JP2013117011A - Two-liquid curable acrylic composition - Google Patents
Two-liquid curable acrylic composition Download PDFInfo
- Publication number
- JP2013117011A JP2013117011A JP2012231411A JP2012231411A JP2013117011A JP 2013117011 A JP2013117011 A JP 2013117011A JP 2012231411 A JP2012231411 A JP 2012231411A JP 2012231411 A JP2012231411 A JP 2012231411A JP 2013117011 A JP2013117011 A JP 2013117011A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- liquid
- curable acrylic
- acrylic composition
- meth
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000007788 liquid Substances 0.000 title claims abstract description 76
- -1 urea compound Chemical class 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 150000003682 vanadium compounds Chemical class 0.000 claims abstract description 23
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 27
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims 1
- 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 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 31
- 238000009792 diffusion process Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 238000002156 mixing Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- 238000003860 storage Methods 0.000 description 17
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 239000003638 chemical reducing agent Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910019142 PO4 Inorganic materials 0.000 description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 9
- 238000013329 compounding Methods 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MDJZGXRFYKPSIM-JCYAYHJZSA-N (2r,3r)-2,3-dihydroxybutanedihydrazide Chemical compound NNC(=O)[C@H](O)[C@@H](O)C(=O)NN MDJZGXRFYKPSIM-JCYAYHJZSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- SNVRDQORMVVQBI-OWOJBTEDSA-N (e)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C\C(=O)NN SNVRDQORMVVQBI-OWOJBTEDSA-N 0.000 description 1
- 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 1
- 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 1
- SNVRDQORMVVQBI-UPHRSURJSA-N (z)-but-2-enedihydrazide Chemical compound NNC(=O)\C=C/C(=O)NN SNVRDQORMVVQBI-UPHRSURJSA-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
- TUMNHQRORINJKE-UHFFFAOYSA-N 1,1-diethylurea Chemical compound CCN(CC)C(N)=O TUMNHQRORINJKE-UHFFFAOYSA-N 0.000 description 1
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- ROFVGYAMRSGUSQ-UHFFFAOYSA-N 1-(2-bromoethyl)piperazine;hydrobromide Chemical compound Br.BrCCN1CCNCC1 ROFVGYAMRSGUSQ-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
- MAAZCMPNIDZFAQ-UHFFFAOYSA-N 2,2-diethoxyethyl dihydrogen phosphate Chemical compound CCOC(COP(=O)(O)O)OCC MAAZCMPNIDZFAQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- ANHAEBWRQNIPEV-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCl ANHAEBWRQNIPEV-UHFFFAOYSA-N 0.000 description 1
- WSOZRQWKNKJOIA-UHFFFAOYSA-N 2-ethoxyethyl dihydrogen phosphate Chemical compound CCOCCOP(O)(O)=O WSOZRQWKNKJOIA-UHFFFAOYSA-N 0.000 description 1
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 description 1
- LGWROMGRXCZCLA-UHFFFAOYSA-N 2-hydroxybutanedihydrazide Chemical compound NNC(=O)CC(O)C(=O)NN LGWROMGRXCZCLA-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FDNAQCWUERCJBK-UHFFFAOYSA-N 3-hydroxynaphthalene-2-carbohydrazide Chemical compound C1=CC=C2C=C(O)C(C(=O)NN)=CC2=C1 FDNAQCWUERCJBK-UHFFFAOYSA-N 0.000 description 1
- SKKXTPQPJYBUEF-UHFFFAOYSA-N 3-phosphonooxypropyl prop-2-enoate Chemical compound OP(O)(=O)OCCCOC(=O)C=C SKKXTPQPJYBUEF-UHFFFAOYSA-N 0.000 description 1
- MTYCXPNDBZCTFX-UHFFFAOYSA-N 4,6-dihydrazinyl-n-methyl-1,3,5-triazin-2-amine Chemical compound CNC1=NC(NN)=NC(NN)=N1 MTYCXPNDBZCTFX-UHFFFAOYSA-N 0.000 description 1
- ZMZGIVVRBMFZSG-UHFFFAOYSA-N 4-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=C(O)C=C1 ZMZGIVVRBMFZSG-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- OFCGAKCSVKXPJK-UHFFFAOYSA-N C(C)(C)(C)OOC(C)(C)C.C(CCCCCCCCC)(=O)O Chemical compound C(C)(C)(C)OOC(C)(C)C.C(CCCCCCCCC)(=O)O OFCGAKCSVKXPJK-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
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- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-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
- 239000007983 Tris buffer Substances 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
- RGJSWMPPIHQBPC-UHFFFAOYSA-N [V+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] Chemical compound [V+5].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] RGJSWMPPIHQBPC-UHFFFAOYSA-N 0.000 description 1
- LPHBWRJXTUNCAI-UHFFFAOYSA-N [V+5].CCC[O-].CCC[O-].CCC[O-].CCC[O-].CCC[O-] Chemical compound [V+5].CCC[O-].CCC[O-].CCC[O-].CCC[O-].CCC[O-] LPHBWRJXTUNCAI-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
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- 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
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- 239000000539 dimer Substances 0.000 description 1
- BXJGUBZTZWCMEX-UHFFFAOYSA-N dimethylhydroquinone Natural products CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 description 1
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- 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
- YTQHSQQSLTYMSL-UHFFFAOYSA-N dodecanohydrazide Chemical compound CCCCCCCCCCCC(=O)NN YTQHSQQSLTYMSL-UHFFFAOYSA-N 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
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- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
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- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
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- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical compound NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 description 1
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- VMFUMDXVTKTZQY-UHFFFAOYSA-N naphthalene-1-carbohydrazide Chemical compound C1=CC=C2C(C(=O)NN)=CC=CC2=C1 VMFUMDXVTKTZQY-UHFFFAOYSA-N 0.000 description 1
- ZWLFGLCGZUVIEA-UHFFFAOYSA-N nonanedihydrazide Chemical compound NNC(=O)CCCCCCCC(=O)NN ZWLFGLCGZUVIEA-UHFFFAOYSA-N 0.000 description 1
- HATIEXJZXOLRAO-UHFFFAOYSA-N octanedihydrazide Chemical compound NNC(=O)CCCCCCC(=O)NN HATIEXJZXOLRAO-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 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
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- BDJXVNRFAQSMAA-UHFFFAOYSA-N quinhydrone Chemical compound OC1=CC=C(O)C=C1.O=C1C=CC(=O)C=C1 BDJXVNRFAQSMAA-UHFFFAOYSA-N 0.000 description 1
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- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
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- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 238000004904 shortening Methods 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
- 229940037312 stearamide Drugs 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
本発明は、接着剤、塗料およびコーティング剤等の分野で広く用いられる二液硬化型アクリル系組成物に関する。 The present invention relates to a two-component curable acrylic composition widely used in the fields of adhesives, paints, coating agents and the like.
二液硬化型アクリル系組成物は、（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、アクリルまたはメタクリルを意味するものとする）および有機過酸化物を含有する第一液と、（メタ）アクリル系モノマーおよび有機過酸化物とレドックス触媒系を形成する還元剤を含有する第二液から構成される。この二液硬化型アクリル系組成物は、混合することにより室温において短時間で硬化し、かつ化学量論的な意味での二液の正確な計量混合を必要とせず、取扱いが簡単であるという特徴から、接着剤、塗料およびコーティング剤等の分野で広く用いられている。 The two-part curable acrylic composition comprises a first liquid containing a (meth) acrylic monomer (in the present invention, (meth) acryl means acrylic or methacrylic) and an organic peroxide ( It is comprised from the 2nd liquid containing the reducing agent which forms a redox catalyst system with a (meth) acrylic-type monomer and an organic peroxide. This two-component curable acrylic composition cures in a short time at room temperature by mixing, and does not require accurate metering of the two components in a stoichiometric sense, and is easy to handle. Due to its characteristics, it is widely used in the fields of adhesives, paints and coating agents.
しかしながら、二液硬化型アクリル系組成物は空気中の酸素により硬化阻害を受け、空気に接触した表面、例えば、接着剤として用いた場合には接着箇所からはみ出し空気に接触する表面部分の硬化が不充分で硬化物表面にベタツキが残り、埃が付着したり、他の部品や作業者の衣服を汚したりするなどの問題を有していた。これに対し、特許文献１には、二液硬化型アクリル系接着剤の第二液へバナジウム化合物を配合することにより、はみ出し部分の硬化性が良好となることが記載されている。しかしながら、バナジウム化合物を第二液に配合した二液硬化型アクリル系組成物は表面硬化性が良好となるものの、硬化させると人体に有害なホルムアルデヒドやアセトアルデヒドなどのアルデヒド類を発生させるという問題がある。特に、密閉された空間で使用する物品、例えば車内で使用するスピーカー、カーナビなどに使用される用途には、硬化時にアルデヒド類の発生が少ない二液硬化型アクリル系組成物が求められている。 However, the two-component curable acrylic composition is subject to inhibition of curing by oxygen in the air, and when used as an adhesive, for example, when used as an adhesive, the surface portion that protrudes from the adhesion area and is in contact with air is cured. Insufficient and sticky surface remains on the surface of the cured product, which causes problems such as adhesion of dust and contamination of other parts and workers' clothes. On the other hand, Patent Document 1 describes that the curability of the protruding portion is improved by blending the vanadium compound into the second liquid of the two-component curable acrylic adhesive. However, although the two-part curable acrylic composition containing the vanadium compound in the second part has good surface curability, there is a problem in that aldehydes such as formaldehyde and acetaldehyde that are harmful to the human body are generated when cured. . In particular, a two-part curable acrylic composition that generates less aldehydes at the time of curing is required for articles used in a sealed space, for example, a speaker used in a car, a car navigation system, and the like.
それに対し、特許文献２には、ホルムアルデヒドやアセトアルデヒドの発生量が少ない二液硬化型アクリル系組成物として、第一液に重合開始剤、第二液に３価のバナジウム化合物を含有してなる硬化性組成物が提案されているが、ホルムアルデヒドやアセトアルデヒド等のアルデヒド類の発生を抑えるには不充分である。さらに、特許文献３には、ホルムアルデヒドやアセトアルデヒドの発生量が少ない二液硬化型アクリル系組成物として、第一液にモノマーとしてアルキル（メタ）アクリレート及びヒドロキシアルキル（メタ）アクリレートを含有してなる（メタ）アクリレートおよび有機過酸化物、第二液に前記モノマーおよびチオ尿素誘導体を含有してなる硬化性組成物が提案されている。この硬化性組成物はバナジウム化合物を含有せず、チオ尿素化合物を用いているためアルデヒド類の発生は少なくなっているものの、表面硬化性が悪いという問題がある。また、アルデヒド類と反応性を有する種々の化合物が知られているが、これらの化合物を二液硬化型アクリル系組成物へ適用すると、硬化し難くなる、あるいは保存安定性が悪くなるなどの問題があった。 On the other hand, in Patent Document 2, as a two-component curable acrylic composition with a small amount of formaldehyde and acetaldehyde generated, a first component contains a polymerization initiator and a second component contains a trivalent vanadium compound. However, it is not sufficient to suppress the generation of aldehydes such as formaldehyde and acetaldehyde. Furthermore, in Patent Document 3, as a two-component curable acrylic composition with a small amount of formaldehyde and acetaldehyde, the first solution contains alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate as monomers ( A curable composition comprising a (meth) acrylate and an organic peroxide and the second liquid containing the monomer and a thiourea derivative has been proposed. Although this curable composition does not contain a vanadium compound and uses a thiourea compound, the generation of aldehydes is reduced, but there is a problem that the surface curability is poor. In addition, various compounds having reactivity with aldehydes are known. However, when these compounds are applied to a two-component curable acrylic composition, problems such as difficulty in curing or poor storage stability. was there.
以上のように、アルデヒド類の発生を抑えるためにバナジウム化合物の代わりにチオ尿素化合物を配合した二液硬化型アクリル系組成物は表面硬化性が悪くなり、表面硬化性を向上させる目的でバナジウム化合物を配合した二液硬化型アクリル系組成物は、硬化させるとホルムアルデヒドやアセトアルデヒドなどのアルデヒド類を発生するという問題がある。特に密閉された空間で使用する物品にバナジウム化合物を配合した二液硬化型アクリル系組成物を用いると、硬化物から放散されたアルデヒド類が人体へ悪影響を与えるという問題がある。 As described above, a two-component curable acrylic composition containing a thiourea compound instead of a vanadium compound in order to suppress the generation of aldehydes has a poor surface curability and is intended to improve the surface curability. The two-component curable acrylic composition containing the compound has a problem of generating aldehydes such as formaldehyde and acetaldehyde when cured. In particular, when a two-component curable acrylic composition containing a vanadium compound is used in an article used in a sealed space, there is a problem that aldehydes diffused from the cured product adversely affect the human body.
本発明は、従来の二液硬化型アクリル系組成物と同等の性能を維持しつつ、硬化物から生じるアルデヒド類の放散量を著しく抑えた二液硬化型アクリル系組成物を提供することを課題とする。 It is an object of the present invention to provide a two-component curable acrylic composition in which the performance equivalent to that of a conventional two-component curable acrylic composition is maintained and the amount of aldehydes generated from the cured product is remarkably suppressed. And
すなわち、本発明は、
（１）（メタ）アクリル系モノマーおよび有機過酸化物を含有する第一液と、バナジウム化合物を含有する第二液とから構成される二液硬化型アクリル系組成物において、ヒドラジド化合物または尿素化合物の中から選ばれる少なくとも一つの化合物が、第一液および／または第二液に配合されてなる二液硬化型アクリル系組成物であり、
（２）ヒドラジド化合物が第一液に配合されてなる（１）記載の二液硬化型アクリル系組成物であり、
（３）ヒドラジド化合物が、二塩基酸とヒドラジンとの反応生成物である（１）または（２）記載の二液硬化型アクリル系組成物であり、
（４）尿素化合物が第二液に配合されてなる（１）乃至（３）記載の二液硬化型アクリル系組成物である。
That is, the present invention
(1) In a two-part curable acrylic composition comprising a first liquid containing a (meth) acrylic monomer and an organic peroxide and a second liquid containing a vanadium compound, a hydrazide compound or a urea compound At least one compound selected from among the two-component curable acrylic composition blended with the first solution and / or the second solution,
(2) The two-component curable acrylic composition according to (1), wherein the hydrazide compound is blended in the first solution.
(3) The two-component curable acrylic composition according to (1) or (2), wherein the hydrazide compound is a reaction product of a dibasic acid and hydrazine,
(4) The two-component curable acrylic composition according to any one of (1) to (3), wherein a urea compound is blended in the second solution.
本発明の二液硬化型アクリル系組成物は、硬化させてもホルムアルデヒドやアセトアルデヒド等のアルデヒド類の発生が極めて少なく、表面硬化性や硬化物の特性が良好であるという効果が得られる。 Even if the two-component curable acrylic composition of the present invention is cured, the generation of aldehydes such as formaldehyde and acetaldehyde is extremely small, and the effect that the surface curability and the properties of the cured product are good is obtained.
以下、本発明をより詳細に説明する。
一般に、二液硬化型アクリル系組成物は重合性を有する（メタ）アクリル系モノマーおよび有機過酸化物を含有する第一液と、有機過酸化物とレドックス触媒系を形成する還元剤を含有する第二液とから構成されるもので、二液主剤型とプライマー型に分類される。そして、二液主剤型は有機過酸化物を含有する第一液と還元剤を含有する第二液とから構成され、第一液、第二液とも重合性（メタ）アクリル系モノマーを主成分として含有するものであり、一方、プライマー型は、重合性を有する（メタ）アクリル系モノマーと有機過酸化物とを含有する主剤と呼ばれる第一液と、プライマーと呼ばれる還元剤を含有する第二液とから構成されるものである。本発明の二液硬化型アクリル系組成物は二液主剤型、プライマー型のいずれのタイプであっても差しつかえない。
Hereinafter, the present invention will be described in more detail.
Generally, a two-component curable acrylic composition contains a polymerizable (meth) acrylic monomer and a first solution containing an organic peroxide, and a reducing agent that forms a redox catalyst system with the organic peroxide. It consists of a second liquid and is classified into a two-liquid main agent type and a primer type. The two-component main component type is composed of a first solution containing an organic peroxide and a second solution containing a reducing agent. Both the first and second solutions are mainly composed of a polymerizable (meth) acrylic monomer. On the other hand, the primer type contains a first liquid called a main agent containing a polymerizable (meth) acrylic monomer and an organic peroxide, and a second containing a reducing agent called a primer. It is comprised from a liquid. The two-component curable acrylic composition of the present invention may be either a two-component main agent type or a primer type.
本発明において（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、メトキシエチル（メタ）アクリレート、エトキシエチル（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、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、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（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る。これらは単独或いは２種以上が組み合わされて用いられ、（メタ）アクリル酸のようにカルボキシル基を有する（メタ）アクリル系モノマーや、ヒドロキシアルキル（メタ）アクリレート等の水酸基を有する（メタ）アクリル系モノマーを適宜併用すると、硬化物に良好な機械的強度と接着性を付与できるので好ましい。 In the present invention, (meth) acrylic monomers include (meth) acrylic acid, (meth) acrylic acid alkyl ester, phenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, cyclohexyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, hydroxyalkyl (meth) acrylate, poly (meth) acrylate of polyhydric alcohol, and (meth) acrylic acid added to epoxy resin Epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, di (meth) acrylate of bisphenol A alkylene oxide adduct, and the like obtained by reaction. It is. These are used singly or in combination of two or more, (meth) acrylic monomers having a carboxyl group such as (meth) acrylic acid, and (meth) acrylic having a hydroxyl group such as hydroxyalkyl (meth) acrylate It is preferable to use a monomer in combination, as it can impart good mechanical strength and adhesiveness to the cured product.
本発明の二液硬化型アクリル系組成物には、第一液および／または第二液に酸性リン酸エステルを配合することもでき、酸性リン酸エステルとしては、モノメチルフォスフェート、ジメチルフォスフェート、モノエチルフォスフェート、ジエチルフォスフェート、モノブチルフォスフェート、ジブチルフォスフェート、モノ−β−クロロエチルフォスフェート、ジ−β−クロロエチルフォスフェート、モノエトキシエチルフォスフェート、ジエトキシエチルフォスフェート、フェニルフォスフェート、ジフェニルフォスフェート、モノ（メタ）アクリロイルオキシエチルフォスフェート、ジ（メタ）アクリロイルオキシエチルフォスフェート、モノ（メタ）アクリロイルオキシプロピルフォスフェート、ジ（メタ）アクリロイルオキシプロピルフォスフェート、ポリプロピレングリコールモノ（メタ）アクリレートフォスフェート等が挙げられ、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 two-part curable acrylic composition of the present invention, an acidic phosphate ester can be blended with the first liquid and / or the second liquid. Examples of the acidic phosphate ester include monomethyl phosphate, dimethyl phosphate, Monoethyl phosphate, diethyl phosphate, monobutyl phosphate, dibutyl phosphate, mono-β-chloroethyl phosphate, di-β-chloroethyl phosphate, monoethoxyethyl phosphate, diethoxyethyl phosphate, phenyl phosphate Fate, diphenyl phosphate, mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, mono (meth) acryloyloxypropyl phosphate, di (meth) acryloyloxypropyl A phosphate, a polypropylene glycol mono (meth) acrylate phosphate, etc. are mentioned, These are used individually or in combination of 2 or more types.
酸性リン酸エステルが第一液に配合される場合は、その配合量は保存安定性の観点から、第一液に配合される（メタ）アクリル系モノマー１００重量部に対して０〜５重量部が好ましく、更には、０〜２重量部がより好ましい。酸性リン酸エステルの配合量が５重量部を超えると保存安定性が低下する恐れがある。酸性リン酸エステルが第二液に配合される場合は、第二液に配合される（メタ）アクリル系モノマー１００重量部に対して０．１〜２０重量部が好ましく、更には、０．５〜１０重量部がより好ましい。酸性リン酸エステルの配合量が０．１重量部未満であると保存安定性を向上させる効果がなく、また、逆に２０重量部を超えると保存安定性が低下する恐れがある。 When acidic phosphate ester is blended in the first liquid, the blending amount is 0 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic monomer blended in the first liquid from the viewpoint of storage stability. Is more preferable, and 0 to 2 parts by weight is more preferable. When the compounding amount of the acidic phosphate exceeds 5 parts by weight, the storage stability may be lowered. When acidic phosphate ester is mix | blended with 2nd liquid, 0.1-20 weight part is preferable with respect to 100 weight part of (meth) acrylic-type monomers mix | blended with 2nd liquid, Furthermore, 0.5 More preferred is 10 parts by weight. If the blending amount of the acidic phosphate ester is less than 0.1 parts by weight, there is no effect of improving the storage stability. Conversely, if it exceeds 20 parts by weight, the storage stability may be lowered.
第一液には有機過酸化物が必須で、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−ブチルパーオキシラウレート、ｔ−ブチルパーオキシベンゾエート、ｔ−ブチルパーオキシドデカノエート等のパーオキシエステル類、１，５−ジ−ｔ−ブチルパーオキシ−３，３，５−トリメチルシクロヘキサン等のパーオキシケタール類、アセト酢酸エチルパーオキサイド等のケトンパーオキサイド類、過酸化ベンゾイル等のジアシルパーオキサイド類を挙げることができ、これらを単独、或いは、２種以上組み合わせて用いることができるが、これらのうちハイドロパーオキサイド類が特に好ましい。有機過酸化物の配合量は第一液に配合される（メタ）アクリル系モノマー１００重量部に対して０．５〜１０重量部が好ましく、更には、１〜５重量部がより好ましい。有機過酸化物の配合量が０．５重量部未満であると、硬化速度が低下し好ましくなく、逆に、１０重量部を超えると第一液の保存安定性が悪化し好ましくない。 An organic peroxide is essential for the first liquid, and examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, and diisopropylbenzene hydroperoxide. Peroxyesters such as t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxide decanoate, 1,5-di-t-butylperoxy-3,3,5-trimethyl Examples include peroxyketals such as cyclohexane, ketone peroxides such as ethyl acetoacetate, and diacyl peroxides such as benzoyl peroxide. These can be used alone or in combination of two or more. Of these, hydroperoxa Earth is particularly preferred. 0.5-10 weight part is preferable with respect to 100 weight part of (meth) acrylic-type monomers mix | blended with a 1st liquid, and, as for the compounding quantity of an organic peroxide, 1-5 weight part is more preferable. When the amount of the organic peroxide is less than 0.5 parts by weight, the curing rate is lowered, which is not preferable. Conversely, when the amount exceeds 10 parts by weight, the storage stability of the first liquid is deteriorated, which is not preferable.
さらには、本発明の第一液中には、硬化速度を速くするための硬化促進剤としてα−ヒドロキシカルボニル化合物を配合することができる。α−ヒドロキシカルボニル化合物としては、乳酸、酒石酸、リンゴ酸、グリコール酸、クエン酸等のα−ヒドロキシカルボン酸、乳酸メチル、乳酸エチル、グリコール酸エチル等のα−ヒドロキシカルボン酸エステル、ヒドロキシアセトン、ジヒドロキシアセトン、アセトイン、ベンゾイン等のα−ケトール類、α−ヒドロキシカルボン酸と、エポキシ化合物あるいはオキサゾリン化合物との付加反応物等が挙げられ、これらを単独で、或いは、２種以上組み合わされて配合することもできる。 Furthermore, in the first liquid of the present invention, an α-hydroxycarbonyl compound can be blended as a curing accelerator for increasing the curing rate. Examples of the α-hydroxycarbonyl compound include α-hydroxycarboxylic acid such as lactic acid, tartaric acid, malic acid, glycolic acid and citric acid, α-hydroxycarboxylic acid ester such as methyl lactate, ethyl lactate and ethyl glycolate, hydroxyacetone, dihydroxy Examples include addition reaction products of α-ketols such as acetone, acetoin, benzoin, α-hydroxycarboxylic acid, and epoxy compounds or oxazoline compounds. These may be used alone or in combination of two or more. You can also.
第一液中にα−ヒドロキシカルボニル化合物を配合する場合は、第一液に配合される（メタ）アクリル系モノマー１００重量部に対して０．０１〜１０重量部が好ましく、更には、０．０５〜５重量部がより好ましい。α−ヒドロキシカルボニル化合物の配合量が０．０１重量部未満であると硬化速度の向上効果が少なく、逆に１０重量部を超えても配合量に比例した硬化速度の向上が見られなくなるだけでなく、保存安定性が低下するため好ましくない。 When the α-hydroxycarbonyl compound is blended in the first liquid, the amount is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic monomer blended in the first liquid. 05 to 5 parts by weight is more preferable. When the blending amount of the α-hydroxycarbonyl compound is less than 0.01 parts by weight, the effect of improving the curing rate is small. Conversely, when the blending amount exceeds 10 parts by weight, the improvement of the curing rate proportional to the blending amount is not seen. And storage stability is lowered, which is not preferable.
一方、本発明の二液硬化型アクリル系組成物には還元剤として第二液にバナジウム化合物が配合される。バナジウム化合物は二液硬化型アクリル系組成物を硬化させる際、表面硬化性を向上させるという効果がある反面、アルデヒド類を発生させるという作用も有する。バナジウム化合物としては、３価または４価のバナジウム化合物であり、具体的に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、バナジルナフテネート、バナジウムベンゾイルアセトネート、バナジウムプロポキシド、バナジウムブトキシド、五酸化バナジウム等が挙げられ、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。バナジウム化合物の配合量は、二液主剤型の場合は、第二液中に配合される重合性（メタ）アクリル系モノマー１００重量部に対して０．０５〜７重量部が好ましく、０．１〜５重量部がより好ましく、更には、０．１〜３重量部が好ましい。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速度が遅いため好ましくない。逆に１０重量部を超えると配合量に比例した硬化速度の向上が見られず、保存安定性が低下すると共に、硬化物からのアルデヒド類の放散量が多くなるため好ましくない。 On the other hand, the vanadium compound is mix | blended with the 2nd liquid as a reducing agent in the two-component curable acrylic composition of this invention. Vanadium compounds have the effect of improving surface curability when curing a two-component curable acrylic composition, but also have the effect of generating aldehydes. The vanadium compound is a trivalent or tetravalent vanadium compound, and specifically includes vanadyl acetylacetonate, vanadyl stearate, vanadyl naphthenate, vanadium benzoylacetonate, vanadium propoxide, vanadium butoxide, vanadium pentoxide, and the like. These may be used alone or in combination of two or more. The compounding amount of the vanadium compound is preferably 0.05 to 7 parts by weight with respect to 100 parts by weight of the polymerizable (meth) acrylic monomer blended in the second liquid in the case of the two-pack main agent type. -5 parts by weight is more preferable, and 0.1-3 parts by weight is more preferable. If the amount of the vanadium compound is less than 0.05 parts by weight, the curing rate is low, which is not preferable. On the other hand, when the amount exceeds 10 parts by weight, the curing rate is not improved in proportion to the blending amount, storage stability is lowered, and the amount of aldehydes emitted from the cured product is increased.
また、二液硬化型アクリル系組成物がプライマー型の場合は、第一液中に配合される（メタ）アクリル系モノマー１００重量部に対して０．０５〜５重量部となるように第二液中に配合するのが好ましい。この場合、バナジウム化合物は、有機溶剤や可塑剤または液状の還元剤等に溶解して使用される。 In addition, when the two-component curable acrylic composition is a primer type, the second amount is 0.05 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic monomer blended in the first liquid. It is preferable to mix in the liquid. In this case, the vanadium compound is used after being dissolved in an organic solvent, a plasticizer, a liquid reducing agent, or the like.
これらのバナジウム化合物は、エチレンチオ尿素、ジメチルチオ尿素、トリメチルチオ尿素、テトラメチルチオ尿素、ジフェニルチオ尿素、アセチルチオ尿素、ベンゾイルチオ尿素等のチオ尿素化合物、サッカリン、α，α−ジピリジル、アスコルビン酸、バルビツール酸、塩化ベンジル、ｐ−トルエンスルホニルクロライド、アルデヒドとアミンとの縮合物等の還元剤と併用してもさしつかえない。前記チオ尿素化合物等の還元剤の配合量は第二液中に配合される（メタ）アクリル系モノマー１００重量部に対して０．０５〜５重量部が好ましく、更には、０．１〜３重量部がより好ましい。チオ尿素化合物等の還元剤の配合量が０．０５重量部未満であると硬化速度が遅いため好ましくなく、逆に５重量部を超えても配合量に比例した硬化速度の向上が見られなくなるだけでなく、保存安定性が低下するため好ましくない。なお、二液硬化型アクリル系組成物の硬化物からのアルデヒド類の放散量を抑えるためにバナジウム化合物の配合量を少なくした場合は、硬化時間を短くするためにチオ尿素化合物等の還元剤の配合量を増やすと良い。 These vanadium compounds include ethylenethiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, diphenylthiourea, acetylthiourea, benzoylthiourea, and other thiourea compounds, saccharin, α, α-dipyridyl, ascorbic acid, barbituric acid , Benzyl chloride, p-toluenesulfonyl chloride, and a reducing agent such as a condensate of aldehyde and amine may be used in combination. The blending amount of the reducing agent such as the thiourea compound is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic monomer blended in the second liquid, and further 0.1 to 3 parts. Part by weight is more preferred. If the blending amount of a reducing agent such as a thiourea compound is less than 0.05 parts by weight, the curing rate is slow, which is not preferable. Conversely, if the blending amount exceeds 5 parts by weight, the curing rate is not improved in proportion to the blending amount. In addition, it is not preferable because the storage stability is lowered. If the amount of the vanadium compound is reduced in order to reduce the amount of aldehydes emitted from the cured product of the two-component curable acrylic composition, a reducing agent such as a thiourea compound is used to shorten the curing time. It is better to increase the amount.
また、二液硬化型アクリル系組成物がプライマー型の場合、前記チオ尿素化合物等の還元剤の配合量は、第一液中に配合される（メタ）アクリル系モノマー１００重量部に対して０．０５〜３重量部となるように第二液中に配合するのが好ましい。この場合、チオ尿素化合物等の還元剤は、有機溶剤や可塑剤等に溶解して使用される。 When the two-component curable acrylic composition is a primer type, the amount of the reducing agent such as the thiourea compound is 0 with respect to 100 parts by weight of the (meth) acrylic monomer compounded in the first solution. It is preferable to mix | blend in a 2nd liquid so that it may become 0.05-3 weight part. In this case, a reducing agent such as a thiourea compound is used after being dissolved in an organic solvent or a plasticizer.
第二液には、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−ｓ−ブトキシド等のアルミニウム化合物を配合することもできる。アルミニウム化合物の配合量は第二液中に配合される（メタ）アクリル系モノマー１００重量部に対して０．１〜５重量部が好ましく、特に０．２〜２．０重量部が好ましい。アルミニウム化合物の配合量が０．１重量部未満であると短い硬化時間を長期間維持することが難しくなり、５重量部を超えても配合量に比例した硬化時間の短縮効果が見られないばかりか、第二液の保存安定性の低下をもたらす。二液硬化型アクリル系組成物の硬化物からのアルデヒド類の放散量を抑えるためにバナジウム化合物の配合量を少なくした場合は、硬化時間を短くするためにアルミニウム化合物の配合量を増やすのが好ましい。前記アルミニウム化合物は、酸性リン酸エステルおよび後述する１置換ハイドロキノンまたは２置換ハイドロキノンの中から選ばれるハイドロキノン系化合物を併用することにより、硬化時間が短く、且つ保存安定性が良好で、経時による硬化時間の変化もほとんどない二液硬化型アクリル系組成物が得られる。 In the second liquid, an aluminum compound such as aluminum tris (acetylacetonate), aluminum tris (ethyl acetoacetate), ethyl acetoacetate aluminum diisopropylate, aluminum isopropoxide, aluminum-s-butoxide can be blended. . 0.1-5 weight part is preferable with respect to 100 weight part of (meth) acrylic-type monomers mix | blended with a 2nd liquid, and, as for the compounding quantity of an aluminum compound, 0.2-2.0 weight part is especially preferable. If the blending amount of the aluminum compound is less than 0.1 parts by weight, it is difficult to maintain a short curing time for a long period of time, and even if it exceeds 5 parts by weight, the effect of shortening the curing time proportional to the blending amount is not seen. Or, the storage stability of the second liquid is lowered. When the compounding amount of the vanadium compound is reduced in order to suppress the emission amount of aldehydes from the cured product of the two-component curable acrylic composition, it is preferable to increase the compounding amount of the aluminum compound in order to shorten the curing time. . The aluminum compound is used in combination with an acidic phosphate ester and a hydroquinone compound selected from mono-substituted hydroquinone or di-substituted hydroquinone, which will be described later. A two-component curable acrylic composition with almost no change in the thickness is obtained.
本発明の二液硬化型アクリル系性組成物には、室温での長期保存安定性の向上を目的に安定剤として、第一液および／または第二液に２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，２−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、１，４−ベンゾキノン、１，４−ナフトキノン、ハイドロキノン、メチルハイドロキノン、ジメチルハイドロキノン、メトキシハイドロキノン、２，５−ジ−ｔ−ブチルハイドロキノン、キンヒドロン、エチレンジアミン四酢酸四ナトリウム、シュウ酸、Ｎ−メチル−Ｎ−ニトロソアニリン、Ｎ−ニトロソジフェニルアミン等の安定剤を適宜選択して用いることができ、これらを単独で、或いは、２種以上組み合わされて配合することができる。 The two-component curable acrylic composition of the present invention contains 2,6-di-t-butyl as a stabilizer for the purpose of improving long-term storage stability at room temperature. -4-methylphenol, 2,2-methylenebis (4-methyl-6-tert-butylphenol), 1,4-benzoquinone, 1,4-naphthoquinone, hydroquinone, methylhydroquinone, dimethylhydroquinone, methoxyhydroquinone, 2,5- Stabilizers such as di-t-butylhydroquinone, quinhydrone, tetrasodium ethylenediaminetetraacetate, oxalic acid, N-methyl-N-nitrosoaniline, N-nitrosodiphenylamine can be appropriately selected and used. Or it can mix | blend combining 2 or more types.
上記の安定剤は、第一液および／または第二液に配合される（メタ）アクリル系モノマー１００重量部に対して０．１〜５重量部が好ましく、更には、０．２〜１重量部がより好ましい。安定剤の配合量が０．１重量部未満であると保存安定性が低下し、逆に５重量部を超えると組成物の硬化時間が長くなるので好ましくない。なお、第二液の安定剤として１置換ハイドロキノンや２置換ハイドロキノンを用いると、保存安定性を維持しつつ硬化時間を短縮することができるので特に好ましい。 The stabilizer is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic monomer blended in the first liquid and / or the second liquid. Part is more preferred. When the blending amount of the stabilizer is less than 0.1 parts by weight, the storage stability is lowered. On the other hand, when it exceeds 5 parts by weight, the curing time of the composition becomes long. In addition, it is particularly preferable to use 1-substituted hydroquinone or 2-substituted hydroquinone as the stabilizer of the second liquid because the curing time can be shortened while maintaining the storage stability.
本発明の二液硬化型アクリル系組成物には、硬化物からのアルデヒド類の放散量を抑える目的で、ヒドラジド化合物または尿素化合物の中から選ばれる少なくとも一つの化合物が、第一液および／または第二液に配合される。ヒドラジン化合物と尿素化合物は、共に−ＮＨ２構造を有しており、ヒドラジン化合物および尿素化合物の当該構造部分がアルデヒド類と反応性を示すため、アルデヒド類の放散を抑える効果を有する。その際、ヒドラジド化合物が配合される場合は第一液に、尿素化合物が配合される場合は第二液に配合するのが好ましい。 In the two-component curable acrylic composition of the present invention, at least one compound selected from a hydrazide compound and a urea compound is contained in the first solution and / or the compound for the purpose of suppressing the amount of aldehydes emitted from the cured product. It is blended in the second liquid. Both the hydrazine compound and the urea compound have an —NH 2 structure, and the structural portion of the hydrazine compound and the urea compound is reactive with aldehydes, and thus has an effect of suppressing the emission of aldehydes. In that case, when a hydrazide compound is mix | blended, it is preferable to mix | blend with a 1st liquid, and when a urea compound is mix | blended, it mix | blends with a 2nd liquid.
ヒドラジド化合物としては、モノヒドラジド化合物、ジヒドラジド化合物、ポリヒドラジド化合物等が挙げられる。
具体的には、モノヒドラジド化合物として、一般式
Ｒ−ＣＯ−ＮＨＮＨ２ （１）
（式中、Ｒは水素原子、炭素数１〜１２の直鎖状または分岐状のアルキル基、フェニル基、ビフェニル基、ナフチル基等のアリール基または置換基を有するアリール基を示す。）で表される化合物を挙げることができる。
Examples of the hydrazide compound include a monohydrazide compound, a dihydrazide compound, and a polyhydrazide compound.
Specifically, as the monohydrazide compound, the general formula R—CO—NHNH 2 (1)
(Wherein R represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group such as a phenyl group, a biphenyl group, or a naphthyl group, or an aryl group having a substituent). Can be mentioned.
上記一般式（１）のヒドラジド化合物としては、ラウリル酸ヒドラジド、サリチル酸ヒドラジド、ホルムヒドラジド、アセトヒドラジド、プロピオン酸ヒドラジド、ｐ−ヒドロキシ安息香酸ヒドラジド、ナフトエ酸ヒドラジド、３−ヒドロキシ−２−ナフトエ酸ヒドラジド等を例示できる。 Examples of the hydrazide compound of the general formula (1) include lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide and the like. Can be illustrated.
ジヒドラジド化合物としては、一般式
Ｈ２ＮＨＮ−Ｘ−ＮＨＮＨ２ （２）
（式中Ｘは基−ＣＯ−又は基−ＣＯ−Ａ−ＣＯ−を示す。Ａは炭素数１〜１２の直鎖状または分岐状アルキレン基、置換基を有するアルキレン基、フェニル基、ビフェニル基、ナフチル基等のアリーレン基または置換基を有するアリーレン基を示す。）で表わされる化合物を挙げることができる。
The dihydrazide compound of the general formula H 2 NHN-X-NHNH 2 (2)
(In the formula, X represents a group -CO- or a group -CO-A-CO-. A represents a linear or branched alkylene group having 1 to 12 carbon atoms, an alkylene group having a substituent, a phenyl group, or a biphenyl group. , An arylene group such as a naphthyl group or an arylene group having a substituent).
上記一般式（２）のジヒドラジド化合物としては、具体的には、例えば、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、スベリン酸ジヒドラジド、アゼライン酸ジヒドラジド、セバシン酸ジヒドラジド、ドデカン−２酸ジヒドラジド、マレイン酸ジヒドラジド、フマル酸ジヒドラジド、ジグリコール酸ジヒドラジド、酒石酸ジヒドラジド、リンゴ酸ジヒドラジド、イソフタル酸ジヒドラジド、テレフタル酸ジヒドラジド、ダイマー酸ジヒドラジド、２，６−ナフトエ酸ジヒドラジド等の各種２塩基酸ジヒドラジド化合物が挙げられる。更に、２，４−ジヒドラジノ−６−メチルアミノ−ｓｙｍ−トリアジン等も本発明のジヒドラジドとして用いることができる。 Specific examples of the dihydrazide compound represented by the general formula (2) include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, and dodecane-2. Dibasic acid dihydrazides such as acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide, 2,6-naphthoic acid dihydrazide Is mentioned. Furthermore, 2,4-dihydrazino-6-methylamino-sym-triazine and the like can also be used as the dihydrazide of the present invention.
さらに、ポリヒドラジド化合物は、具体的には、ポリアクリル酸ヒドラジド等を例示できる。これらの中でも、ジヒドラジド化合物が好ましく、ジヒドラジド化合物は二液硬化型アクリル系組成物が硬化反応過程で発生するアルデヒド類を効率よく捕捉し、硬化物からのアルデヒド類の放散量を著しく低減させる。 Further, specific examples of the polyhydrazide compound include polyacrylic hydrazide. Among these, a dihydrazide compound is preferable, and the dihydrazide compound efficiently captures aldehydes generated in the curing reaction process by the two-part curable acrylic composition, and significantly reduces the amount of aldehydes emitted from the cured product.
前記のヒドラジド化合物は、二液硬化型アクリル系組成物の第二液へ配合すると第二液の保存安定性が悪くなる恐れがあるが、第一液へ配合した場合は二液硬化型アクリル系組成物の硬化特性および第一液の保存安定性等を阻害しない。したがって、ヒドラジド化合物は第一液に配合するのが好ましい。第一液中に配合されるヒドラジド化合物の配合量は、（メタ）アクリル系モノマー１００重量部に対して０．５〜５重量部が好ましい。ヒドラジド化合物の配合量が０．５重量部未満であると硬化物より発生するアルデヒド類の量を低減させる効果が少なく、逆に５重量部を超えると硬化物の表面硬化性が悪くなるので好ましくない。 When the hydrazide compound is blended into the second liquid of the two-part curable acrylic composition, the storage stability of the second liquid may deteriorate, but when blended into the first liquid, the two-part curable acrylic It does not hinder the curing characteristics of the composition and the storage stability of the first liquid. Therefore, it is preferable to mix the hydrazide compound in the first liquid. As for the compounding quantity of the hydrazide compound mix | blended in a 1st liquid, 0.5-5 weight part is preferable with respect to 100 weight part of (meth) acrylic-type monomers. If the blending amount of the hydrazide compound is less than 0.5 parts by weight, the effect of reducing the amount of aldehydes generated from the cured product is small. Conversely, if it exceeds 5 parts by weight, the surface curability of the cured product is deteriorated. Absent.
硬化物からのアルデヒド類の放散量を抑えるために本発明の二液硬化型アクリル系組成物に配合される尿素化合物としては、尿素、メチル尿素、ジメチル尿素、エチレン尿素、ジエチル尿素、アセチル尿素などを挙げることができる。尿素化合物は、二液硬化型アクリル系組成物の第一液へ配合すると尿素化合物が第一液中に配合した有機過酸化物と反応する可能性があるため、第一液の保存安定性が悪くなる恐れがあるが、第二液へ配合した場合は二液硬化型アクリル系組成物の硬化特性および第二液の保存安定性等を阻害しない。したがって、尿素化合物は第二液に配合するのが好ましい。第二液に配合される尿素化合物の配合量は、（メタ）アクリル系モノマー１００重量部に対して０．５〜５重量部が好ましい。尿素化合物の配合量が０．５重量部未満であると硬化物から発生するアルデヒド類の量を低減させる効果が少なく、逆に５重量部を超えると硬化物の表面硬化性が悪くなるので好ましくない。 Urea compounds blended in the two-part curable acrylic composition of the present invention in order to suppress the amount of aldehydes emitted from the cured product include urea, methylurea, dimethylurea, ethyleneurea, diethylurea, acetylurea, etc. Can be mentioned. When urea compounds are blended into the first liquid of the two-component curable acrylic composition, the urea compound may react with the organic peroxide blended in the first liquid, so the storage stability of the first liquid is improved. Although it may deteriorate, when it is blended in the second liquid, it does not hinder the curing characteristics of the two-part curable acrylic composition, the storage stability of the second liquid, and the like. Therefore, it is preferable to mix the urea compound in the second liquid. The blending amount of the urea compound blended in the second liquid is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic monomer. If the blending amount of the urea compound is less than 0.5 parts by weight, the effect of reducing the amount of aldehydes generated from the cured product is small. Conversely, if it exceeds 5 parts by weight, the surface curability of the cured product is deteriorated, which is preferable. Absent.
本発明においては、その他に、第一液中および／または第二液中に、改質剤として、粘度調整および硬化物の柔軟性を向上させることを目的に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、アクリロニトリル−ブタジエン−スチレン共重合体、メタクリル酸エステル−ブタジエン−スチレン共重合体、メタクリル酸エステル−ブタジエン−アクリロニトリル−スチレン共重合体等の熱可塑性樹脂、スチレン−ブタジエンゴム、ポリブタジエンゴム、ポリイソプレンゴム、クロロプレンゴム、ニトリルゴム、塩化ゴム、アクリルゴム、エピクロルヒドリンゴム等のゴム、液状ポリブタジエン、末端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を配合することができる。また、揺変性の付与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を配合することができる。さらに、空気接触面の硬化性を改良するためのパラフィン、蜜ロウ等および着色のための染料や顔料を配合することができる。 In the present invention, in addition, polymethyl methacrylate, polyvinyl butyral, acrylonitrile-, as a modifier in the first liquid and / or the second liquid, for the purpose of adjusting the viscosity and improving the flexibility of the cured product. Styrene copolymer, acrylonitrile-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene copolymer, thermoplastic resin such as methacrylic ester-butadiene-acrylonitrile-styrene copolymer, styrene-butadiene rubber, polybutadiene rubber , Rubber such as polyisoprene rubber, chloroprene rubber, nitrile rubber, chlorinated rubber, acrylic rubber, epichlorohydrin rubber, liquid rubber such as liquid polybutadiene, terminal acrylic modified liquid polybutadiene, liquid acrylonitrile-butadiene copolymer Rukoto can. For the purpose of imparting thixotropy, thixotropic agents such as finely powdered polyethylene, dibenzylidene-D-sorbitol, cellulose triacetate, stearamide, bentonite, and finely powdered silicic acid can be blended. Furthermore, paraffin, beeswax and the like for improving the curability of the air contact surface, and dyes and pigments for coloring can be blended.
本発明の二液硬化型アクリル系組成物をプライマー型とする場合に用いられる溶剤としては、バナジウム化合物やチオ尿素化合物等の還元剤を溶解し、揮発性を有するものが用いられる。これらの溶剤としては、具体的には、トルエン、キシレン、酢酸エチル、プロピオン酸エチル、アセトン、メチルエチルケトン、メチルブチルケトン、メタノール、エタノール、イソプロピルアルコール等を挙げることができる。 As the solvent used when the two-component curable acrylic composition of the present invention is used as a primer type, a solvent that dissolves a reducing agent such as a vanadium compound or a thiourea compound and has volatility is used. Specific examples of these solvents include toluene, xylene, ethyl acetate, ethyl propionate, acetone, methyl ethyl ketone, methyl butyl ketone, methanol, ethanol, isopropyl alcohol, and the like.
以下に、本発明を実施例により更に詳細に説明する。なお、これらの例において、添加量の部は、重量部を表す。また、以下の実施例および比較例のアルデヒド類の放散量、可使時間、表面硬化開始時間、引張剪断強度の測定は次の方法で行った。 Hereinafter, the present invention will be described in more detail with reference to examples. In these examples, the added amount part represents part by weight. Further, the following methods were used to measure the aldehyde emission amount, pot life, surface hardening start time, and tensile shear strength of the following Examples and Comparative Examples.
（１）アルデヒド類の放散量
ポリエチレン製のチャック袋に二液硬化型アクリル系組成物の硬化物（１ｍｍ×１００ｍｍ×１００ｍｍ）を入れ、窒素ガスを２Ｌ充填し、チャック袋ごと６５℃のオーブン中に２時間放置した。その後、チャック袋をオーブンから取り出して２３℃まで冷却し、チャック袋中のホルムアルデヒドを北川式ガス検知管171SC（光明理化学工業株式会社製）にて測定し、アセトアルデヒドを気体検知管No.92L（株式会社ガステック製）にて測定した。
(1) Dissipation amount of aldehydes A cured product (1 mm × 100 mm × 100 mm) of a two-component curable acrylic composition is placed in a polyethylene chuck bag, filled with 2 L of nitrogen gas, and the entire chuck bag is in an oven at 65 ° C. For 2 hours. Thereafter, the chuck bag is taken out of the oven and cooled to 23 ° C., formaldehyde in the chuck bag is measured with a Kitagawa type gas detector tube 171SC (manufactured by Komyo Chemical Co., Ltd.), and acetaldehyde is detected with a gas detector tube No. 92L (stock) (Measured by Gastech).
（２）可使時間
第一液０．５ｇ、第二液０．５ｇを２３℃で１０秒間混合し、混合後に粘度上昇が始まるまでの時間を測定した。
(2) Pot life Time 0.5 g of the first liquid and 0.5 g of the second liquid were mixed at 23 ° C. for 10 seconds, and the time until the viscosity increase after mixing was measured.
（３）表面硬化開始時間
第一液０．１ｇ、第二液０．１ｇを２３℃で１０秒間混合し、混合物の表面にパラフィンが浮き出し、タック性が少なくなるまでの時間を測定した。
(3) Surface curing start time 0.1 g of the first liquid and 0.1 g of the second liquid were mixed at 23 ° C. for 10 seconds, and the time until the paraffin emerged on the surface of the mixture and the tackiness decreased was measured.
（４）引張剪断強度
２３℃の雰囲気中で、長さ１００ｍｍ×幅２５ｍｍ×厚さ１．６ｍｍの冷間圧延鋼板の一方に第一液、第二液を等量塗布し、その後、もう一方の冷間圧延鋼鈑を１２ｍｍのラップで擦り合わせるようにして貼り合わせて固定し、２４時間後に２３℃雰囲気中でＡＳＴＭ Ｄ １００２−６４に準拠して引張剪断強度を測定した。
(4) Tensile shear strength In an atmosphere of 23 ° C., an equal amount of the first liquid and the second liquid are applied to one side of a cold rolled steel sheet having a length of 100 mm × width of 25 mm × thickness of 1.6 mm, and then the other side The cold-rolled steel plates were bonded and fixed so as to be rubbed with a 12 mm lap, and after 24 hours, the tensile shear strength was measured in a 23 ° C. atmosphere in accordance with ASTM D 1002-64.
［実施例１〜５］
表１に示した二液硬化型アクリル系組成物の第一液へヒドラジド化合物を配合・調製し、調製した各組成物について、アルデヒド類の放散量、可使時間、表面硬化開始時間および冷間圧延鋼鈑を接着した際の引張剪断強度を測定した。測定結果を表１に示す。
[Examples 1 to 5]
A hydrazide compound was blended and prepared in the first liquid of the two-part curable acrylic composition shown in Table 1, and the aldehyde emission amount, pot life, surface hardening start time, and cold for each prepared composition The tensile shear strength when the rolled steel sheet was bonded was measured. The measurement results are shown in Table 1.
［実施例６］
表１に示した二液硬化型アクリル系組成物の第二液へ尿素化合物を配合・調製し、調製した組成物について、アルデヒド類の放散量、可使時間、表面硬化開始時間および冷間圧延鋼鈑を接着した際の引張剪断強度を測定した。測定結果を表１に併せて示す。
[Example 6]
A urea compound is blended and prepared in the second liquid of the two-part curable acrylic composition shown in Table 1, and the aldehyde emission amount, pot life, surface hardening start time, and cold rolling are prepared for the prepared composition. The tensile shear strength when the steel sheet was bonded was measured. The measurement results are also shown in Table 1.
［比較例１〜５］
表１に示した二液硬化型アクリル系組成物（ヒドラジド化合物及び尿素化合物を配合しない組成物）を調製し、調製した組成物について、アルデヒド類の放散量、可使時間、表面硬化開始温度および冷間圧延鋼鈑を接着した際の引張剪断強度を測定した。測定結果を表１に併せて示す。
[Comparative Examples 1-5]
A two-component curable acrylic composition (a composition not containing a hydrazide compound and a urea compound) shown in Table 1 was prepared, and for the prepared composition, the aldehyde emission amount, pot life, surface curing start temperature, and The tensile shear strength when the cold rolled steel sheet was bonded was measured. The measurement results are also shown in Table 1.
表１より明らかなように、バナジウム化合物の配合量が０．７５重量部である実施例１と比較例１とを比較すると、ヒドラジド化合物を配合する実施例１はホルムアルデヒドおよびアセトアルデヒドのアルデヒド類の放散量がともに比較例１の１／２以下と大幅に減少し、ヒドラジド化合物を配合した効果が見られた。また、バナジウム化合物の配合量が０．２重量部である実施例２乃至６と比較例２乃至４とを比較しても、ヒドラジド化合物または尿素化合物を配合する実施例２乃至６はホルムアルデヒド放散量が２／３〜１／８、アセトアルデヒド放散量が１／２〜１／８と大幅に減少し、ヒドラジド化合物および尿素化合物を配合した効果が見られた。そして、ヒドラジド化合物および尿素化合物を配合したことによる表面硬化性および接着性への悪影響もほとんど見られず、二液硬化型アクリル系組成物としての優れた性能を維持していた。尚、実施例１乃至６はバナジウム化合物の代わりにチオ尿素化合物を配合した比較例５よりも表面硬化性が良い結果となった。 As is clear from Table 1, when Example 1 in which the compounding amount of the vanadium compound is 0.75 parts by weight is compared with Comparative Example 1, Example 1 in which the hydrazide compound is compounded is emission of aldehydes of formaldehyde and acetaldehyde. Both amounts were significantly reduced to 1/2 or less of Comparative Example 1, and the effect of blending the hydrazide compound was observed. Further, even when Examples 2 to 6 in which the compounding amount of the vanadium compound is 0.2 parts by weight and Comparative Examples 2 to 4 are compared, Examples 2 to 6 in which the hydrazide compound or the urea compound is compounded are in the formaldehyde emission amount. Was reduced to 2/3 to 1/8 and the acetaldehyde emission amount was reduced to 1/2 to 1/8, and the effect of blending the hydrazide compound and the urea compound was observed. And the bad influence on surface curability and adhesiveness by mix | blending a hydrazide compound and a urea compound was hardly seen, but the outstanding performance as a two-component curable acrylic composition was maintained. In addition, Example 1 thru | or 6 brought the result whose surface curability was better than the comparative example 5 which mix | blended the thiourea compound instead of the vanadium compound.
本発明の二液硬化型アクリル系組成物は、従来の二液硬化型アクリル系組成物と同様な表面硬化性および他の材料との接着強度が大きいばかりでなく、硬化物からのアルデヒド放散量が著しく少ないため、接着剤、塗料およびコーティング剤等の分野に広く用いることができる。
The two-component curable acrylic composition of the present invention not only has the same surface curability and adhesion strength to other materials as the conventional two-component curable acrylic composition, but also the amount of aldehyde emitted from the cured product. Can be widely used in fields such as adhesives, paints and coating agents.
Claims (4)
The two-component curable acrylic composition according to any one of claims 1 to 3, wherein the urea compound is blended in the second solution.
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| JPS60179407A (en) * | 1984-02-27 | 1985-09-13 | Okura Ind Co Ltd | Cure accelerator solution |
| JPS6134082A (en) * | 1984-07-26 | 1986-02-18 | Okura Ind Co Ltd | Lowly odorous two-pack acrylic adhesive having excellent adhesion |
| JP2005146205A (en) * | 2003-11-19 | 2005-06-09 | Dainippon Ink & Chem Inc | Covering material, covering material for civil engineering and construction industry and paint for wood working |
| JP2006188627A (en) * | 2005-01-07 | 2006-07-20 | Okura Ind Co Ltd | Agent b for two part main agent type acrylic adhesive |
| JP2008024819A (en) * | 2006-07-21 | 2008-02-07 | Okura Ind Co Ltd | Two pack type acrylic adhesive for inorganic material for civil engineering/construction |
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| JPS60179407A (en) * | 1984-02-27 | 1985-09-13 | Okura Ind Co Ltd | Cure accelerator solution |
| JPS6134082A (en) * | 1984-07-26 | 1986-02-18 | Okura Ind Co Ltd | Lowly odorous two-pack acrylic adhesive having excellent adhesion |
| JP2005146205A (en) * | 2003-11-19 | 2005-06-09 | Dainippon Ink & Chem Inc | Covering material, covering material for civil engineering and construction industry and paint for wood working |
| JP2006188627A (en) * | 2005-01-07 | 2006-07-20 | Okura Ind Co Ltd | Agent b for two part main agent type acrylic adhesive |
| JP2008024819A (en) * | 2006-07-21 | 2008-02-07 | Okura Ind Co Ltd | Two pack type acrylic adhesive for inorganic material for civil engineering/construction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015218200A (en) * | 2014-05-14 | 2015-12-07 | 電気化学工業株式会社 | Composition |
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