know that.
[0004]
However, since the tertiary amine compound is colored yellow, the reaction cured product of the epoxy resin and the reactive silicon group-containing polyoxyalkylene polymer tends to be yellow, and the appearance after curing is important. There is a problem that it cannot be used in coating applications and adhesive applications.
[0005]
[Patent Document 1]
JP-A-61-268720
[Patent Document 2]
JP-A 63-273625
[Patent Document 3]
Japanese Patent Laid-Open No. 9-279047
[0006]
[Problems to be solved by the invention]
An object of this invention is to obtain the curable composition which has moderate intensity | strength and elongation of hardened | cured material, suitable adhesive strength, and suppressed yellowing after hardening.
[0007]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have intensively studied. By using a hydroxyl group-free tertiary amine compound as an epoxy resin curing agent, the cured product has an appropriate strength and elongation, and suitable adhesion. It has been found that a curable composition having strength and suppressed yellowing can be obtained, and the present invention has been completed.
[0008]
That is, the present invention provides (A) a reactive silicon group-containing polyoxyalkylene polymer and (B) (meth) acrylic acid alkyl ester copolymer in a weight ratio of 100/0 to 1/99. A curable composition comprising (C) 1 to 150 parts by weight of an epoxy group-containing compound and (D) 0.1 to 120 parts by weight of a hydroxyl group-free tertiary amine compound with respect to 100 parts by weight of the mixed components. Related to things.
[0009]
As a preferred embodiment, (A) a reactive silicon group-containing polyoxyalkylene polymer and (B) (meth) acrylic acid alkyl ester copolymer are used in a weight ratio of 100/0 to 1/99. (C) 1 to 150 parts by weight of an epoxy group-containing compound, (D) 0.1 to 120 parts by weight of a hydroxyl group-free tertiary amine compound, and (E) a condensation catalyst 0.1 to 100 parts by weight of the mixed components. The present invention relates to a curable composition comprising 10 parts by weight and (F) 0.1 to 20 parts by weight of a silane coupling agent.
[0010]
Furthermore, as a preferable embodiment, the reactive silicon group of the polyoxyalkylene polymer as the component (A) is represented by the general formula (1):
-Si (R1 3-c) Xc (1)
(Wherein R1Represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and X represents a hydroxyl group or a hydrolyzable group. c represents 1, 2 or 3. It is related with the said curable composition characterized by these.
[0011]
As a more preferred embodiment, the present invention relates to any one of the above curable compositions, wherein the main chain skeleton of the polyoxyalkylene polymer as the component (A) is composed of polyoxypropylene.
[0012]
Furthermore, in a preferred embodiment, the component (B) has a molecular chain substantially (a) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 1 to 8 carbon atoms and (b) carbon. The curable composition according to any one of the above, which is a copolymer comprising a (meth) acrylic acid alkyl ester monomer unit having several tens or more alkyl groups.
[0013]
Furthermore, as a preferred embodiment, the present invention relates to any one of the above curable compositions, wherein the component (B) is a copolymer having a reactive silicon group.
[0014]
Furthermore, as a preferred embodiment, the present invention relates to any one of the above curable compositions, wherein the component (C) is an epoxy resin.
Furthermore, as a preferred embodiment, the present invention relates to any one of the above curable compositions, wherein the component (D) is a non-heterocyclic structure hydroxyl group-free tertiary amine compound.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The curable composition of the present invention comprises (A) a reactive silicon group-containing polyoxyalkylene polymer and (B) a (meth) acrylic acid alkyl ester copolymer in a weight ratio of 100/0 to 1/99. (C) 1 to 150 parts by weight of an epoxy group-containing compound and (D) 0.1 to 120 parts by weight of a hydroxyl group-free tertiary amine compound are included with respect to 100 parts by weight of the components mixed at a ratio of
Further, the curable composition of the present invention may further include (E) 0.1 to 10 parts by weight of a condensation catalyst and (F) 0.1 to 20 parts by weight of a silane coupling agent. It is a thing.
[0016]
The reactive silicon group in the reactive silicon group-containing polyoxyalkylene polymer of the component (A) used in the present invention is particularly limited as long as it is a silicon-containing group that can be crosslinked by forming a siloxane bond. Although it is not a thing, when a typical thing is shown, for example, general formula (i):
-[Si (R2 2-b) (XbO]mSi (R1 3-a) Xa (I)
(Wherein R1, R2Each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and X represents a hydroxyl group or a hydrolyzable group. a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m represents an integer of 0 or more. However, a + Σb is 1 or more. ) Is represented.
In view of economy and the like, a preferred reactive silicon group is represented by the general formula (1):
-Si (R1 3-c) Xc (1)
(Wherein R1, X is the same as above. c represents 1, 2 or 3. ) Is represented.
[0017]
The hydrolyzable group in X is not particularly limited as long as it is a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group are particularly preferable because they are mildly hydrolyzable and easy to handle.
1 to 3 hydroxyl groups and hydrolyzable groups as X can be bonded to one silicon atom, and when two or more reactive silicon groups are present, they may be the same. May be different.
[0018]
R in the above general formulas (i) and (1)1, R2Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, and a stearyl group. 1 to 10 alkyl groups.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group, and an aryl group having 6 to 10 carbon atoms is preferable.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group, and an aralkyl group having 7 to 10 carbon atoms is preferable.
R1Is particularly preferably a methyl group.
In general formula (i), R1Or R2However, when two or more of each exist, they may be the same or different. In the general formula (1), R1When two or more exist, they may be the same or different.
[0019]
The main chain structure of the polyoxyalkylene polymer of the component (A) used in the present invention may be a polymer having a structure represented by -RO- as a repeating unit, and at this time, R is Any divalent alkylene group having 1 to 20 carbon atoms may be used. Moreover, the homopolymer in which all the repeating units are the same may be sufficient, and the copolymer containing a 2 or more types of repeating unit may be sufficient. Furthermore, the main chain may have a branched structure.
[0020]
R is not particularly limited as long as it is a divalent alkylene group having 1 to 20 carbon atoms, specifically, —CH2CH2-, -CH (CH3) CH2-, -CH (C2H5) CH2-, -C (CH3)2CH2-, -CH2CH2CH2CH2-Etc. are mentioned. Preferred is a divalent alkylene group having 1 to 10 carbon atoms, particularly —CH (CH3) CH2-Is preferred.
[0021]
The main chain skeleton of the polyoxyalkylene polymer (A) can be obtained, for example, by ring-opening polymerization of a monoepoxide in the presence of an initiator and a catalyst.
Specific examples of the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, bisphenol A, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene Examples thereof include alcohols such as glycol, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylol methane, trimethylol propane, and pentaerythritol, dihydric alcohols, polyhydric alcohols, and various oligomers having a hydroxyl group.
[0022]
Specific examples of the monoepoxide include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene oxide, and other alkylene oxides; methyl glycidyl ether, ethyl glycidyl Examples include alkyl glycidyl ethers such as ether, isopropyl glycidyl ether, and butyl glycidyl ether; allyl glycidyl ethers; aryl glycidyl ethers and the like.
[0023]
As the catalyst, known catalysts such as alkali catalysts such as KOH and NaOH, acidic catalysts such as trifluoroborane etherate, double metal cyanide complex catalysts such as aluminoporphyrin metal complex and cobalt zinc cyanide-glyme complex catalyst are used. . In particular, the use of a double metal cyanide complex catalyst with few side reactions is preferable, but other than that may be used.
[0024]
In addition, the main chain skeleton of the polyoxyalkylene polymer is a hydroxyl group-terminated polyoxyalkylene polymer, which is a basic compound such as KOH, NaOH, KOCH.3, NaOCH3In the presence of bifunctional or higher functional alkyl halides such as CH2Cl2, CH2Br2It can also be obtained by chain extension or the like. Moreover, the method etc. which chain-extend a hydroxyl-terminated polyoxyalkylene polymer with a bifunctional or trifunctional isocyanate compound are also mentioned.
[0025]
The molecular weight of the polyoxyalkylene polymer is not particularly limited, but the number average molecular weight in terms of polystyrene in GPC is preferably 500 to 100,000. Further, 1,000 to 70,000 is preferable from the viewpoint of ease of handling.
[0026]
The method for introducing the reactive silicon group into the polyoxyalkylene polymer is not particularly limited, and various methods can be used.
In particular, the general formula (2) per molecule:
CH2= C (R4-R3-O- (2)
(Wherein R3Is a divalent organic group having 1 to 20 carbon atoms, R4Is a hydrogen atom or an unsaturated group represented by a hydrocarbon group having 1 to 10 carbon atoms),
General formula (3):
H- [Si (R2 2-b) (XbO]mSi (R1 3-a) Xa (3)
(Wherein R1, R2, X, a, b, m are the same as above. The method in which the reactive silicon group-containing compound represented by (1) is reacted in the presence of a Group VIII transition metal catalyst is preferred.
[0027]
R1, R2Or when two or more X exists, they may be the same or different.
In addition, the compound represented by the general formula (3) typically has m = 0, and in this case, preferable a is 2 or 3.
[0028]
R3The divalent organic group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 20 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and the like. 1 to 10 alkylene groups.
R4The hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.
[0029]
In addition, the reaction between a hydroxyl group-terminated polyoxyalkylene polymer and a reactive silicon group-containing isocyanate compound, the reaction between an isocyanate group-terminated polyoxyalkylene polymer and a reactive silicon group-containing amine compound, an isocyanate group-terminated polyoxyalkylene A reactive silicon group-containing polyoxyalkylene polymer can also be obtained by reaction of the polymer with a reactive silicon group-containing mercaptan compound or the like.
[0030]
As a method for producing a polyoxyalkylene polymer having an unsaturated group represented by the general formula (2) at the terminal, a conventionally known method may be used. For example, an unsaturated bond is added to a hydroxyl-terminated polyoxyalkylene polymer. Examples thereof include a method in which a compound having a reaction is allowed to react with each other by an ether bond, an ester bond, a urethane bond, or a carbonate bond.
[0031]
For example, when an unsaturated group is introduced by an ether bond, -OM (M is Na or K or the like) is generated by metal oxidation of a hydroxyl group terminal of a polyoxyalkylene polymer, and then the general formula (4):
CH2= C (R4-R3-X2 (4)
(Wherein R3, R4Is the same as above. X2Is a method of reacting an unsaturated group-containing compound represented by (halogen atom).
[0032]
X2Examples of the halogen atom include a chlorine atom and a bromine atom.
Specific examples of the unsaturated group-containing compound represented by the general formula (4) include CH2= CH-CH2-Cl, CH2= CH-CH2-Br, CH2= CH-C2H4-Cl, CH2= C (CH3) -CH2-Cl, CH2= C (CH3) -CH2-Br, CH2= C (CH2CH3) -CH2-Cl etc. are mentioned. Especially from the point of reactivity, CH2= CH-CH2-Cl, CH2= C (CH3) -CH2-Cl is preferred.
[0033]
As other methods for introducing unsaturated groups, CH2= CH-CH2-Group or CH2= C (CH3) -CH2An isocyanate compound having a group or the like, a carboxylic acid, an epoxy compound, or the like can be used.
[0034]
As the group VIII transition metal catalyst, a metal complex catalyst selected from group VIII transition metal elements such as platinum, rhodium, cobalt, palladium and nickel is effectively used. For example, H2PtCl6・ 6H2O, platinum-vinylsiloxane complex, platinum-olefin complex, Pt metal, RhCl (PPh3)3, RhCl3, Rh / Al2O3, RuCl3, IrCl3, FeCl3, PdCl2・ 2H2O, NiCl2Compounds such as can be used. From the point of reactivity of hydrosilylation, H2PtCl6・ 6H2O, platinum-vinylsiloxane complex, or platinum-olefin complex is particularly preferable.
[0035]
Methods for producing such reactive silicon group-containing polyoxyalkylene polymers are described in, for example, Japanese Patent No. 1396791, Japanese Patent No. 1727750, Japanese Patent No. 2135575, and Japanese Patent Laid-Open No. 3-72527. Yes.
[0036]
In the curable composition of this invention, the following (B) component can be added as needed.
As the monomer unit of the (meth) acrylic acid alkyl ester copolymer (hereinafter referred to as polymer (B)) which is the component (B) used in the present invention, conventionally known ones can be widely used. Methyl acid, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, undecyl acrylate, acrylic Lauryl acid, tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methacryl Acid n-hexyl, metac Le 2-ethylhexyl can be mentioned decyl methacrylate, undecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, myristyl, cetyl methacrylate, stearyl methacrylate and the like.
[0037]
The molecular chain of the polymer (B) is substantially composed of one or more (meth) acrylic acid alkyl ester monomer units. Here, “consisting essentially of the above monomer units” means that the proportion of the total amount of (meth) acrylic acid alkyl ester monomer units present in the polymer (B) exceeds 50% by weight. And preferably 70% by weight or more.
[0038]
Among these monomer combinations, in view of compatibility and stability, the (meth) acrylic acid alkyl ester monomer has a molecular chain substantially having (a) an alkyl group having 1 to 8 carbon atoms. A copolymer comprising a unit and (b) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms (hereinafter referred to as copolymer (B) -a) is preferred.
[0039]
The (a) (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 8 carbon atoms in this copolymer has the general formula (5):
CH2= C (R5COOR6 (5)
(Wherein R5Is a hydrogen atom or a methyl group, R6Represents an alkyl group having 1 to 8 carbon atoms. ).
[0040]
R in the general formula (5)6Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, and a 2-ethylhexyl group, and preferably have 1 to 4 carbon atoms. Preferably, a C1-C2 alkyl group can be mentioned.
In addition, the monomer represented by General formula (5) may be used alone or in combination of two or more.
[0041]
In addition, (b) a (meth) acrylic acid alkyl ester monomer having an alkyl group having 10 or more carbon atoms has the general formula (6):
CH2= C (R5COOR7 (6)
(Wherein R5Is the same as above. R7Represents an alkyl group having 10 or more carbon atoms. ).
[0042]
R in the general formula (6)7Examples of the alkyl group having 10 or more carbon atoms include a lauryl group, a tridecyl group, a cetyl group, a stearyl group, and an alkyl group having 22 carbon atoms, preferably 10 to 30 carbon atoms, more preferably 10 to 20 carbon atoms. Long chain alkyl groups.
In addition, the monomer shown by General formula (6) may be one type, for example, the monomer which mixed 2 or more types like the mixture of C12 and C13 may be sufficient.
[0043]
In the copolymer (B) -a, “the molecular chain consists essentially of the monomer units (a) and (b)” means that the copolymer (B) -a exists in the copolymer (B) -a. It means that the ratio of the total amount of the monomer units (b) exceeds 50% by weight, and preferably 70% by weight or more. When the proportion of the total amount of the monomer units (a) and (b) is less than 50% by weight, the compatibility between the polyoxyalkylene polymer (A) and the copolymer (B) -a is reduced, There is a tendency to become cloudy or to easily deteriorate the adhesive properties.
[0044]
The ratio of the monomer unit (a) to the monomer unit (b) is preferably 95: 5 to 40:60, more preferably 90:10 to 60:40, in weight ratio. When the ratio is larger than 95: 5, the compatibility tends to be lowered, and when it is smaller than 40:60, the cost tends to be disadvantageous.
[0045]
In addition to the (meth) acrylic acid alkyl ester monomer unit, the polymer (B) may contain a monomer unit having copolymerizability with these. For example, acrylic acid such as acrylic acid and methacrylic acid; monomers containing amide groups such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylol methacrylamide; monomers containing epoxy groups such as glycidyl acrylate and glycidyl methacrylate Monomers containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc. And monomers.
[0046]
Although there is no restriction | limiting in particular in the molecular weight of a polymer (B) component, The thing whose number average molecular weights by polystyrene conversion in GPC are 500 to 100,000 is preferable. Furthermore, the thing of 1,000-20,000 is preferable from points, such as the ease of handling.
[0047]
The polymer (B) can be obtained by a usual vinyl polymerization method. For example, it can be obtained by polymerizing by a solution polymerization method or a bulk polymerization method by radical reaction, but is not particularly limited to these methods. The reaction is usually carried out by adding the monomer, radical initiator, chain transfer agent, solvent and the like and reacting at 50 to 150 ° C.
[0048]
Examples of the radical initiator include azobisisobutyronitrile and benzoyl peroxide. Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, lauryl mercaptan, and halogen-containing compounds. As the solvent, it is preferable to use non-reactive solvents such as ethers, hydrocarbons and esters.
[0049]
The polymer (B) preferably has a reactive silicon group from the viewpoint of the final adhesive strength.
There are various methods for introducing a reactive silicon group into the polymer (B). For example,
(I) a method of copolymerizing a compound having a polymerizable unsaturated bond and a reactive silicon group together with one or more (meth) acrylic acid alkyl ester monomers;
(II) A compound having a polymerizable unsaturated bond and a reactive functional group (hereinafter referred to as Y group) (for example, acrylic acid) is copolymerized together with one or more (meth) acrylic acid alkyl ester monomers. Thereafter, the resulting copolymer has a functional group capable of reacting with a reactive silicon group and a Y group (hereinafter referred to as a Y ′ group) (for example, an isocyanate group and —Si (OCH3)3A compound having a group),
(III) a method of copolymerizing one or two or more (meth) acrylic acid alkyl ester monomers in the presence of a mercaptan containing a reactive silicon group as a chain transfer agent;
(IV) A method of copolymerizing one or two or more (meth) acrylic acid alkyl ester monomers using an azobisnitrile compound or disulfide compound containing a reactive silicon group as an initiator,
(V) a method of polymerizing one or two or more (meth) acrylic acid alkyl ester monomers by a living radical polymerization method and introducing a reactive silicon group at a molecular terminal;
However, it is not particularly limited to these.
[0050]
Also, the methods (I) to (V) can be arbitrarily combined. For example, as a combination of (I) and (III), one or more compounds having a polymerizable unsaturated bond and a reactive silicon group in the presence of a mercaptan containing a reactive silicon group as a chain transfer agent It is also possible to take a method of copolymerizing with the (meth) acrylic acid alkyl ester monomer.
[0051]
The compound having a polymerizable unsaturated bond and a reactive silicon group described in (I) is represented by the general formula (7):
CH2= C (R5COOR8-[Si (R2 2-b) (XbO]mSi (R1 3-a) Xa (7)
(Wherein R1, R2, R5, X, a, b, m are the same as above. R8Represents a divalent alkylene group having 1 to 6 carbon atoms. ) Or general formula (8):
CH2= C (R5)-[Si (R2 2-b) (XbO]mSi (R1 3-a) Xa (8)
(Wherein R1, R2, R5, X, a, b, m are the same as above. ).
[0052]
R in the general formula (7)8Examples of the divalent alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group, and a divalent alkylene group having 1 to 4 carbon atoms is preferable.
R1, R2Or when two or more X exists, they may be the same or different.
In addition, the compound represented by the general formula (7) or (8) is typically m = 0, and in this case, preferable a is 2 or 3.
[0053]
Examples of the compound represented by the general formula (7) or (8) having a polymerizable unsaturated bond and a reactive silicon group include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylalkylpolyalkoxysilane such as γ-methacryloxypropyltriethoxysilane; γ- such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane Examples include acryloxypropylalkylpolyalkoxysilanes; vinylalkylpolyalkoxysilanes such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and vinyltriethoxysilane. These compounds may be used alone or in combination of two or more.
[0054]
Examples of the Y group and Y ′ group described in (II) include a combination of various groups. For example, an amino group, a hydroxyl group, and a carboxylic acid group may be used as the Y group, and an isocyanate group may be used as the Y ′ group. it can. As another example, as described in JP-A-54-36395, JP-A-1-272654, JP-A-2-214759, the Y group is an allyl group, and the Y ′ group is Mention may be made of silicon hydride groups (H—Si). In this case, the Y group and the Y ′ group can be bonded by a hydrosilylation reaction in the presence of a Group VIII transition metal.
[0055]
Examples of the mercaptan containing a reactive silicon group used as the chain transfer agent described in (III) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and γ-mercaptopropyltriethoxysilane. it can.
In addition, as described in JP-A-59-78222, one or two or more (meth) acrylic acid alkyl ester monomers are used as a bifunctional radical polymerizable compound and an alkoxysilyl as a chain transfer agent. A method of copolymerization in the presence of a mercaptan containing group is also possible.
[0056]
Examples of the azobisnitrile compound or disulfide compound containing a reactive silicon group described in (IV) include alkoxysilyl groups described in JP-A-60-23405, JP-A-62-70405, and the like. Examples thereof include azobisnitrile compounds containing alkenyl and disulfide compounds containing alkoxysilyl groups.
[0057]
Examples of the method described in (V) include the methods described in JP-A-9-272714.
In addition, there is a method in which mercaptan having a reactive silicon group and a radical polymerization initiator having a reactive silicon group are used in combination as described in JP-A-59-168014, JP-A-60-228516, etc. Can be mentioned.
[0058]
When the polymer (B) contains a reactive silicon group, the number of reactive silicon groups to be contained is not particularly limited, but the polymer (B ) The average is 0.1 or more and 3.0 or less, preferably 0.5 or more and 2.5 or less on average in one molecule.
[0059]
The (A) component and the (B) component are mixed at a weight ratio of 100/0 to 1/99, but in order to express effects such as improvement in adhesiveness by mixing the (B) component. The weight ratio of (A) component / (B) component is preferably in the range of 99/1 to 10/90, more preferably 95/5 to 40/60.
[0060]
As the epoxy group-containing compound as the component (C) of the present invention, conventionally known compounds can be widely used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, Contains hydrogenated epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, novolac type epoxy resin, urethane modified epoxy resin having urethane bond, fluorinated epoxy resin, polybutadiene or NBR Rubber modified epoxy resin, flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxy Aminopropyltriethoxysilane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane epoxy group-containing silane such as and the like. These epoxy group-containing compounds may be used alone or in combination of two or more. Among these epoxy group-containing compounds, an epoxy resin is preferable from the viewpoints of workability, curability, adhesive strength, adherend versatility, and the like, and a bisphenol A type epoxy resin is more preferable from the viewpoint of water resistance and durability.
[0061]
Such an epoxy group-containing compound is usually used in the range of about 1 to 150 parts by weight, preferably in the range of 5 to 120 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). Is good. If it is less than 1 part by weight, the adhesive strength and water resistance will be insufficient, and if it exceeds 150 parts by weight, impact resistance will be lowered, which is not preferable.
[0062]
The component (D) of the present invention is a hydroxyl group-free tertiary amine compound, and the following compounds can be exemplified. For example, triethylamine, tributylamine, n-butylethylmethylamine, N, N-dimethyl-n-propylamine, N, N-dimethyl-n-butylamine, N, N-dimethylisobutylamine, N, N-dimethyl-sec -Butylamine, N, N-dimethyl-tert-butylamine, N, N-dimethyl-n-hexylamine, N, N-dimethyl-n-octylamine, N, N-dimethylisooctylamine, N, N, N ' , N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-diaminopropane, N, N, N ′, N′-tetramethyl-1,4-diaminobutane, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N, N, N ′, N′-teto Aliphatic tertiary amines such as methyl-1,6-diaminohexane, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine; N, N-dimethylaniline, N, N, N ′, N '-Tetramethyl-1,4-phenylenediamine, N, N-dimethylbenzylamine, α-methylbenzyldimethylamine, 1,4-bis (dimethylaminomethyl) benzene, 1,3,5-tris (dimethylaminomethyl) ) Aromatic tertiary amines such as benzene; N, N-dimethylcyclohexylamine, N, N-dimethyl-2-methylcyclohexylamine, N, N-dimethyl-4-methylcyclohexylamine, 1,2-bis ( Dimethylamino) cyclohexane, 1,4-bis (dimethylamino) cyclohexane, N, N, N ′, N′-tetramethylisophoronedia Alicyclic tertiary amines such as N, N, N ′, N′-tetramethylnorbornanediamine, bis (4-dimethylaminocyclohexyl) methane, bis (4-dimethylamino-3-methylcyclohexyl) methane; N-methylpyrrolidine, N-methylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 4- (dimethylamino) -1,2,2,6,6-pentamethylpiperidine, 4,4′- Trimethylenebis (1-methylpiperidine), N, N′-dimethylpiperazine, 1,3,5-trimethylhexahydro-1,3,5-triazine, N-methylmorpholine, 4- [2- (dimethylamino) Ethyl] morpholine, 2- (dimethylamino) pyridine, 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU), 6-dibutylamino -1,8-diazabicyclo (5,4,0) -undecene-7, 4- [2- (dimethylamino) ethyl] morpholine, bis (morpholinoethyl) ether, bis (2,6-dimethylmorpholinoethyl) ether And heterocyclic tertiary amines such as bis (3,5-dimethylmorpholinoethyl) ether. These hydroxyl group-free tertiary amine compounds may be used alone or in combination of two or more. Among these hydroxyl group-free tertiary amine compounds, those having a non-heterocyclic structure are more preferable from the viewpoints of curability, non-yellowing, and balance of physical properties.
[0063]
Such a hydroxyl group-free tertiary amine compound is usually in the range of about 0.1 to 120 parts by weight, preferably about 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). Good to be used in range. If it is less than 0.1 part by weight, the epoxy resin is not sufficiently cured, and the impact resistance is lowered. On the other hand, if it exceeds 120 parts by weight, bleeding to the interface occurs and the adhesiveness is lowered, which is not preferable.
[0064]
As the condensation catalyst which is the component (E) of the present invention, conventionally known ones used for condensation of reactive silicon group-containing polymers can be widely used. For example, dibutyltin dilaurate, bis (dibutyltin laurate) oxide, dibutyltin Rate, dibutyltin diacetate, tin 2-ethylhexanoate, tin naphthenate, tin versatate, reaction product of dibutyltin oxide and phthalate ester, reaction product of dibutyltin oxide and maleate ester, dibutyltin oxide and ethylsilicate Reaction products, organotin compounds such as dibutyltin bisacetylacetonate; titanates such as tetrabutyltitanate and tetrapropyltitanate; aluminum trisacetylacetonate, aluminum trisethylacetoacetate , Organoaluminum compounds such as diisopropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; bismuth tris (2-ethylhexanoate); zinc octylate; octylamine; Amine compounds such as laurylamine, 2,4,6-tris (dimethylaminomethyl) phenol, or carboxylates thereof; acidic phosphate ester; reaction product of acidic phosphate ester and amine; saturated or unsaturated polyvalent Carboxylic acid or acid anhydride; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, N- (β-amino Ethyl) aminopropyl Silane coupling agent having an amino group such as chill dimethoxysilane; like silanol condensation catalyst, even other acidic catalysts, known silanol condensation catalysts such as basic catalyst, and the like. These catalysts may be used alone or in combination of two or more. Among these condensation catalysts, organotin compounds are preferred from the viewpoints of curability, storage stability, and physical property balance. In particular, a tetravalent tin catalyst is preferable from the viewpoint of curing speed and storage stability.
[0065]
Such a condensation catalyst is usually in the range of about 0.1 to 10 parts by weight, preferably 0.2 to 100 parts by weight of the total amount of the components (A) and (B), from the viewpoint of curability and adhesiveness. It is good to be used in the range of ˜6 parts by weight.
[0066]
Examples of the silane coupling agent that is the component (F) of the present invention include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- ( 2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Amino group-containing silanes such as trimethoxysilane and γ-anilinopropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldi Ethoxy Mercapto group-containing silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as trimethoxysilane; carboxysilanes such as β-carboxylethylphenylbis (2-methoxyethoxy) silane and N-β- (N-carboxylmethylaminoethyl) -γ-aminopropyltrimethoxysilane ; Ketiminated silanes obtained by dehydration condensation of amino group-containing silanes and various ketones; reaction product of amino group-containing silanes and epoxy group-containing silanes; mercapto group-containing silanes and epoxy group-containing silanes Reaction product: Reaction product of amino group-containing silane and epoxy resin Reaction products of mercapto group-containing silanes and epoxy resins; ethyl silicates such as tetraethoxysilane, tetraethoxysilane tetramer, tetraethoxysilane hexamer; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane Vinyl silanes such as; methacryloxy silanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and the like. These silane coupling agents may be used alone or in combination of two or more. From the viewpoint of adhesiveness, amino group-containing silanes and epoxy group-containing silanes are preferred.
[0067]
Such a silane coupling agent is usually in the range of about 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B) from the viewpoints of adhesiveness, storage stability, and curability. Preferably, it is added in the range of about 0.2 to 10 parts by weight.
[0068]
If necessary, water, a filler, a thixotropic agent, a plasticizer, a reactive diluent, a stabilizer, a colorant, and the like can be added to the curable composition of the present invention.
Specific examples of fillers include reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic Examples include fillers such as bentonite, kaolin, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil, and shirasu balloon; and fibrous fillers such as asbestos, glass fibers, and filaments. These fillers may be used alone or in combination of two or more.
[0069]
The curable composition of the present invention can be used by weighing and mixing various compounding agents immediately before use, but can also be used in a two-component type. In this case, the present curable composition may be applied to the adherend in a bead shape, may be applied by spraying, or may be poured or brushed depending on the case. The curable composition may be cured by heating after coating, or may be allowed to cure at room temperature.
[0070]
The curable composition of the present invention can be widely used in various fields such as a coating agent, a sealing agent, an injection material, a joint material, an adhesive, an adhesive, a surface treatment material such as concrete, and a putty material.
[0071]
【Example】
In order to further clarify the present invention, specific examples will be described below, but the present invention is not limited thereto.
[0072]
(Synthesis Example 1)
Propylene oxide was polymerized using polypropylene glycol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene glycol having an average molecular weight of 10,000. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyether oligomer to distill off the methanol, and 3-chloro-1-propene was further added to remove the terminal hydroxyl group. Converted to an allyl group. Next, 10 g of hexane was added to 500 g of the obtained polymer, azeotropic dehydration was performed at 90 ° C., and hexane was distilled off under reduced pressure, followed by nitrogen substitution. To this, 30 μl of platinum divinyldisiloxane complex (3 wt% xylene solution in terms of platinum) was added, and 9.0 g of dimethoxymethylsilane (DMS) was slowly added dropwise with stirring. The mixed solution was reacted at 90 ° C. for 2 hours, and then unreacted DMS was distilled off under reduced pressure to obtain a reactive silicon group-containing polyoxypropylene polymer. Of the resulting polymer1From the 1 H-NMR analysis, it was confirmed that the reactive silicon group introduction rate at the terminal was 82% (Polymer A).
[0073]
(Synthesis Example 2)
In 43 g of toluene heated to 110 ° C., 6.0 g of butyl acrylate, 66 g of methyl methacrylate, 13 g of stearyl methacrylate, 5.4 g of γ-methacryloxypropylmethyldimethoxysilane, 7.0 g of γ-mercaptopropylmethyldimethoxysilane and A solution prepared by dissolving 2.6 g of azobisisobutyronitrile as a polymerization initiator in a mixture of 23 g of toluene was dropped over 4 hours, followed by post-polymerization for 2 hours, with a GPC ( A copolymer having a number average molecular weight (Mn) of 2,200 in terms of polystyrene was obtained.
The polymer A obtained in Synthesis Example 1 and this copolymer were blended at a solid content ratio (weight ratio) of 60/40, and devolatilized under heating at 110 ° C. under reduced pressure using an evaporator. A transparent and viscous liquid having a concentration of 99% or more was obtained (Polymer B).
[0074]
(Examples 1-6 and Comparative Examples 1-5)
Formulations were prepared with the compositions shown in Table 1, and the appearance, tensile physical properties, and adhesive strength of the cured products were evaluated. In addition, the addition amount of the tertiary amine compound used in Examples 1 to 6 and Comparative Example 2 is approximately the same as the tertiary nitrogen atom of 2,4,6-tris (dimethylaminomethyl) phenol used in Comparative Example 1. It set so that it might become. Moreover, the addition amount of the primary amine compound used by Comparative Examples 3-5 was set so that an active hydrogen group might become a quantity comparable as the glycidyl group of an epoxy resin.
[0075]
The evaluation method of the appearance, tensile properties and adhesive strength of the cured product is as follows.
(1) Appearance
The mixture was allowed to stand at 23 ° C. for 2 days, then heated at 50 ° C. for 3 days, and the degree of yellowing of the resulting cured product surface was visually evaluated. A: Almost no yellowing, O: Slightly yellowing but no problem, x: Yellowing.
[0076]
(2) Dumbbell tensile physical properties
The composition was cured at a thickness of about 3 mm under the above conditions (23 ° C. × 2 days, 50 ° C. × 3 days), and a JIS K6251 No. 3 dumbbell test piece was punched out. A tensile test was conducted at a humidity of 50%. M50 and M100 indicate the tensile strength when the elongation is 50% and 100%, TB indicates the breaking strength, and EB indicates the elongation at break.
[0077]
(3) Adhesive strength
Tensile shear bond strength and T-peel bond strength were evaluated.
In the tensile shear adhesion test, the composition was applied to a 100 × 25 × 2 mm aluminum substrate (A1050P), and then the two substrates were superposed and bonded together at a length of 12.5 mm. 2 days, 50 ° C. × 3 days), and a tensile test was performed at a tensile speed of 50 mm / min, a temperature of 23 ° C., and a humidity of 50%.
In the peel adhesion test, the composition was applied to a 200 × 25 × 0.1 mm aluminum base material (A1050P), the two base materials were bonded together, and a roller having a weight of 3 kg was reciprocated twice. C. × 2 days, 50 ° C. × 3 days), and a T-shaped peel test was performed at a pulling rate of 200 mm / min, a temperature of 23 ° C., and a humidity of 50%.
The composition and the evaluation results are shown in Table 1.
[0078]
[Table 1]
[0079]
In Examples 1 to 6 in which the hydroxyl group-free tertiary amine compound was used, none was colored, and appropriate strength and elongation were obtained, and suitable adhesive strength was obtained. On the other hand, in Comparative Example 1 using a hydroxyl group-containing tertiary amine, the degree of yellowing of the cured product was large, and in Comparative Examples 3 to 5 using a primary amine, the balance of physical properties was greatly lowered.
[0080]
【The invention's effect】
By using the curable composition of the present invention, the cured product has appropriate strength and elongation, suitable adhesive strength, and can suppress yellowing.
Claims (8)
−Si(R1 3−c)Xc (1)
(式中、R1は炭素数1から20のアルキル基、炭素数6から20のアリール基または炭素数7から20のアラルキル基を示し、Xは水酸基または加水分解性基を示す。cは1、2または3を示す。)で表されることを特徴とする請求項1または2記載の硬化性組成物。The reactive silicon group of component (A) is represented by the general formula (1):
-Si (R 1 3-c ) X c (1)
(Wherein R 1 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, and c represents 1) The curable composition according to claim 1, wherein the curable composition is represented by 2 or 3.
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