JP2011241342A - Two-component curing type acrylic adhesive - Google Patents
Two-component curing type acrylic adhesive Download PDFInfo
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- JP2011241342A JP2011241342A JP2010116506A JP2010116506A JP2011241342A JP 2011241342 A JP2011241342 A JP 2011241342A JP 2010116506 A JP2010116506 A JP 2010116506A JP 2010116506 A JP2010116506 A JP 2010116506A JP 2011241342 A JP2011241342 A JP 2011241342A
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- 239000003522 acrylic cement Substances 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 90
- -1 aluminum compound Chemical class 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000003585 thioureas Chemical class 0.000 claims abstract description 19
- 230000002378 acidificating effect Effects 0.000 claims abstract description 18
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims abstract description 9
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical group NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 39
- 230000001070 adhesive effect Effects 0.000 abstract description 39
- 238000003860 storage Methods 0.000 abstract description 37
- 238000002360 preparation method Methods 0.000 abstract description 17
- 239000004615 ingredient Substances 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000002123 temporal effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 238000013329 compounding Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 5
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 4
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 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 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- NEUOBESLMIKJSB-UHFFFAOYSA-J tetrasodium;tetraacetate Chemical compound [Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O NEUOBESLMIKJSB-UHFFFAOYSA-J 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 125000005287 vanadyl group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 1
- LWDSLGBDZZTIHN-UHFFFAOYSA-N 2,5-diethoxybenzene-1,4-diol Chemical compound CCOC1=CC(O)=C(OCC)C=C1O LWDSLGBDZZTIHN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- AFHIIJICYLMCSH-VOTSOKGWSA-N 5-amino-2-[(e)-2-(4-benzamido-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C(C(=C1)S(O)(=O)=O)=CC=C1NC(=O)C1=CC=CC=C1 AFHIIJICYLMCSH-VOTSOKGWSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- MNOILHPDHOHILI-UHFFFAOYSA-N Tetramethylthiourea Chemical compound CN(C)C(=S)N(C)C MNOILHPDHOHILI-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- BFYHFSGFMZUISQ-UHFFFAOYSA-N dibutyl dibutoxyphosphoryl phosphate Chemical compound CCCCOP(=O)(OCCCC)OP(=O)(OCCCC)OCCCC BFYHFSGFMZUISQ-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- WKEWCYHGACEYTR-UHFFFAOYSA-N tert-butyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(C)(C)C WKEWCYHGACEYTR-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、（メタ）アクリル系モノマー（本発明において（メタ）アクリルは、アクリル又はメタクリルをいうものとする。）と重合開始剤からなるＡ液と、（メタ）アクリル系モノマーと重合促進剤からなるＢ液とからなる、レドックス反応を利用した２液硬化型アクリル系接着剤に関する。詳しくは、重合開始剤として有機過酸化物、重合促進剤としてバナジウム化合物、及びチオ尿素誘導体を用いた２液硬化型アクリル系接着剤に関する。 The present invention includes a (meth) acrylic monomer (in the present invention, (meth) acrylic means acrylic or methacrylic) and a liquid A comprising a polymerization initiator, a (meth) acrylic monomer and a polymerization accelerator. The present invention relates to a two-component curable acrylic adhesive using a redox reaction, which is composed of a liquid B consisting of: Specifically, the present invention relates to a two-part curable acrylic adhesive using an organic peroxide as a polymerization initiator, a vanadium compound as a polymerization accelerator, and a thiourea derivative.
（メタ）アクリル系モノマーと有機過酸化物を必須成分とするＡ液と、（メタ）アクリル系モノマーとバナジウム化合物を必須成分とするＢ液からなる、レドックス反応を利用した２液硬化型アクリル系接着剤は、取扱いが簡単で、接着強度に優れており、電機、機械、建築などの分野で多く使用されている。このような接着剤として本発明者らは、前に特許文献１の発明を開示した。特許文献１の接着剤は、Ａ液が（メタ）アクリル系モノマー、有機ハイドロパーオキサイドを必須成分とし、Ｂ液が（メタ）アクリル系モノマー、バナジウム化合物、チオ尿素又はその誘導体、及びＮ−ニトロソジフェニルアミンを必須成分とする２液主剤型アクリル系接着剤であり、硬化時間が短く、しかも長期間保存することもできる接着剤であった。しかしながらこの接着剤には、Ｂ液の重合促進効果が時間の経過と共に低下するという問題があった。即ち、長期間保存したＢ液を使用すると、調製直後のＢ液よりも、硬化に時間を要するのである。 A two-component curable acrylic system utilizing a redox reaction, which consists of a liquid A containing (meth) acrylic monomer and organic peroxide as essential components and a liquid B containing (meth) acrylic monomer and vanadium compound as essential components. Adhesives are easy to handle and have excellent adhesive strength, and are often used in fields such as electrical machinery, machinery, and architecture. The present inventors previously disclosed the invention of Patent Document 1 as such an adhesive. In the adhesive of Patent Document 1, the liquid A has (meth) acrylic monomer and organic hydroperoxide as essential components, and the liquid B is a (meth) acrylic monomer, vanadium compound, thiourea or a derivative thereof, and N-nitroso. It was a two-component main component acrylic adhesive containing diphenylamine as an essential component, and had a short curing time and could be stored for a long time. However, this adhesive has a problem that the polymerization promoting effect of the B liquid decreases with time. That is, when the B solution stored for a long period of time is used, it takes longer to cure than the B solution immediately after preparation.
尚、（メタ）アクリル系モノマーを主成分とし、重合開始剤として有機過酸化物を、重合促進剤としてバナジウム化合物を使用した接着剤が特許文献２〜５に開示されている。特許文献２記載の接着剤組成物はジビニル化合物、有機過酸化物及びビニルモノマーと、アクリロニトリル−ブタジエン−スチレン三元共重合体、アクリロニトリル−ブタジエンゴム又はカルボキシル化アクリロニトリル−ブタジエンゴムから選ばれる１種以上からなる接着剤組成物と、チオ尿素誘導体、α・α’−ジピリジル及びバナジウム等の有機酸塩又は無機酸塩と、更に揮発性有機溶剤とからなる硬化促進剤組成物の２液からなる。特許文献３の発明は、特定構造を有する（メタ）アクリル系モノマー、有機過酸化物及び合成ゴムからなる接着剤組成物に関する発明であり、好適に使用される重合促進剤として、バナジルアセチルアセトネート等のアセチルアセトンの金属塩やチオ尿素誘導体等が例示されている。 Patent Documents 2 to 5 disclose adhesives containing a (meth) acrylic monomer as a main component, an organic peroxide as a polymerization initiator, and a vanadium compound as a polymerization accelerator. The adhesive composition described in Patent Document 2 is at least one selected from divinyl compounds, organic peroxides and vinyl monomers, and acrylonitrile-butadiene-styrene terpolymer, acrylonitrile-butadiene rubber, or carboxylated acrylonitrile-butadiene rubber. And a curing accelerator composition comprising an adhesive composition comprising: an organic acid salt or inorganic acid salt such as a thiourea derivative, α • α′-dipyridyl and vanadium; and a volatile organic solvent. The invention of Patent Document 3 is an invention relating to an adhesive composition comprising a (meth) acrylic monomer having a specific structure, an organic peroxide, and a synthetic rubber, and vanadyl acetylacetonate is preferably used as a polymerization accelerator. Examples thereof include metal salts of acetylacetone such as thiourea derivatives and the like.
特許文献４記載の接着剤は（メタ）アクリル系モノマー等のビニル化合物と過酸化物とパラフィン又はワックスからなる接着剤主剤と、（Ａ）チオ尿素誘導体、（Ｂ）バナジルトリスアセチルアセトネート等のβ−ジケトンキレート又はβ−ケトエステルキレート及び（Ｃ）これらを溶解又は分散せしめる媒体からなる硬化促進剤とからなる。この接着剤は（Ｂ）β−ジケトンキレート又はβ−ケトエステルキレートが一種しか用いられておらず、複数の（Ｂ）β−ジケトンキレート又はβ−ケトエステルキレートを併用することについては記載されていない。
尚、特許文献２〜４に開示されている接着剤は、いずれも接着強度等は優れるがその硬化時間の経時変化について言及するものではない。
The adhesive described in Patent Document 4 includes an adhesive main agent comprising a vinyl compound such as a (meth) acrylic monomer, a peroxide and paraffin or wax, (A) a thiourea derivative, (B) vanadyl trisacetylacetonate, and the like. β-diketone chelate or β-ketoester chelate and (C) a curing accelerator comprising a medium in which these are dissolved or dispersed. In this adhesive, only one kind of (B) β-diketone chelate or β-ketoester chelate is used, and there is no description about using a plurality of (B) β-diketone chelates or β-ketoester chelates in combination.
Note that the adhesives disclosed in Patent Documents 2 to 4 are all excellent in adhesive strength and the like, but do not mention changes with time in the curing time.
特許文献５は重合性組成物に関するものであり、（メタ）アクリレートとｔ−ブチルヒドロペルオキシドを含む第一成分と、（メタ）アクリレートとチオ尿素誘導体及びバナジウム化合物とを含む第二成分からなる。該組成物は保存安定性がよく、長期間保存した後に使用しても硬化時間の変化はほとんど見られなかったが、実施例を見ると硬化時間が６〜１３分程度であり、十分に短いとはいえないものであった。 Patent Document 5 relates to a polymerizable composition, and includes a first component containing (meth) acrylate and t-butyl hydroperoxide, and a second component containing (meth) acrylate, a thiourea derivative and a vanadium compound. The composition has good storage stability, and almost no change in the curing time was observed even after use for a long period of time, but the curing time was about 6 to 13 minutes according to the examples and was sufficiently short. It wasn't.
尚、非特許文献１には不飽和ポリエステル樹脂を硬化させるための促進剤として、アルミニウムアセチルアセトネートが記載されており、「バナジル系促進剤と併用し促進効果を強める」という記載がある。そこで本発明者らは、（メタ）アクリル系モノマーとバナジウム化合物を必須成分とするＢ液に、更にアルミニウムアセチルアセトネートを加えて２液硬化型アクリル系接着剤を製造したところ、接着剤の硬化時間が短縮することを確認できた。しかしながら該Ｂ液は保存安定性が悪く、調製後数日でゲルが発生し、使用できなくなった。 Non-Patent Document 1 describes aluminum acetylacetonate as an accelerator for curing an unsaturated polyester resin, and there is a description that “in combination with a vanadyl accelerator, the acceleration effect is enhanced”. Accordingly, the present inventors produced a two-component curable acrylic adhesive by adding aluminum acetylacetonate to the B liquid containing the (meth) acrylic monomer and the vanadium compound as essential components. It was confirmed that the time was shortened. However, the solution B was poor in storage stability, a gel was generated within a few days after preparation, and could not be used.
本発明は、（メタ）アクリル系モノマー、及び有機過酸化物を必須成分とするＡ液と、（メタ）アクリル系モノマー、バナジウム化合物、及びチオ尿素誘導体を必須成分とするＢ液からなる、レドックス反応を利用した２液硬化型アクリル系接着剤において、接着剤調製直後の硬化時間（即ち、Ａ液とＢ液とを混合してから硬化するまでの時間）が非常に短く、尚且つ保存安定性が良好（即ち、長期間保存してもゲル等が発生せず、接着剤の性質がほとんど変化しない）で、更に硬化時間の経時による増加もほとんど見られない２液硬化型接着剤の提供を目的とする。 The present invention is a redox comprising a liquid A containing (meth) acrylic monomer and organic peroxide as essential components and a liquid B containing (meth) acrylic monomer, vanadium compound and thiourea derivative as essential components. In a two-part curable acrylic adhesive that uses a reaction, the curing time immediately after preparation of the adhesive (that is, the time from mixing the A and B liquids to curing) is very short, and the storage is stable. Providing a two-part curable adhesive that exhibits good properties (ie, gels do not occur even when stored for a long period of time, and the properties of the adhesive hardly change), and the curing time hardly increases over time. With the goal.
本発明者らは鋭意研究を行った結果、Ｂ液にバナジウム化合物、チオ尿素誘導体及び酸性リン化合物を配合すると共に、アルミニウム化合物を配合することにより、接着剤の硬化時間を短くできること、更にバナジウム化合物とアルミニウム化合物の併用によって低下するＢ液の保存安定性を、特定構造のハイドロキノン系化合物を配合することにより回復できることを見出し、上記課題を解決するに至った。すなわち本発明は以下の通りである。 As a result of diligent research, the inventors of the present invention can shorten the curing time of the adhesive by blending the B liquid with a vanadium compound, a thiourea derivative and an acidic phosphorus compound, and blending an aluminum compound. It has been found that the storage stability of liquid B, which is lowered by the combined use of aluminum and an aluminum compound, can be recovered by blending a hydroquinone compound having a specific structure, and the above-mentioned problems have been solved. That is, the present invention is as follows.
（メタ）アクリル系モノマー１００重量部、及び有機過酸化物１〜１０重量部を必須成分とするＡ液、並びに（メタ）アクリル系モノマー１００重量部、バナジウム化合物０．０５〜０．４５重量部、チオ尿素誘導体０．１〜５重量部、アルミニウム化合物０．１〜５重量部、酸性リン化合物０．６〜１０重量部、及び１置換又は２置換のハイドロキノン系化合物０．１〜５重量部を必須成分とするＢ液からなることを特徴とする２液硬化型アクリル系接着剤。
ハイドロキノン系化合物が、２置換ハイドロキノンである前記２液硬化型アクリル系接着剤。
チオ尿素誘導体が、モノベンゾイルチオ尿素である前記２液硬化型アクリル系接着剤。
酸性リン化合物の配合量が、０．６〜４重量部である前記２液硬化型アクリル系接着剤。
Liquid A containing 100 parts by weight of (meth) acrylic monomer and 1 to 10 parts by weight of organic peroxide as essential components, and 100 parts by weight of (meth) acrylic monomer, 0.05 to 0.45 parts by weight of vanadium compound 0.1 to 5 parts by weight of a thiourea derivative, 0.1 to 5 parts by weight of an aluminum compound, 0.6 to 10 parts by weight of an acidic phosphorus compound, and 0.1 to 5 parts by weight of a mono- or di-substituted hydroquinone compound A two-component curable acrylic adhesive, characterized in that it consists of a B-component containing as an essential component.
The two-component curable acrylic adhesive, wherein the hydroquinone compound is a disubstituted hydroquinone.
The two-component curable acrylic adhesive, wherein the thiourea derivative is monobenzoylthiourea.
The said 2 liquid hardening type acrylic adhesive whose compounding quantity of an acidic phosphorus compound is 0.6-4 weight part.
本発明の２液硬化型アクリル系接着剤は、Ｂ液にバナジウム化合物とチオ尿素誘導体及びアルミニウム化合物が配合されているので、Ｂ液調製直後から長期にわたって硬化時間が非常に短い。更にＢ液には酸性リン化合物と共に、１置換又は２置換のハイドロキノン（以下、単にハイドロキノン系化合物と称す。）が併せて配合されており、Ｂ液の保存安定性が良好で、経時により接着剤中にゲル等が発生したり、接着剤の硬化時間が変化したりしにくい。 In the two-component curable acrylic adhesive of the present invention, the vanadium compound, the thiourea derivative, and the aluminum compound are blended in the liquid B, so that the curing time is very short for a long time immediately after the preparation of the liquid B. Furthermore, the B liquid contains a mono- or di-substituted hydroquinone (hereinafter simply referred to as a hydroquinone compound) together with an acidic phosphorus compound, and the B liquid has good storage stability, and the adhesive over time. It is difficult for gels or the like to be generated inside or for the adhesive curing time to change.
本発明においてＡ液、Ｂ液の主成分として用いられる（メタ）アクリル系モノマーとしては、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、フェノキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、（メタ）アクリル酸ヒドロキシアルキルエステル、多価アルコールのポリ（メタ）アクリレート、エポキシ樹脂に（メタ）アクリル酸を付加反応させて得られるエポキシ（メタ）アクリレート、ウレタンポリ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ビスフェノールＡ又はビスフェノールＳのアルキレンオキサイド付加物のジ（メタ）アクリレート等が挙げられ、これらが単独で、或いは、２種以上組み合わせて用いられる。 In the present invention, the (meth) acrylic monomer used as the main component of the liquid A and liquid B includes (meth) acrylic acid, (meth) acrylic acid alkyl ester, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid hydroxyalkyl ester, poly (meth) acrylate of polyhydric alcohol, epoxy (meth) acrylate obtained by addition reaction of (meth) acrylic acid to epoxy resin, urethane poly Examples include (meth) acrylates, polyester (meth) acrylates, di (meth) acrylates of alkylene oxide adducts of bisphenol A or bisphenol S, and these are used alone or in combination of two or more.
またＡ液中に配合される有機過酸化物としては、ｔ−ブチルハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド等のハイドロパーオキサイド類、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシデカノエート等のパーオキシエステル類が挙げられ、これらが単独、或いは、２種以上組み合わせて用いられるが、接着性が優れていることからハイドロパーオキサイド類が特に好適に用いられる。有機過酸化物の配合量はＡ液に配合される（メタ）アクリル系モノマー１００重量部に対して１〜１０重量部とし、特に３〜６重量部が好ましい。有機過酸化物の配合量が１重量部未満であると硬化時間が長くなる恐れがあり、１０重量部を超えるとＡ液の保存安定性が低下し、Ｂ液と混合する前にモノマーの重合が進む恐れがある。 Moreover, as an organic peroxide mix | blended in A liquid, hydroperoxides, such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl peroxide Examples thereof include peroxyesters such as oxybenzoate and t-butylperoxydecanoate, and these are used singly or in combination of two or more, but hydroperoxides are particularly preferred because of their excellent adhesiveness. Preferably used. The compounding amount of the organic peroxide is 1 to 10 parts by weight, particularly 3 to 6 parts by weight, based on 100 parts by weight of the (meth) acrylic monomer blended in the liquid A. If the amount of the organic peroxide is less than 1 part by weight, the curing time may be prolonged. If the amount exceeds 10 parts by weight, the storage stability of the liquid A is lowered, and the monomer polymerization is performed before mixing with the liquid B. There is a risk of progress.
Ｂ液中に配合されるバナジウム化合物としては、バナジルアセチルアセトネート、バナジルステアレート、バナジウムナフテネート、バナジウムアセチルアセトネート、バナジウムベンゾイルアセトネート等が挙げられ、これらが単独で、或いは、２種以上組み合わされて用いられる。バナジウム化合物の配合量はＢ液中に配合される（メタ）アクリル系モノマー１００重量部に対して０．０５〜０．４５重量部であり、０．１〜０．３５重量部がより好ましい。バナジウム化合物の配合量が０．０５重量部未満であると硬化時間が長くなり、逆に０．４５重量部を超えるとＢ液の保存安定性が低下し、経時によってＢ液が変質する恐れが生じる。 Examples of the vanadium compound to be blended in the liquid B include vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium acetylacetonate, vanadium benzoylacetonate, and these are used alone or in combination of two or more. To be used. The compounding quantity of a vanadium compound is 0.05-0.45 weight part with respect to 100 weight part of (meth) acrylic-type monomers mix | blended in B liquid, and 0.1-0.35 weight part is more preferable. When the compounding amount of the vanadium compound is less than 0.05 parts by weight, the curing time becomes long. Conversely, when it exceeds 0.45 parts by weight, the storage stability of the B liquid is lowered, and the B liquid may be deteriorated over time. Arise.
Ｂ液中に配合されるチオ尿素誘導体とは、チオ尿素を包含し、エチレンチオ尿素、１，３−ジメチルチオ尿素、１，３−ジエチルチオ尿素、トリメチルチオ尿素、テトラメチルチオ尿素、モノアセチルチオ尿素、モノベンゾイルチオ尿素、１，３−ジフェニルチオ尿素、１，３−ジシクロヘキシルチオ尿素等が挙げられ、これらが単独で、或いは、２種以上組み合わされ用いられる。尚、短い硬化時間を維持しつつ、Ｂ液の変質を長期に渡って防止するためには、該チオ尿素誘導体としてモノベンゾイルチオ尿素が特に適する。
チオ尿素誘導体の配合量はＢ液中に配合される（メタ）アクリル系モノマー１００重量部に対して０．１〜５重量部であり、０．５〜３重量部がより好ましい。該配合量が０．１重量部未満であるとＢ液の保存安定性が低下し、逆に５重量部を超えると（メタ）アクリル系モノマーへの溶解が困難になり、更に接着強度が低下する恐れが生じる。
The thiourea derivative blended in the liquid B includes thiourea, and includes ethylenethiourea, 1,3-dimethylthiourea, 1,3-diethylthiourea, trimethylthiourea, tetramethylthiourea, monoacetylthiourea, mono Examples include benzoylthiourea, 1,3-diphenylthiourea, 1,3-dicyclohexylthiourea, and the like. These may be used alone or in combination of two or more. Note that monobenzoylthiourea is particularly suitable as the thiourea derivative in order to prevent the deterioration of the liquid B over a long period of time while maintaining a short curing time.
The compounding quantity of a thiourea derivative is 0.1-5 weight part with respect to 100 weight part of (meth) acrylic-type monomers mix | blended in B liquid, and 0.5-3 weight part is more preferable. When the blending amount is less than 0.1 parts by weight, the storage stability of the liquid B is lowered. On the other hand, when it exceeds 5 parts by weight, it becomes difficult to dissolve in the (meth) acrylic monomer, and the adhesive strength is further lowered. The fear of doing.
Ｂ液中に配合されるアルミニウム化合物としては、アルミニウムトリス（アセチルアセトネート）、アルミニウムトリス（エチルアセトアセテート）、エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムイソプロポキシド、アルミニウムｓｅｃ−ブトキシド等が挙げられ、これらが単独で、或いは、２種以上組み合わされて用いられる。アルミニウム化合物の配合量はＢ液中に配合される（メタ）アクリル系モノマー１００重量部に対して０．１〜５重量部であり、特に０．２〜２．０重量部が適する。該配合量が０．１重量部未満であるとＢ液調製直後の短い硬化時間を長期間維持することが困難となり、５重量部を超えても配合量に比例した硬化時間の短縮は見られず、Ｂ液の保存安定性の低下をもたらすだけである。 Examples of the aluminum compound blended in the liquid B include aluminum tris (acetylacetonate), aluminum tris (ethyl acetoacetate), ethyl acetoacetate aluminum diisopropylate, aluminum isopropoxide, aluminum sec-butoxide, and the like. These may be used alone or in combination of two or more. The compounding quantity of an aluminum compound is 0.1-5 weight part with respect to 100 weight part of (meth) acrylic-type monomers mix | blended in B liquid, and 0.2-2.0 weight part is especially suitable. If the blending amount is less than 0.1 parts by weight, it is difficult to maintain a short curing time immediately after preparation of the liquid B for a long period of time, and even if it exceeds 5 parts by weight, a shortening of the curing time proportional to the blending amount is observed. However, only the storage stability of the B liquid is lowered.
Ｂ液中には更に、酸性リン化合物が配合されている。酸性リン化合物はＢ液の保存安定性に寄与し、更にレドックス反応の助剤としても作用しうる。該酸性リン化合物としては、メチルアシッドホスフェート、エチルアシッドホスフェート、ブチルアシッドホスフェート、β−クロロエチルアシッドホスフェート、エトキシエチルアシッドホスフェート、エチレングリコールアシッドホスフェート、ブチルピロホスフェート、フェニルホスフェート、ジフェニルホスフェート、２−（メタ）アクリロイルオキシエチルアシッドホスフェート、２−（メタ）アクリロイルオキシプロピルアシッドホスフェート等の酸性リン化合物が挙げられるが、接着強度を考慮すると（メタ）アクリロイルオキシ基を有する酸性リン化合物が好ましく、これらが単独で、或いは、２種以上組み合わされて用いられる。酸性リン化合物の配合量は、保存安定性の観点からＢ液に配合される（メタ）アクリル系モノマー１００重量部に対して０．６〜１０重量部とする。配合量が０．６〜１０重量部より少なくても、また多くてもＢ液保存中にゲルが発生する恐れがある。
尚、酸性リン化合物は保存中にＢ液が変質することを防止するが、配合量によっては若干ではあるが硬化時間を長くする場合がある。よって硬化時間を重視する場合は、酸性リン化合物の配合量を４重量部以下とすることが望ましい。
In the liquid B, an acidic phosphorus compound is further blended. The acidic phosphorus compound contributes to the storage stability of the B liquid and can also act as an aid for the redox reaction. Examples of the acidic phosphorus compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, β-chloroethyl acid phosphate, ethoxyethyl acid phosphate, ethylene glycol acid phosphate, butyl pyrophosphate, phenyl phosphate, diphenyl phosphate, 2- (meta ) Acidic phosphorus compounds such as acryloyloxyethyl acid phosphate and 2- (meth) acryloyloxypropyl acid phosphate are mentioned, but considering the adhesive strength, acidic phosphorus compounds having a (meth) acryloyloxy group are preferable, and these are independent. Or, two or more kinds are used in combination. The compounding quantity of an acidic phosphorus compound shall be 0.6-10 weight part with respect to 100 weight part of (meth) acrylic-type monomers mix | blended with B liquid from a viewpoint of storage stability. If the blending amount is less than 0.6 to 10 parts by weight or at most, gel may be generated during storage of the B liquid.
The acidic phosphorus compound prevents the liquid B from being altered during storage, but the curing time may be lengthened depending on the amount. Therefore, when importance is attached to the curing time, it is desirable that the amount of the acidic phosphorus compound is 4 parts by weight or less.
更にまたＢ液には、室温での長期保存安定性の向上を目的として、メチルハイドロキノン、ｔ−ブチルハイドロキノン等の１置換ハイドロキノン、又は２，５−ジ−ｔ−ブチルハイドロキノン、２，５−ジ−ｔ−アミルハイドロキノン、２，５−ジエトキシハイドロキノン等の２置換ハイドロキノンから選ばれるハイドロキノン系化合物が配合される。ハイドロキノン系化合物の配合量は、（メタ）アクリル系モノマー１００重量部に対して０．１〜５重量部であり、更には、０．２〜１重量部がより好ましい。ハイドロキノン系化合物の配合量が０．１未満であると保存安定性が低下し、保存中にＢ液にゲルが発生する恐れがある。また逆に５重量部を超えると接着剤の硬化時間が長くなる。
尚、ハイドロキノン系化合物として２置換ハイドロキノンを採用すると、１置換ハイドロキノンを採用した場合よりも、更に接着剤調製直後の硬化時間を短縮することができ、この短い短縮時間を長期間にわたって維持することができる。
Furthermore, for the purpose of improving long-term storage stability at room temperature, the liquid B is monosubstituted hydroquinone such as methylhydroquinone and t-butylhydroquinone, or 2,5-di-t-butylhydroquinone, 2,5-di A hydroquinone compound selected from 2-substituted hydroquinones such as -t-amylhydroquinone and 2,5-diethoxyhydroquinone is blended. The compounding quantity of a hydroquinone type compound is 0.1-5 weight part with respect to 100 weight part of (meth) acrylic-type monomers, Furthermore, 0.2-1 weight part is more preferable. Storage stability will fall that the compounding quantity of a hydroquinone type compound is less than 0.1, and there exists a possibility that a gel may generate | occur | produce in B liquid during storage. Conversely, if it exceeds 5 parts by weight, the curing time of the adhesive becomes long.
In addition, when 2 substituted hydroquinone is employ | adopted as a hydroquinone type compound, the hardening time immediately after adhesive preparation can be further shortened rather than the case where 1 substituted hydroquinone is employ | adopted, and this short shortening time can be maintained over a long period of time. it can.
その他、本発明においてはＡ液及び／又はＢ液に、粘度調整及び硬化物の柔軟性を向上させることを目的として、ポリメチルメタクリレート、ポリビニルブチラール、アクリロニトリル−スチレン共重合体（ＡＳ樹脂）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、メタクリル酸エステル−ブタジエン共重合体（ＭＢ樹脂）、メタクリル酸エステル−ブタジエン−スチレン共重合体（ＭＢＳ樹脂）、メタクリル酸エステル−ブタジエン−アクリロニトリル−スチレン共重合体（ＭＢＡＳ樹脂）等の熱可塑性樹脂、スチレン−ブタジエンゴム（ＳＢＲ）、ポリブタジエンゴム（ＢＲ）、ポリイソプレンゴム（ＩＲ）、クロロプレンゴム（ＣＲ）、ニトリルゴム（ＮＢＲ）、塩化ゴム、アクリルゴム、エピクロルヒドリンゴム等の未加硫ゴム、液状ポリブタジエン、末端（メタ）アクリル変性液状ポリブタジエン、液状アクリロニトリル−ブタジエン共重合体等の液状ゴム、揺変性を付与することを目的として微粉末ポリエチレン、ジベンジリデン−Ｄ−ソルビトール、セルローストリアセテート、ステアリン酸アミド、ベントナイト、微粉末ケイ酸等の揺変性付与剤、表面硬化性を促進するためのパラフィンや蜜ろう、及び着色のための染料や顔料を配合することができる。 In addition, in the present invention, for the purpose of adjusting viscosity and improving flexibility of the cured product in the liquid A and / or liquid B, polymethyl methacrylate, polyvinyl butyral, acrylonitrile-styrene copolymer (AS resin), acrylonitrile. -Butadiene-styrene copolymer (ABS resin), methacrylate ester-butadiene copolymer (MB resin), methacrylate ester-butadiene-styrene copolymer (MBS resin), methacrylate ester-butadiene-acrylonitrile-styrene copolymer Thermoplastic resin such as polymer (MBAS resin), styrene-butadiene rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), chloroprene rubber (CR), nitrile rubber (NBR), chlorinated rubber, acrylic rubber , Epichlorohydrin Unvulcanized rubber such as rubber, liquid polybutadiene, terminal (meth) acryl-modified liquid polybutadiene, liquid rubber such as liquid acrylonitrile-butadiene copolymer, fine powder polyethylene and dibenzylidene-D- for the purpose of imparting thixotropy Thixotropic agents such as sorbitol, cellulose triacetate, stearamide, bentonite, fine powder silicic acid, paraffin and beeswax for promoting surface curability, and dyes and pigments for coloring can be blended.
以下、実施例を挙げて本発明を更に詳細に説明するが、これらの実施例により本発明の範囲が限定的に解釈されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, the scope of the present invention is not limitedly interpreted by these Examples.
実施例及び比較例における各接着剤を、以下の（１）〜（３）の項目について評価した。
（１）保存安定性
Ａ液又はＢ液を２５０ｃｃのポリエチレン製容器に２５０ｇ入れて、４０℃に保たれた乾燥機内に保管し、ゲルを生じるまでの日数を測定した。
（２）硬化時間
２３℃、５０％ＲＨの恒温恒湿室内で寸法１．６×２５×１００ｍｍの冷間圧延鋼板を、ラップ長さ１２ｍｍ（ラップ面積２５×１２ｍｍ2）でＡ液、Ｂ液を等量混合して接着し、５ｋｇｆの荷重をかけても剥がれなくなるまでの時間を測定した。
（３）接着強度
２３℃、５０％ＲＨの恒温恒湿室内で寸法１．６×２５×１００ｍｍの冷間圧延鋼板をラップ長さ１２ｍｍ（ラップ面積２５×１２ｍｍ２）でＡ液、Ｂ液を等量混合して接着し、２４時間養生後にＡＳＴＭ Ｄ１０２２−６４に準拠して引張せん断強度（Ｎ／ｍｍ２）を測定した。
Each adhesive in Examples and Comparative Examples was evaluated for the following items (1) to (3).
(1) Storage stability 250g of A liquid or B liquid was put into a 250cc polyethylene container, stored in a drier kept at 40 ° C, and the number of days until gel formation was measured.
(2) Curing time A cold rolled steel sheet with dimensions of 1.6 × 25 × 100 mm in a constant temperature and humidity chamber at 23 ° C. and 50% RH, with a lap length of 12 mm (lap area of 25 × 12 mm 2 ), A liquid and B liquid Equal amounts were mixed and adhered, and the time until peeling did not occur even when a load of 5 kgf was applied was measured.
(3) Adhesive strength Cold rolled steel sheet of dimensions 1.6 × 25 × 100 mm in a constant temperature and humidity chamber at 23 ° C. and 50% RH with A and B liquids with a lap length of 12 mm (lap area 25 × 12 mm 2 ) Equal amounts were mixed and adhered, and after 24 hours of curing, the tensile shear strength (N / mm 2 ) was measured according to ASTM D1022-64.
［実施例１〜８、比較例１〜８］
下記に示すＡ液を調製し、４０℃に保たれた乾燥機内に保管して保存安定性を評価したところ、３０日以上ゲルが発生せず安定であった。なお、このＡ液は実施例９〜１１、及び比較例９〜１２にも共通に使用した。更に下記に示す組成で各Ｂ液を調製した。尚、Ｂ液の一部（バナジルアセチルアセトネート、アルミニウムトリス（アセチルアセトネート）、モノベンゾイルチオ尿素、２−メタクリロイルオキシエチルアシッドホスフェート）については配合量を表１に記す。また、以下の実施例、比較例において「部」は「重量部」を表すものである。
各Ｂ液の保存安定性と、Ａ液と混合した際の硬化時間及び接着強度を測定し、表２に記す。尚、硬化時間及び接着強度は調製直後のＡ液及びＢ液を用いた場合と、４０℃３０日間保存後のＡ液及びＢ液を用いた場合の双方について測定した。
[Examples 1-8, Comparative Examples 1-8]
The solution A shown below was prepared and stored in a dryer kept at 40 ° C. to evaluate the storage stability. As a result, no gel was generated for 30 days or more and the solution was stable. In addition, this A liquid was used also in Examples 9-11 and Comparative Examples 9-12 in common. Furthermore, each B liquid was prepared with the composition shown below. In addition, about 1 part of B liquid (vanadyl acetylacetonate, aluminum tris (acetylacetonate), monobenzoyl thiourea, 2-methacryloyloxyethyl acid phosphate), compounding quantity is described in Table 1. In the following examples and comparative examples, “part” represents “part by weight”.
The storage stability of each B liquid, the curing time and the adhesive strength when mixed with the A liquid are measured and are shown in Table 2. The curing time and adhesive strength were measured both when the A liquid and the B liquid immediately after preparation were used and when the A liquid and the B liquid after storage at 40 ° C. for 30 days were used.
Ａ液の組成
２−ヒドロキシプロピルメタクリレート ５０部
２−エチルヘキシルメタクリレート ３０部
２，２−ビス［４−（メタクリロキシエトキシ）フェニル］プロパン ２０部
ＭＢＳ樹脂１） ５０部
ｐ−ベンゾキノン ０．１５部
エチレンジアミン４酢酸４ナトリウム塩 ０．１部
クエン酸 １．０部
クメンハイドロパーオキサイド ５部
Composition of Liquid A 2-hydroxypropyl methacrylate 50 parts 2-ethylhexyl methacrylate 30 parts 2,2-bis [4- (methacryloxyethoxy) phenyl] propane 20 parts MBS resin 1) 50 parts p-benzoquinone 0.15 parts ethylenediamine 4 Acetic acid tetrasodium salt 0.1 part Citric acid 1.0 part Cumene hydroperoxide 5 parts
Ｂ液の組成
２−ヒドロキシプロピルメタクリレート ５０部
２−エチルヘキシルメタクリレート ３０部
２，２−ビス［４−（メタクリロキシエトキシ）フェニル］プロパン ２０部
ＭＢＳ樹脂１） ５０部
２，５−ジ−ｔ−ブチルハイドロキノン ０．３部
バナジルアセチルアセトネート（「ＶＯＡＡ２」と略す）
アルミニウムトリス（アセチルアセトネート）（「ＡｌＡＡ３」と略す）
モノベンゾイルチオ尿素（「ＢＴＵ」と略す）
２−メタクリロイルオキシエチルアシッドホスフェート２）（「Ｐ−１Ｍ」と略す）
１）（株）カネカ製 カネエースＢ−５６
２）共栄社化学（株）製 ライトエステルＰ−１Ｍ
Composition of Liquid B 2-hydroxypropyl methacrylate 50 parts 2-ethylhexyl methacrylate 30 parts 2,2-bis [4- (methacryloxyethoxy) phenyl] propane 20 parts MBS resin 1) 50 parts 2,5-di-t-butyl Hydroquinone 0.3 part Vanadyl acetylacetonate (abbreviated as “VOAA 2 ”)
Aluminum tris (acetylacetonate) (abbreviated as “AlAA 3 ”)
Monobenzoylthiourea (abbreviated as “BTU”)
2-Methacryloyloxyethyl acid phosphate 2) (abbreviated as “P-1M”)
1) Kane Ace B-56 manufactured by Kaneka Corporation
2) Light Ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.
表２より、バナジウム化合物（ＶＯＡＡ２）、チオ尿素化合物（ＢＴＵ）、及び酸性リン化合物（Ｐ−１Ｍ）が本発明において開示された範囲内において使用した実施例１〜８は、酸性リン化合物が本発明において開示された量に満たない比較例１〜３、チオ尿素化合物が含まれていない比較例４、比較例６、バナジウム化合物の配合量が多い比較例７、８と比較して保存安定性が優れていることが分かる。また実施例１〜８の接着剤は硬化時間、接着強度のいずれもが、調製直後も４０℃３０日保存後も良好であった。しかしながら、酸性リン化合物（Ｐ−１Ｍ）が５重量部配合されたＢ液を用いた実施例４は、実施例１〜実施例３及び実施例５〜実施例８と比較すると、若干ではあるが調製直後の硬化時間が長く、４０℃３０日保存後の硬化時間も長かった。また比較例５の接着剤は、接着強度の低下は少ないものの、硬化時間が著しく長くなった。これによりアルミニウム化合物（ＡｌＡＡ３）が含まれていない為、Ｂ液の重合促進効果が経時で低下した為である。 From Table 2, Examples 1 to 8 in which the vanadium compound (VOAA 2 ), the thiourea compound (BTU), and the acidic phosphorus compound (P-1M) are used within the scope disclosed in the present invention are the acidic phosphorus compounds. Storage stability compared to Comparative Examples 1 to 3, less than the amount disclosed in the present invention, Comparative Example 4 and Comparative Example 6 containing no thiourea compound, and Comparative Examples 7 and 8 having a large amount of vanadium compound It can be seen that the properties are excellent. In addition, the adhesives of Examples 1 to 8 were good in curing time and adhesive strength both immediately after preparation and after storage at 40 ° C. for 30 days. However, Example 4 using the B liquid in which 5 parts by weight of the acidic phosphorus compound (P-1M) is blended is slightly different from Examples 1 to 3 and Examples 5 to 8. The curing time immediately after preparation was long, and the curing time after storage at 40 ° C. for 30 days was also long. Further, the adhesive of Comparative Example 5 had a markedly long curing time, although there was little decrease in adhesive strength. This is because the aluminum compound (AlAA 3 ) is not contained, so that the polymerization promoting effect of the B liquid is lowered with time.
［実施例９〜１１、比較例９〜１２］
２，５−ジ−ｔ−ブチルハイドロキノンを表３に記す安定剤に変えた以外は、実施例３と同じ組成で各Ｂ液を調製した。各Ｂ液の４０℃での保存安定性と、前述したＡ液と混合した際の硬化時間及び接着強度を測定し、表４に記す。尚、硬化時間及び接着強度は調製直後のＡ液及びＢ液を用いた場合と、４０℃３０日間保存後のＡ液及びＢ液を用いた場合の双方について測定した。
[Examples 9 to 11, Comparative Examples 9 to 12]
Each liquid B was prepared with the same composition as in Example 3 except that 2,5-di-t-butylhydroquinone was changed to the stabilizer shown in Table 3. The storage stability of each B liquid at 40 ° C. and the curing time and adhesive strength when mixed with the above-mentioned A liquid are measured and are shown in Table 4. The curing time and adhesive strength were measured both when the A liquid and the B liquid immediately after preparation were used and when the A liquid and the B liquid after storage at 40 ° C. for 30 days were used.
表４より、安定剤として本発明において開示された１置換又は２置換ハイドロキノンを使用した実施例９〜１１は、他の安定剤を使用した比較例９〜１２に比べ、保存安定性が優れていることが分かる。また実施例９〜１１は硬化時間が調製時、４０℃３０日保存後の何れも良好であった。特に、２置換ハイドロキノンである２，５−ジ−ｔ−アミルハイドロキノンを用いた実施例１１は、硬化時間が調製時、４０℃３０日保存後の何れも、非常に短かった。 From Table 4, Examples 9-11 which used 1 substituted or 2 substituted hydroquinone disclosed in this invention as a stabilizer were excellent in storage stability compared with Comparative Examples 9-12 which used another stabilizer. I understand that. In Examples 9 to 11, the curing time was good at the time of preparation and after storage at 40 ° C. for 30 days. In particular, Example 11 using 2,5-di-t-amylhydroquinone, which is a 2-substituted hydroquinone, had a very short curing time at the time of preparation and after storage at 40 ° C. for 30 days.
［実施例１２〜１３］
下記に示すＡ液を調製し、４０℃における保存安定性を評価したところ、３０日以上安定であった。更に下記に示す組成で各Ｂ液を調製した。尚、各実施例においてアルミニウム化合物及びチオ尿素誘導体は、表５に示すものを用いた。各Ｂ液の４０℃における保存安定性と、Ａ液と混合した際の硬化時間及び接着強度を測定し、表６に記す。尚、硬化時間及び接着強度は調製直後のＡ液及びＢ液を用いた場合と、４０℃３０日間保存後のＡ液及びＢ液を用いた場合の双方について測定した。
[Examples 12 to 13]
The liquid A shown below was prepared, and the storage stability at 40 ° C. was evaluated, and it was stable for 30 days or more. Furthermore, each B liquid was prepared with the composition shown below. In each example, the aluminum compounds and thiourea derivatives shown in Table 5 were used. The storage stability of each B liquid at 40 ° C., the curing time when mixed with the A liquid, and the adhesive strength are measured and are shown in Table 6. The curing time and adhesive strength were measured both when the A liquid and the B liquid immediately after preparation were used and when the A liquid and the B liquid after storage at 40 ° C. for 30 days were used.
Ａ液の組成
２−ヒドロキシプロピルメタクリレート ５０部
２−エチルヘキシルメタクリレート ３０部
２，２−ビス［４−（メタクリロキシエトキシ）フェニル］プロパン ２０部
ＭＢＳ樹脂１） ５０部
ｐ−ベンゾキノン ０．１５部
エチレンジアミン４酢酸４ナトリウム塩 ０．１部
クエン酸 １部
ｔ−ブチルハイドロパーオキサイド ４部
Composition of Liquid A 2-hydroxypropyl methacrylate 50 parts 2-ethylhexyl methacrylate 30 parts 2,2-bis [4- (methacryloxyethoxy) phenyl] propane 20 parts MBS resin 1) 50 parts p-benzoquinone 0.15 parts ethylenediamine 4 Acetic acid tetrasodium salt 0.1 part Citric acid 1 part t-Butyl hydroperoxide 4 parts
Ｂ液の組成
２−ヒドロキシプロピルメタクリレート ５０部
２−エチルヘキシルメタクリレート ３０部
２，２−ビス［４−（メタクリロキシエトキシ）フェニル］プロパン ２０部
ＭＢＳ樹脂１） ５０部
バナジルアセチルアセトネート ０．３部
２，５−ジ−ｔ−ブチルハイドロキノン ０．３部
アルミニウム化合物（表５参照） ０．３部
チオ尿素誘導体（表５参照） １部
２−メタクリロイルオキシエチルアシッドホスフェート２） ３部
１）（株）カネカ製 カネエースＢ−５６
２）共栄社化学（株）製 ライトエステルＰ−１Ｍ
Composition of Liquid B 2-hydroxypropyl methacrylate 50 parts 2-ethylhexyl methacrylate 30 parts 2,2-bis [4- (methacryloxyethoxy) phenyl] propane 20 parts MBS resin 1) 50 parts vanadyl acetylacetonate 0.3 part 2 , 5-Di-t-butylhydroquinone 0.3 part Aluminum compound (see Table 5) 0.3 part Thiourea derivative (see Table 5) 1 part 2-Methacryloyloxyethyl acid phosphate 2) 3 parts
1) Kane Ace B-56 manufactured by Kaneka Corporation
2) Light Ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.
表６より、実施例１２及び１３で用いられたＢ液は保存安定性に優れていることが分かる。またこれらの接着剤は、調製時から硬化時間が短く、４０℃３０日保存後も接着時間の変化が少なく、接着強度の低下もみられない。特にチオ尿素誘導体としてモノベンゾイルチオ尿素を用いた実施例１２は、調製時の硬化時間が短く、３０日保存後も硬化時間の変化が余り見られない。 From Table 6, it turns out that B liquid used in Example 12 and 13 is excellent in storage stability. In addition, these adhesives have a short curing time from the time of preparation, there is little change in the adhesion time even after storage at 40 ° C. for 30 days, and no decrease in adhesive strength is observed. In particular, Example 12 using monobenzoylthiourea as the thiourea derivative has a short curing time at the time of preparation, and the change in the curing time is not significantly observed even after storage for 30 days.
本発明の２液硬化型アクリル系接着剤は、保存安定性が良好であり、各液を調製した直後はもちろん、長期間保存した後であっても硬化時間が短く、電機、機械、建築等、幅広い分野で好適に利用可能である。 The two-component curable acrylic adhesive of the present invention has good storage stability, and the curing time is short even after storage for a long period of time as well as immediately after preparation of each solution. Can be suitably used in a wide range of fields.
Claims (4)
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| JP2014152190A (en) * | 2013-02-05 | 2014-08-25 | Denki Kagaku Kogyo Kk | Energy ray-curable resin composition |
| EP2866798A4 (en) * | 2012-06-27 | 2016-03-16 | Henkel IP & Holding GmbH | Accelerators for two part curable compositions |
| JP2019065081A (en) * | 2017-09-28 | 2019-04-25 | デンカ株式会社 | Composition |
| JP2019065084A (en) * | 2017-09-28 | 2019-04-25 | デンカ株式会社 | Composition |
| JP2020517775A (en) * | 2017-04-21 | 2020-06-18 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Adhesive composition |
| WO2023017788A1 (en) * | 2021-08-11 | 2023-02-16 | 大倉工業株式会社 | Anaerobic adhesive composition |
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| JP2019065084A (en) * | 2017-09-28 | 2019-04-25 | デンカ株式会社 | Composition |
| WO2023017788A1 (en) * | 2021-08-11 | 2023-02-16 | 大倉工業株式会社 | Anaerobic adhesive composition |
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| JP5543844B2 (en) | 2014-07-09 |
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