JPS63108048A - Curable composition and curing method - Google Patents
Curable composition and curing methodInfo
- Publication number
- JPS63108048A JPS63108048A JP62119835A JP11983587A JPS63108048A JP S63108048 A JPS63108048 A JP S63108048A JP 62119835 A JP62119835 A JP 62119835A JP 11983587 A JP11983587 A JP 11983587A JP S63108048 A JPS63108048 A JP S63108048A
- Authority
- JP
- Japan
- Prior art keywords
- group
- monomer
- weight
- aluminum
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims description 49
- 238000001723 curing Methods 0.000 title claims description 23
- 239000000178 monomer Substances 0.000 claims abstract description 61
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 39
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 19
- 125000000466 oxiranyl group Chemical group 0.000 claims abstract description 18
- 239000013522 chelant Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 8
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- -1 acrylic ester Chemical class 0.000 abstract description 26
- 239000007983 Tris buffer Substances 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000704 physical effect Effects 0.000 abstract description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 229920006163 vinyl copolymer Polymers 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 125000005372 silanol group Chemical group 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- 150000007513 acids Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- DWZBSOVYCROKJR-UHFFFAOYSA-N 4-(2-methylphenyl)butan-1-ol Chemical compound CC1=CC=CC=C1CCCCO DWZBSOVYCROKJR-UHFFFAOYSA-N 0.000 description 2
- GAKWESOCALHOKH-UHFFFAOYSA-N 4-methoxybutyl prop-2-enoate Chemical compound COCCCCOC(=O)C=C GAKWESOCALHOKH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- RLXFIMBFXGDTGQ-UHFFFAOYSA-N 4-[dimethoxy(phenyl)silyl]butyl prop-2-enoate Chemical compound C=CC(=O)OCCCC[Si](OC)(OC)C1=CC=CC=C1 RLXFIMBFXGDTGQ-UHFFFAOYSA-N 0.000 description 1
- VXASQTMYWZHWMX-UHFFFAOYSA-N 4-ethoxybutyl 2-methylprop-2-enoate Chemical compound CCOCCCCOC(=O)C(C)=C VXASQTMYWZHWMX-UHFFFAOYSA-N 0.000 description 1
- OYFJWLSZXKXLAT-UHFFFAOYSA-N 4-ethoxybutyl prop-2-enoate Chemical compound CCOCCCCOC(=O)C=C OYFJWLSZXKXLAT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WVXZWORMZBXJQT-UHFFFAOYSA-N C(C=C)(=O)OCCC[SiH](OC)CC1=CC=CC=C1 Chemical compound C(C=C)(=O)OCCC[SiH](OC)CC1=CC=CC=C1 WVXZWORMZBXJQT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 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
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 241000750042 Vini Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-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
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- RDASHQZXQNLNMG-UHFFFAOYSA-N butan-2-olate;di(propan-2-yloxy)alumanylium Chemical compound CCC(C)O[Al](OC(C)C)OC(C)C RDASHQZXQNLNMG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- BKXVGDZNDSIUAI-UHFFFAOYSA-N methoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC)C1=CC=CC=C1 BKXVGDZNDSIUAI-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、新規な硬化性組成物及び硬化方法に関する。[Detailed description of the invention] Industrial applications The present invention relates to novel curable compositions and curing methods.
従来の技術及びその問題点
従来、常温乃至１００°Ｃの比較的低い温度で架橋硬化
できる組成物としてアルコキシシラン含有ビニル重合体
に、酸、塩基、有機金属触媒等を添加したものが公知で
ある。例えば、特開昭６０＝６７５５３号にはメタクリ
ロキシプロピルトリメトキシシラン等のアルコキシシラ
ンを含有するビニル重合体にアルミニウムキレート化合
物を配合した組成物が開示されている。BACKGROUND TECHNOLOGIES AND THEIR PROBLEMS Conventionally, compositions in which acids, bases, organometallic catalysts, etc. are added to alkoxysilane-containing vinyl polymers have been known as compositions that can be crosslinked and cured at relatively low temperatures of room temperature to 100°C. . For example, JP-A-60-67553 discloses a composition in which an aluminum chelate compound is blended with a vinyl polymer containing an alkoxysilane such as methacryloxypropyltrimethoxysilane.
しかしながら、上記従来の組成物には、アルコキシシラ
ンが加水分解して生じるシラノール基のみが架橋官能基
であるため硬化には多量の水を要すること、従ってこの
加水分解時にアルコール等の副生物が多量に生ずるため
硬化物の物性が低下すること、又空気中の水分のみで層
化させる場合空気と接触する表面のみが硬化して内部が
殆んど硬化しないため表面と内部との硬化の差により硬
化物にチヂミを生じ易いこと等の欠点があった。However, in the conventional compositions described above, since the silanol group produced by hydrolysis of alkoxysilane is the only crosslinking functional group, a large amount of water is required for curing, and therefore a large amount of by-products such as alcohol are produced during this hydrolysis. The physical properties of the cured product deteriorate due to the difference in hardening between the surface and the inside because only the surface that comes in contact with the air is hardened and the inside is hardly hardened when stratifying with only moisture in the air. There were drawbacks such as the tendency for stiffness to occur in the cured product.
問題点を解決するための手段
本発明の目的は、少量の水で充分に硬化する新規な硬化
性組成物及び硬化方法を提供することにある。Means for Solving the Problems An object of the present invention is to provide a novel curable composition and a curing method that can be sufficiently cured with a small amount of water.
本発明の他の目的は、硬化物の物性に優れた新−３＝ 規硬化性組成物及び硬化方法を提供することにある。Another object of the present invention is to provide a cured product with excellent physical properties. An object of the present invention is to provide a hardenable composition and a hardening method.
本発明の他の目的は、空気中の水分のみで硬化させる場
合に表面と内部の硬化の差が少なくチヂミを生じない新
規硬化性組成物及び硬化方法を提供することにある。Another object of the present invention is to provide a new curable composition and a curing method that have a small difference in curing between the surface and the inside and do not cause sagging when cured using only moisture in the air.
本発明のこれら及び更に他の目的は、以下の記載により
明らかにされるであろう。These and further objects of the invention will become clear from the description below.
本発明は、一般式
Ｒ４は水素原子又はメチル基を、Ｒ２は炭素数１〜６の
２価の脂肪族飽和炭化水素基を、Ｒ３及びＲ４は同−又
は異なってフェニル基、炭素数１〜６のアルキル基又は
炭素数１〜６＝ ４ −
のアルコキシ基を Ｒ５は炭素数１〜６のアルキル基を
それぞれ示す。ｎは１〜１００の整数を示す。〕
で表わされる化合物であるアルコキシシラン基含有ビニ
ル単量体とオキシラン基含有ビニル単量体とを単量体成
分として含有してなる共重合体に、架橋反応硬化剤とし
てアルミニウムキレート化合物を配合してなることを特
徴とする硬化性組成物並びに当該組成物を、水分の存在
下に１００℃以下で架橋させることを特徴とする硬化方
法に係る。In the present invention, the general formula R4 is a hydrogen atom or a methyl group, R2 is a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R3 and R4 are the same or different, and are a phenyl group, R5 represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. n represents an integer of 1 to 100. ] An aluminum chelate compound is blended as a crosslinking reaction curing agent into a copolymer containing as monomer components an alkoxysilane group-containing vinyl monomer and an oxirane group-containing vinyl monomer, which is a compound represented by The present invention relates to a curable composition characterized by comprising: and a curing method characterized by crosslinking the composition at 100° C. or lower in the presence of moisture.
本発明者は、前記公報記載の従来の硬化性組成物の諸欠
点を解消するべく鋭意研究しプこ結果、次の様な新たな
事実を見出した。The inventor of the present invention conducted extensive research in order to eliminate the various drawbacks of the conventional curable compositions described in the above-mentioned publication, and as a result, discovered the following new facts.
（１）アルコキシシラン基を含有するビニル重合体に更
にオキシラン基を含有せしめることにより、シラノール
基のみならず該オキシラン基も架橋官能基となるため少
量の水分の存在下で充分に硬化する。(1) By further incorporating an oxirane group into a vinyl polymer containing an alkoxysilane group, not only the silanol group but also the oxirane group becomes a crosslinking functional group, so that it is sufficiently cured in the presence of a small amount of water.
（２）従って、硬化時のアルコール等の副生物が極く少
量であるため硬化物の物性の低下が殆んどなく、得られ
る硬化物の物性が優れている。(2) Therefore, since the amount of by-products such as alcohol during curing is extremely small, there is almost no deterioration in the physical properties of the cured product, and the physical properties of the resulting cured product are excellent.
（３） 空気中の水分のみで硬化させる場合、空気と
接触する表面のシラノール基による架橋硬化に伴ないオ
キシラン基による架橋硬化が連鎖的に内部にまで起こる
ため、表面と内部の硬化の差が少なくチヂミを生じない
。(3) When curing with only moisture in the air, crosslinking and curing by silanol groups on the surface in contact with the air and crosslinking and curing by oxirane groups occur in a chain reaction to the inside, so there is a difference in hardening between the surface and the inside. It does not cause stiffness.
前記本発明は、かかる新たな諸知見に基づいて完成され
たものである。The present invention has been completed based on these new findings.
一般式（Ｉ）において、ｎは好ましくは１〜１０の整数
である。In general formula (I), n is preferably an integer of 1 to 10.
一般式（１）において、Ｒ２によって示される炭素数１
〜６の２価の脂肪族飽和炭化水素基としては、直鎖又は
分枝状のアルキレン基例えばメチレン、エチレン、プロ
ピレン、テトラメチレン、エチルエチレン、ペンタメチ
レン、ヘキサメチレン基等を挙げることができる。Ｒ３
、Ｒ４及びＲ５で示される炭素数１〜６のアルキル基と
しては、直鎖又は分枝状のアルキル基例えばメチル、エ
チル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソ
ブチル、５ｅｃ−ブチル、ｔｅｒｔ−ブチル、ｎ−ペン
チル、イソペンチル、ネオペンチル、ｎ−ヘキシル、イ
ソヘキシル基等を挙げることができる。Ｒ３及びＲ４で
表わされる炭素数１〜６のアルコキシ基としては、直鎖
又は分枝状のアルコキシ基例えばメトキシ、エトキシ、
ｎ−プロポキシ、イソプロポキシ、η−ブトキシ、イン
ブトキシ、５ｅｃ−ブトキシ、ｔｅｒｔ−ブトキシ、ｎ
−ペントキシ、イソペントキシ、ｎ−へキシルオキシ、
イソへキシルオキシ基等を挙げることができる。また、
一般式（１）において、ｎが２以上のとき、Ｒ３同志及
びＲ４同志は、同じで７あっても異なっていても良い。In the general formula (1), the number of carbon atoms represented by R2 is 1
-6 divalent aliphatic saturated hydrocarbon groups include linear or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. R3
, R4 and R5 are linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5ec-butyl, tert- Examples include butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, and isohexyl groups. The alkoxy group having 1 to 6 carbon atoms represented by R3 and R4 includes straight chain or branched alkoxy groups such as methoxy, ethoxy,
n-propoxy, isopropoxy, η-butoxy, imbutoxy, 5ec-butoxy, tert-butoxy, n
-pentoxy, isopentoxy, n-hexyloxy,
Examples include isohexyloxy group. Also,
In general formula (1), when n is 2 or more, R3 and R4 may be the same 7 or different.
本発明において単量体として用いられる一般式％式％
（Ｉ）の化合物の内、Ａが一〇−〇−であるものとして
は、例えばγ−（メタ）アクリロキシプロピルトリメト
キシシラン、γ−（メタ）アクリロキシプロピルトリエ
トキシシラン、γ−（メタ）アクリロキシプロピルトリ
プロポキシシラン、γ−（メタ）アクリロキシプロピル
メチルジメトキシシラン、γ−（メタ）アクリロキシプ
ロピルメチルジェトキシシラン、γ−（メタ）アクリロ
キシプロピルメチルジプロポキシシラン、γ−（メタ）
アクリロキシブチルフェニルジメトキシシラン、γ−（
メタ）アクリロキシブチルフェニルジエトキシシラン、
γ−（メタ）アクリロキシブチルフェニルジエトキシシ
ラン、γ−（メタ）アクリロキシプロピルジメチルメト
キシシラン、γ−（メタ）アクリロキシプロピルジメチ
ルエトキシシラン、γ−（メタ）アクリロキシプロピル
フェニルメチルメトキシシラン、γ−（メタ）アクリロ
キシプロピルフェニルメチルエトキシシラン、（Ｘ；Ｒ
３（Ｘ；Ｒ３０ＣＭ３
を挙げることができる。Among the compounds of the general formula % (I) used as monomers in the present invention, examples of compounds in which A is 10-0- include γ-(meth)acryloxypropyltrimethoxysilane, γ- (meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropyltripropoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyljethoxysilane, γ-( meth)acryloxypropylmethyldipropoxysilane, γ-(meth)
Acryloxybutylphenyldimethoxysilane, γ-(
meth)acryloxybutylphenyldiethoxysilane,
γ-(meth)acryloxybutylphenyldiethoxysilane, γ-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane, γ-(meth)acryloxypropylphenylmethylmethoxysilane, γ-(meth)acryloxypropylphenylmethylethoxysilane, (X;R
3(X;R30CM3).
等を挙げることができる。etc. can be mentioned.
また、オキシラン基含有ビニル単量体としては、分子中
にオキシラン基を含有する各種のビニル単母体を用い得
る。Further, as the oxirane group-containing vinyl monomer, various vinyl monomers containing an oxirane group in the molecule can be used.
殊に、脂環式オキシラン基を含有するビニル単量体を用
いるのが硬化性等の点から好ましい。即ち、脂環式オキ
シラン基含有ビニル単量体を用いる場合には、オキシラ
ン基の開環重合反応の反応性が高いため、硬化が早く又
硬化塗膜の物性がより向上するという効果が得られる。In particular, it is preferable to use a vinyl monomer containing an alicyclic oxirane group from the viewpoint of curability and the like. That is, when using a vinyl monomer containing an alicyclic oxirane group, the reactivity of the ring-opening polymerization reaction of the oxirane group is high, so that the effect of quick curing and further improvement of the physical properties of the cured coating film can be obtained. .
特に好ましいものは脂環式オキシラン基を含有するアク
リル酸又はメタクリル酸エステルであり、具体的には例
えば下記の各一般式（ＩＩ）〜（ＸＩＩｒ）で表わされ
るもの等を挙げることができる。Particularly preferred are acrylic acid or methacrylic esters containing an alicyclic oxirane group, and specific examples include those represented by the following general formulas (II) to (XIIr).
Ｒ６００
１ＩＩ
（ＸＩＩ）
（Ｘ■）
〔各一般式中、Ｒ６は水素原子又はメチル基を示す。Ｒ
７は炭素数１〜６の２価の脂肪族飽和炭化水素基を示す
。Ｒ８は炭素数１〜１．０の２価の炭化水素基を示す。R600 1II (XII) (X■) [In each general formula, R6 represents a hydrogen atom or a methyl group. R
7 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms. R8 represents a divalent hydrocarbon group having 1 to 1.0 carbon atoms.
〕
上記において、Ｒ７によって示される炭素数１〜６の２
価の脂肪族飽和炭化水素基としては、直鎖又は分枝状の
アルキレン基例えばメチレン、エチレン、プロピレン、
テトラメチレン、エチルエチレン、ペンタメチレン、ヘ
キサメチレン基等を挙げることができる。また、Ｒ８に
よって示される炭素数１〜コ−０の２価の炭化水素基と
しては、例えばメチレン、エチレン、プロピレン、テト
ラメチレン、エチルエチレン、ペンタメチレン、ヘキサ
メチレン、ポリメチレン、フェニレン、ことができる。] In the above, 2 having 1 to 6 carbon atoms represented by R7
Examples of aliphatic saturated hydrocarbon groups include linear or branched alkylene groups such as methylene, ethylene, propylene,
Examples include tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 0 carbon atoms represented by R8 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, and phenylene.
また、脂環式以外のオキシラン基含有ビニル単量体の代
表的なものとしては、例えば下記一般式（ＸＩＶ）で表
わされるもの等を挙げることができる。Furthermore, typical examples of vinyl monomers containing non-alicyclic oxirane groups include those represented by the following general formula (XIV).
〔式中、Ｒ６及びＲ７は前記に同じ。〕本発明硬化性組
成物において樹脂成分として用いられる共重合体は、一
般式（１）で表わされる化合物であるアルコキシシラン
基含有ビニル単量体（以下、単量体Ａという）とオキシ
ラン基含有ビニル単量体（以下、単量体Ｂという）とを
単量体成分として含有してなる共重合体である。即ち、
単量体Ａと単量体Ｂを必須単量体成分として用いて得ら
れる共重合体である。ここで、単量体Ａと単量体Ｂとの
使用割合は、通常、重量比でＡ：Ｂ＝１：０．０２〜１
００００程度とするのが良い。[In the formula, R6 and R7 are the same as above. ] The copolymer used as the resin component in the curable composition of the present invention is composed of an alkoxysilane group-containing vinyl monomer (hereinafter referred to as monomer A), which is a compound represented by the general formula (1), and an oxirane group-containing vinyl monomer (hereinafter referred to as monomer A). It is a copolymer containing a vinyl monomer (hereinafter referred to as monomer B) as a monomer component. That is,
It is a copolymer obtained using monomer A and monomer B as essential monomer components. Here, the ratio of monomer A and monomer B used is usually A:B=1:0.02 to 1 in weight ratio.
It is best to set it to about 0000.
Ｂがこの範囲より多くなると硬化性が低下する傾向にあ
り、又Ｂがこの範囲より少なくなると硬化物の物性が低
下し、チヂミが発生し易くなる傾向にあるので好ましく
ない。好ましい使用量は、重量比でＡ：Ｂ＝１：０．１
〜１０００程度である。If the B content exceeds this range, the curability tends to decrease, and if the B content decreases below this range, the physical properties of the cured product tend to deteriorate and wrinkles tend to occur, which is not preferable. The preferred usage amount is A:B=1:0.1 in weight ratio.
~1000.
特に好ましい使用量は、重量比で１Ｂ＝ｌ：０．２５〜
１００程度である。A particularly preferable usage amount is 1B=l:0.25 to 0.25 by weight.
It is about 100.
当該共重合体には、必須の単量体である単量体Ａ及びＢ
に加えて、更に必要によりこれら以外のα、β−エチレ
ン性不飽和単量体を併用することもできる。この場合の
該α、β−エチレン性不飽和単量体の使用量は、本発明
所期の効果を損なわないためには、通常全単量体の約９
９重量％以下、好ましくは約９７重量％以下とするのが
良い。The copolymer contains monomers A and B, which are essential monomers.
In addition to these, α,β-ethylenically unsaturated monomers other than these may also be used in combination, if necessary. In this case, the amount of the α,β-ethylenically unsaturated monomer used is usually about 90% of the total monomers in order not to impair the desired effect of the present invention.
The content is preferably 9% by weight or less, preferably about 97% by weight or less.
上記共重合体は、一般的な方法、条件で製造することが
でき、その数平均分子量は約３０００〜１０００００程
度の範囲が好ましい。The above-mentioned copolymer can be produced by conventional methods and conditions, and its number average molecular weight is preferably in the range of about 3,000 to 100,000.
上記共重合体において任意の単量体成分として使用する
ことができるα、β−エチレン性不飽和単量体としては
、望まれる性能に応じて広範に選一 １６ −
択することができる。斯かる不飽和単量体の代表例を示
せば次の通りである。The α,β-ethylenically unsaturated monomer that can be used as an arbitrary monomer component in the above copolymer can be selected from a wide range depending on the desired performance. Representative examples of such unsaturated monomers are as follows.
（ａ） アクリル酸又はメタクリル酸のエステル：例
えば、アクリル酸メチル、アクリル酸エチル、アクリル
酸プロピル、アクリル酸イソプロピル、アクリル酸ブチ
ル、アクリル酸ヘキシル、アクリル酸オクチル、アクリ
ル酸ラウリル、メタクリル酸メチル、メタクリル酸エチ
ル、メタクリル酸プロピル、メタクリル酸イソプロピル
、メタクリル酸ブチル、メタクリル酸ヘキシル、メタク
リル−酸オクチル、メタクリル酸ラウリル等のアクリル
酸又はメタクリル酸の炭素数１〜１８のアルキルエステ
ル；アクリル酸メトキシブチル、メタクリル酸メトキシ
ブチル、アクリル酸メトキシエチル、メタクリル酸メト
キシエチル、アクリル酸エトキシブチル、メタクリル酸
エトキシブチル等のアクリル酸又はメタクリル酸の炭素
数２〜１８のアルコキシアルキルエステル；アリルアク
リレート、アリルメタクリレート等のアクリル酸又はメ
タクリル酸の炭素数２〜８のアルケニルエステル；ヒド
ロキシエチルアクリレート、ヒドロキシエチルメタクリ
レート、ヒドロキシプロピルアクリレート、ヒドロキシ
プロピルメタクリレート等のアクリル酸又はメタクリル
酸の炭素数２〜８のヒドロキシアルキルエステル；アリ
ルオキシエチルアクリレート、アリルオキシメタクリレ
ート等のアクリル酸又はメタクリル酸の炭素数３〜１８
のフルケニルオキシアルキルエステル。(a) Esters of acrylic acid or methacrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylate. C1-18 alkyl esters of acrylic acid or methacrylic acid such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; methoxybutyl acrylate, methacrylate C2-18 alkoxyalkyl esters of acrylic acid or methacrylic acid such as methoxybutyl acrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate; acrylic acids such as allyl acrylate and allyl methacrylate or alkenyl esters of methacrylic acid having 2 to 8 carbon atoms; hydroxyalkyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; allyloxyethyl acrylate , acrylic acid or methacrylic acid such as allyloxymethacrylate having 3 to 18 carbon atoms
Flukenyloxyalkyl ester of.
（ｂ） ビニル芳香族化合物：例えば、スチレン、α
−メチルスチレン、ビニルトルエン、ｐ−クロルスチレ
ン。(b) Vinyl aromatic compounds: for example, styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene.
（Ｃ） ポリオレフィン系化合物：例えば、ブタジェ
ン、イソプレン、クロロプレン。(C) Polyolefin compounds: for example, butadiene, isoprene, chloroprene.
（ｄ） その他：アクリロニトリル、メタクリレート
リル、メチルイソプロペニルケトン、酢酸ビニル、ベオ
バモノマ−（シェル化学製品）、ビニルプロピオネート
、ビニルピバレートなど。(d) Others: acrylonitrile, methacrylaterile, methyl isopropenyl ketone, vinyl acetate, beoba monomer (Shell Chemicals), vinyl propionate, vinyl pivalate, etc.
本発明硬化性組成物は、単量体Ａと単量体Ｂとを単量体
成分として含有してなる共重合体に、架橋反応硬化剤と
してアルミニウムキレート化合物を配合したものである
。The curable composition of the present invention is a copolymer containing monomer A and monomer B as monomer components, and an aluminum chelate compound as a crosslinking reaction curing agent.
本発明において架橋反応硬化剤として用いるアルミニウ
ムキレ−１・化合物は、それ自体公知のものであるが、
中でも、有機アルミニウムをキレート化剤で処理するこ
とにより得られるものが好適であり、該有機アルミニウ
ムとしては特に下記一般式
％式％（）
〔式中、Ｒ９、Ｒ４゜及びＲ１１のうち少なくとも１つ
は、炭素数１〜１３のアルコキシ基（例：メトキシ、エ
トキシ、ｎ−プロポキシ、イソプロポキシ、ｎ−ブトキ
シ、イソブトキシ、５ｅｅ−ブトキシ、ｔｅｒｔ−ブト
キシ、ｎ−ペントキシ、イソアミルオキシ、ｎ−へキシ
ルオキシ、ｎ−へブチルオキシ、ｎ−オクチルオキシな
ど）又は炭素数３〜］０のアルコキシアルコキシ基（例
：メトキシメトキシ、メトキシエトキシエトキシブトキ
シ、ブトキシペントキシを表わし且つ残・りは炭素数１
〜６のアルキル基（例：メチル、エチル、ｎ−プロピル
、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブ
チル、ｔｅｒｔ−ブチル、アミル基など）、アリール基
（殊にフェニル、トルイル基）、アルケニル基（例：ビ
ニル、アリル基など）又はメルカプト基もしくはアミノ
基で置換された炭素数１〜６のアルキル基（例：γーメ
ルカプトプロピル、アミノエチル、アミノプロピル、ア
ミノブチル基など）を表わす〕
で示される化合物が好適であり、具体的には例えば、ア
ルミニウムイソプロピレート、アルミニラムｓｅｅ−ブ
チレート、アルミニウムｔｅｒｔーブチレートなどが挙
げられる。The aluminum chelate-1 compound used as a crosslinking reaction curing agent in the present invention is known per se.
Among these, those obtained by treating organoaluminum with a chelating agent are preferable, and the organoaluminum has the following general formula % () [wherein at least one of R9, R4° and R11] is an alkoxy group having 1 to 13 carbon atoms (e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 5ee-butoxy, tert-butoxy, n-pentoxy, isoamyloxy, n-hexyloxy, n-hebutyloxy, n-octyloxy, etc.) or an alkoxyalkoxy group having 3 to 0 carbon atoms (e.g. methoxymethoxy, methoxyethoxyethoxybutoxy, butoxypentoxy, and the remainder has 1 carbon number)
-6 alkyl groups (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl groups, etc.), aryl groups (especially phenyl, tolyl groups), alkenyl groups (e.g. vinyl, allyl group, etc.) or an alkyl group having 1 to 6 carbon atoms substituted with a mercapto group or an amino group (e.g. γ-mercaptopropyl, aminoethyl, aminopropyl, aminobutyl group, etc.) The compounds shown are suitable, and specific examples include aluminum isopropylate, aluminum see-butyrate, aluminum tert-butyrate, and the like.
上記有機アルミニウムと反応せしめられるキレ−）−化
剤としては、例えば、低級アルカノールアミン類（例ニ
トリエタノールアミン、ジェタノールアミン、ジメチル
アミノエタノールなど）、アセト酢酸エステル（例：ア
セト酢酸メチル、アセト酢酸エチルなど）、ジケトンア
ルコール（例ニジアセトンアルコールなど）、ジケトン
類（例ニアセチルアセトンなど）、グリコール類（例：
ユチレングリコール、オクチレングリロールなど）、オ
キシカルボン酸（例：乳酸、酒石酸など）、ジカルボン
酸又はそのエステル（例：マレイン酸、マロン酸エチル
など）、その他サルチル酸、カテコール、ピロガロール
等が挙げられ、中でも低級アルカノールアミン類、オキ
シカルボン酸、ジケトン類が好適である。Examples of the chelating agent that can be reacted with the organoaluminum include lower alkanolamines (e.g., nitriethanolamine, jetanolamine, dimethylaminoethanol, etc.), acetoacetate (e.g., methyl acetoacetate, acetoacetate, etc.) ethyl, etc.), diketone alcohols (e.g. diacetone alcohol, etc.), diketones (e.g. niacetylacetone, etc.), glycols (e.g.
Examples include oxycarboxylic acids (e.g., lactic acid, tartaric acid, etc.), dicarboxylic acids or their esters (e.g., maleic acid, ethyl malonate, etc.), salicylic acid, catechol, pyrogallol, etc. Among these, lower alkanolamines, oxycarboxylic acids, and diketones are preferred.
しかして、本発明において有利に用いられるアルミニウ
ムキレート化合物としては、具体的には例えば次のもの
を挙げることができる。即ち、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
テート）、トリストリフルオロアセチルアセトナドアル
ミニウム、トリストリフルオロアセチルアセトナドアル
ミニウム、トリスエチルアセドアセクトアルミニウム、
トリス（ｎ−プロピルアセドアセクト）アルミニウム、
トリス（ｉｓｏ−プロピルアセドアセクト）アルミニウ
ム、トリス（ηープチルアセトアセタト）アルミニウム
、）・リスサリチルアルデヒダトアルミニウム、イソプ
ロポキシビスユチルアセトアセクトアルミニウム、２、
２，６．６−チトラメチルー３，５−へブタジオナトア
ルミニウム、）・リス（２−工）・キシカルボニルフエ
ノラ−１・）アルミニウム、ジイソプロポキシエチルア
セトアセタトアルミニウｌい、トリス（アセチルアセト
す１・）アルミニウム、）・リス（エチルアセトナト）
アルミニウム、トリス（サリチルアルデヒダト）アルミ
ニウム、エチルアセトナトアルミニウムジイソプロピレ
−１・、モノアセチルアセトナト ビス（エチルアセト
ナト）アルミニウム、トリス（ｉｓｏ−プロピレート）
アルミニウム、トリス（ｓｅｅ−ブチレート）アルミニ
ウム、モノーｓｅｃーブトキシアルミニウムジイソプロ
ピレート等であり、これらは部分的に縮合したものであ
っても良い。Specifically, examples of aluminum chelate compounds advantageously used in the present invention include the following. Namely, aluminum ethyl acetoacetate diisopropylate tate), aluminum tristrifluoroacetylacetonado, aluminum tristrifluoroacetylacetonado, aluminum aluminum trisethyl acetate,
tris(n-propylacedoacetate) aluminum,
tris(iso-propylacetoacetate)aluminum, tris(η-butylacetoacetate)aluminum, )・lissalicylaldehydatoaluminum, isopropoxybisbutylacetoacetatealuminum, 2,
2,6.6-titramethyl-3,5-hebutadionatoaluminum, )・Lis(2-ethylated)・xycarbonylphenol-1・)aluminum, diisopropoxyethylacetoacetatoaluminum, tris(acetyl Acetosu1・) Aluminum, )・Lisu(ethyl acetonate)
Aluminum, tris(salicylaldehydato)aluminum, ethylacetonatoaluminumdiisopropylate-1, monoacetylacetonatobis(ethylacetonato)aluminum, tris(iso-propylate)
Aluminum, tris(see-butyrate)aluminum, monosec-butoxyaluminum diisopropylate, etc., and these may be partially condensed.
本発明においては、架橋反応硬化剤としてアルミニウム
キレート化合物のいずれか１種を用いても良いし、２種
以上を適宜併用しても良い。架橋反応硬化剤の配合量は
、前記共重合体１００重量部に対して０．０１〜３０重
量部程度とするのが適当である。この範囲より少ないと
架橋硬化性が低下する傾向にあり、又この範囲より多い
と硬化物中に残存して耐水性を低下させる傾向にあるの
で好ましくない。好ましい配合量は０．１〜１０重量部
で、より好ましい配合量は１〜５重量部である。In the present invention, any one type of aluminum chelate compound may be used as the crosslinking reaction curing agent, or two or more types may be used in combination as appropriate. It is appropriate that the amount of the crosslinking reaction curing agent is about 0.01 to 30 parts by weight based on 100 parts by weight of the copolymer. If the amount is less than this range, crosslinking curability tends to decrease, and if it is more than this range, it tends to remain in the cured product and reduce water resistance, which is not preferable. The preferred amount is 0.1 to 10 parts by weight, and the more preferred amount is 1 to 5 parts by weight.
本発明の硬化性組成物には、必要に応じて、体質顔料、
着色顔料、染料等を添加することができる。また、必要
に応じて、−官能性又は多官能性のエポキシ化合物、ト
リフェニルメトキシシラン、ジフェニルジメトキシシラ
ン等の低分子量のシラン化合物等や、一般的なアルコキ
シシラン基を有するシリコン樹脂等の他の樹脂を添加す
ることもできる。The curable composition of the present invention may optionally include an extender pigment,
Color pigments, dyes, etc. can be added. In addition, if necessary, other materials such as -functional or polyfunctional epoxy compounds, low molecular weight silane compounds such as triphenylmethoxysilane and diphenyldimethoxysilane, and silicone resins having general alkoxysilane groups may be used. Resins can also be added.
本発明の硬化性組成物は、例えば塗料、接着剤、インク
等に好適に使用できる。The curable composition of the present invention can be suitably used, for example, in paints, adhesives, inks, and the like.
本発明の硬化性組成物は、水分の存在下に１００°Ｃ以
下の低温で容易に架橋硬化することができる。即ち、本
発明によれば、当該組成物に水を添加後塗布するか、或
いは当該組成物を塗布後学気中にさらすのみで、何ら加
熱せずとも通常８時間〜７日間程度で充分に硬化させる
ことができる。また、例えば４０〜１００℃に加熱した
場合には５分〜３時間程度で充分に硬化させることがで
きる。また、硬化の際必要な水分は、空気中の湿気程度
の少量で充分である。塗布前に水を添加する場合は、通
常０．１〜１重量％程度の添加量で充分である。The curable composition of the present invention can be easily crosslinked and cured at a low temperature of 100°C or less in the presence of moisture. That is, according to the present invention, by simply adding water to the composition and then applying it, or simply exposing the composition to a chemical atmosphere after application, the composition can be cured normally in about 8 hours to 7 days without any heating. Can be hardened. For example, when heated to 40 to 100°C, it can be sufficiently cured in about 5 minutes to 3 hours. Furthermore, a small amount of moisture, comparable to that in the air, is sufficient for curing. When water is added before coating, an amount of about 0.1 to 1% by weight is usually sufficient.
本発明の硬化性組成物が、少量の水分の存在下、低温で
容易に架橋硬化する理由は、次の様に考えられる。即ち
、一段目の反応として、単量体Ａに由来するアルコキシ
基が、水分の存在下、アルミニウムキレート化合物を触
媒として加水分解してシラノール基を生じる。次に二段
目の反応としてシラノール基同志の脱水縮合による架橋
やアルミニウムキレート化合物と反応して
とによる架橋が起こる。更に三段目の反応とじて位して
シラノール基を分極させ、この分極したシラノール基が
単量体Ｂに由来するオキシラン基を開環重合させること
による架橋が起こる。The reason why the curable composition of the present invention is easily crosslinked and cured at low temperature in the presence of a small amount of water is considered to be as follows. That is, as a first-stage reaction, an alkoxy group derived from monomer A is hydrolyzed in the presence of moisture using an aluminum chelate compound as a catalyst to generate a silanol group. Next, as a second reaction, crosslinking occurs due to dehydration condensation of silanol groups or crosslinking due to reaction with an aluminum chelate compound. Further, in the third stage of reaction, the silanol group is polarized, and the polarized silanol group causes ring-opening polymerization of the oxirane group derived from monomer B, thereby causing crosslinking.
従来の場合と比較すると、従来のこの種の硬化性組成物
では、上記二段目の反応のみで架橋硬化されていたのに
対して、本発明の硬化性組成物では特に単量体Ｂを用い
たことにより上記二段目の反応と三段目の反応が連鎖的
に平行して起こって架橋硬化されるので、少量の水分で
低温下Ｊこ好逼に硬化できるものと考えられる。Compared to the conventional case, in the conventional curable composition of this type, crosslinking and curing was performed only by the second reaction, whereas in the curable composition of the present invention, monomer B is particularly It is thought that by using the above-mentioned second-stage reaction and third-stage reaction occur in parallel in a chain, resulting in crosslinking and curing, so that it can be cured easily at low temperatures with a small amount of moisture.
発明の効果
本発明の硬化性組成物によれば、特に樹脂成分として用
いられる共重合体が単量体Ａ及び単量体Ｂの両者を単量
体成分として含有していることにより、次の様な格別顕
著な効果が奏される。Effects of the Invention According to the curable composition of the present invention, since the copolymer used as the resin component contains both monomer A and monomer B as monomer components, the following properties can be achieved. This produces particularly remarkable effects.
（１）わずかの水分、例えば空気中の湿気程度の水分存
在下で、１００℃以下の低温で容易に架橋硬化できる。(1) It can be easily crosslinked and cured at a low temperature of 100° C. or lower in the presence of a small amount of moisture, for example, moisture in the air.
（２）前記縮合反応等による架橋と前記開環重合反応に
よる架橋とが併行して起こるため、表面と内部の硬化性
の差が少なく、チヂミを生じない。(2) Since the crosslinking by the condensation reaction etc. and the crosslinking by the ring-opening polymerization reaction occur in parallel, there is little difference in hardenability between the surface and the inside, and no stiffness occurs.
（３）アルコール等の副生物が少ないため、物性ニ優れ
た硬化物が得られる。特に、耐水性、耐候性、耐衝撃性
、上塗り適性、可とう性、耐汚染性等の物性に優れる。(3) Since there are few by-products such as alcohol, a cured product with excellent physical properties can be obtained. In particular, it has excellent physical properties such as water resistance, weather resistance, impact resistance, suitability for overcoating, flexibility, and stain resistance.
（４）貯蔵安定性に優れ、水分のない状態で１年以上安
定である。(4) It has excellent storage stability and is stable for more than one year in a moisture-free state.
実施例
以下、実施例及び比較例を挙げて、本発明を更に具体的
に説明する。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１ 下記単量体組成のビニル共重合体を合成した。Example 1 A vinyl copolymer having the following monomer composition was synthesized.
ｎ−ブチルメタアクリレ−）−３０，５重量％得られた
ビニル共重合体の５０重量％トルエン溶液は、ガードナ
ー粘度計でＨの粘度を示した。A 50% by weight toluene solution of the obtained vinyl copolymer (n-butyl methacrylate)-30.5% showed a viscosity of H on a Gardner viscometer.
また、ＧＰＣ分子量は、１５０００にピーク分子量を示
した。この５０重量％）・ルエン樹脂液１００ｇに、２
ｇのトリス（ｎ−プロピルアセドアセクト）アルミニウ
ムを添加して、本発明硬化性組成物を得た。Further, the GPC molecular weight showed a peak molecular weight at 15,000. 50% by weight)・100g of luene resin liquid, 2
g of tris(n-propylacedoacet)aluminum was added to obtain a curable composition of the present invention.
実施例２ 下記単量体組成のビニル共重合体を合成した。Example 2 A vinyl copolymer having the following monomer composition was synthesized.
得られた共重合体の７０重量％イソブチルアセテート溶
液は、ガードナー粘度計でＺの粘度を示した。また、Ｇ
ＰＣ分子量は５０００にピーク分子量を示した。この７
０重量％イソブチルアセテート樹脂液１００ｇに２０ｇ
のトリス（サリチルアルデヒダト）アルミニウムを添加
して、本発明硬化性組成物を得た。A 70% by weight solution of the obtained copolymer in isobutyl acetate showed a viscosity of Z on a Gardner viscometer. Also, G
The PC molecular weight showed a peak molecular weight at 5,000. This 7
20g in 100g of 0% by weight isobutyl acetate resin liquid
of tris(salicylaldehydato)aluminum was added to obtain a curable composition of the present invention.
実施例３ 下記単量体組成のビニル共重合体を合成した。Example 3 A vinyl copolymer having the following monomer composition was synthesized.
γ−アクリロキシプロピル
フェニルメチルメトキシシラン ５重量％ス
チ し ン ５
５重量％この共重合体の５０重量％トルエン溶液のガー
ドナー粘度は、Ｗであった。また、ＧＰＣのピーク分子
量は、２５０００であった。この５０重量％トルエン樹
脂液１００ｇに１ｇのトリス（エチルアセドアセクト）
アルミニウムを添加して、本発明組成物を得た。γ-Acryloxypropylphenylmethylmethoxysilane 5% by weight
Chin 5
The Gardner viscosity of a 50% by weight toluene solution of this copolymer was W. Moreover, the peak molecular weight of GPC was 25,000. 1g of Tris (ethyl acetate) in 100g of this 50% by weight toluene resin solution
Aluminum was added to obtain the composition of the present invention.
実施例４ 下記単量体組成のビニル共重合体を合成した。Example 4 A vinyl copolymer having the following monomer composition was synthesized.
γ−メタクリロキシプロピル
トリメトキシシラン ５０重ｆｉ％メ
チルアクリレート ３５重量％この
共重合体の５０重量％トルエン溶液のガードナー粘度は
、Ｘであった。また、ＧＰＣピーク分子量は、４０００
０であった。この５０重量％トルエン樹脂液１００ｇに
、１０ｇのトリス（アセチルアセトナト）アルミニウム
を添加して、本発明組成物を得た。γ-Methacryloxypropyltrimethoxysilane 50% by weight Methyl acrylate 35% by weight A 50% by weight toluene solution of this copolymer had a Gardner viscosity of X. In addition, the GPC peak molecular weight is 4000
It was 0. To 100 g of this 50% by weight toluene resin liquid was added 10 g of tris(acetylacetonato)aluminum to obtain a composition of the present invention.
実施例５ 下記単量体組成のビニル共重合体を合成した。Example 5 A vinyl copolymer having the following monomer composition was synthesized.
メチルメタアクリレート ９４重量％この共
重合体の５０重量％トルエン−ブタノール（１：、１）
溶液のガードナー粘度は、Ｓであった。また、ＧＰＣ分
子量は、２８０００にピークを示した。この５０重量％
トルエン−ブタノール樹脂液１００ｇに、５０ｇのルチ
ル型チタン白を添加し、よく分散した後、トリス（アセ
チルアセトナト）アルミニウムを１ｇ添加して、本発明
組酸物を得た。Methyl methacrylate 94% by weight of this copolymer 50% by weight Toluene-butanol (1:,1)
The Gardner viscosity of the solution was S. Moreover, the GPC molecular weight showed a peak at 28,000. This 50% by weight
After adding 50 g of rutile-type titanium white to 100 g of toluene-butanol resin liquid and thoroughly dispersing it, 1 g of tris(acetylacetonato)aluminum was added to obtain the acid complex of the present invention.
実施例６ 下記単量体組成のビニル共重合体を合成した。Example 6 A vinyl copolymer having the following monomer composition was synthesized.
オキシジシクロペンテニル
アクリレート ２０６５重量％スチレ
ン ４０．５重量％ｎ−ブチルア
クリレート ２９．０重量％γ−メタアクリロキ
シプロピル
メチルジメトキシシラン １０．０重量％この共
重合体の５０重量％トルエン溶液は、ガードナー粘度計
でＸの粘度を示した。また、ＧＰＣ分子量では、３５０
００にピーク分子量を示した。この５０重量％トルエン
樹脂液１００ｇに１０ｇのトリス（エチルアセトナト）
アルミニウムを添加して、本発明組成物を得た。Oxydicyclopentenyl acrylate 2065% by weight Styrene 40.5% by weight n-butyl acrylate 29.0% by weight γ-methacryloxypropylmethyldimethoxysilane 10.0% by weight A 50% by weight toluene solution of this copolymer was prepared by Gardner The viscometer showed a viscosity of X. In addition, the GPC molecular weight is 350
The peak molecular weight is shown at 00. 10g of Tris (ethyl acetonate) in 100g of this 50% by weight toluene resin solution
Aluminum was added to obtain the composition of the present invention.
実施例７ 下記単量体組成のビニル共重合体を合成した。Example 7 A vinyl copolymer having the following monomer composition was synthesized.
５０重量％
メチルメタアクリレート ４０重量％γ−メ
タアクリロキシプロピル
ジメチルメトキシシラン １０重量％この共
重合体の５０重量％トルエン溶液は、ガードナー粘度計
で２２の粘度を示した。また、ＧＰＣ分子量では８８０
０にピーク分子量を示した。この５０重量％トルエン樹
脂液１００ｇに０．５ｇのトリス（サリチルアルデヒダ
ト）アルミニウムを添加して、本発明組成物を得た。50% by weight Methyl methacrylate 40% by weight γ-methacryloxypropyldimethylmethoxysilane 10% by weight A 50% by weight toluene solution of this copolymer showed a viscosity of 22 on a Gardner viscometer. In addition, the GPC molecular weight is 880
The peak molecular weight is shown at 0. A composition of the present invention was obtained by adding 0.5 g of tris(salicylaldehydato)aluminum to 100 g of this 50% by weight toluene resin liquid.
実施例８ 下記単量体組成のビニル共重合体を合成しプこ。Example 8 Synthesize a vinyl copolymer with the following monomer composition.
メチルメタアクリレート ２０重量％エチル
アクリレ−ｈ ２ＯｒｆＬ量％〇Ｃ
ｌｌ３
３０重量％
この共重合体の５０重量％トルエン溶液は、ガードナー
粘度計でＴＵの粘度を示した。また、ＧＰＣ分子量では
１２０００にピーク分子量を示した。この５０重量％ト
ルエン樹脂液１００ｇに１ｇの１リス（エチルアセドア
セクト）アルミニウムを添加して、本発明組成物を得プ
こ。Methyl methacrylate 20% by weight Ethyl acrylate-h 2OrfL amount%〇C
ll3 30% by weight A 50% by weight toluene solution of this copolymer showed a viscosity of TU on a Gardner viscometer. Moreover, the peak molecular weight was shown at 12,000 in GPC molecular weight. To 100 g of this 50% by weight toluene resin liquid, 1 g of 1 lithium (ethylacedoacetate) aluminum was added to obtain the composition of the present invention.
実施例９ 丁記単量体別成のビニル共重合体を合成した。Example 9 A vinyl copolymer with separate monomers was synthesized.
９０重量％
■
ＣＨ３
１０重量％
この共重合体の５０重量％トルエン溶液は、ガードナー
粘度計で２２の粘度を示した。また、ＧＰＣ分子量では
２００００にピーク分子量を示した。この５０重量％ト
ルエン樹脂液１００ｇに１０ｇのトリス（アセチルアセ
トナト）アルミニウムを添加して、本発明組成物を得た
。90% by weight CH3 10% by weight A 50% by weight toluene solution of this copolymer showed a viscosity of 22 on a Gardner viscometer. Moreover, the peak molecular weight was shown at 20,000 in GPC molecular weight. 10 g of tris(acetylacetonato)aluminum was added to 100 g of this 50% by weight toluene resin liquid to obtain a composition of the present invention.
実施例１０ 下記単量体組成のビニル共重合体を合成した。Example 10 A vinyl copolymer having the following monomer composition was synthesized.
Ｏ
ＩＩ
メチルメタアクリレート ４０重量％Ｃ２Ｈ
５
１０重量％
この共重合体の５０重量％トルエン溶液は、ガードナー
粘度計でＷの粘度を示した。また、ＧＰＣ分子量では１
００００にピーク分子量を示した。この５０重量％トル
エン樹脂液１ｏｏｇに１ｇのトリス（アセチルアセトナ
ト）アルミニウムを添加して、本発明組成物を得九つ
比較例１
下記単量体組成のビニル共重合体を合成した。O II Methyl methacrylate 40% by weight C2H
5 10% by weight A 50% by weight toluene solution of this copolymer showed a viscosity of W on a Gardner viscometer. Also, the GPC molecular weight is 1
The peak molecular weight is shown at 0000. 1 g of tris(acetylacetonato)aluminum was added to 10 g of this 50% by weight toluene resin solution to obtain nine compositions of the present invention.Comparative Example 1 A vinyl copolymer having the following monomer composition was synthesized.
ｎ−ブチルメタアクリレ−１−９５，０重量％γ−メタ
クリＶキシプｖピル
トリメトキシシラン ５．０重ｆｊｋ％こ
の共重合体の５０重量％トルエン溶液のガードナー粘度
は、Ｎであった。また、ＧＰＣ分子量は、２８０００に
ピークを示した。この５０重量％トルエン樹脂液１００
ｇに、３ｇのトリス（アセチルアセトン）アルミニウム
を添加して、比較の硬化性組成物を得た。n-Butyl methacrylate-1-95.0% by weight γ-methacrylate Vxipv pyrutrimethoxysilane 5.0% by weight fjk The Gardner viscosity of a 50% by weight toluene solution of this copolymer was N. Moreover, the GPC molecular weight showed a peak at 28,000. This 50% by weight toluene resin liquid 100
A comparative curable composition was obtained by adding 3 g of tris(acetylacetone)aluminum to g.
比較例２
実施例１において ・
ＣＨ３
を使用しない他は、実施例１と同様にして比較の組成物
を得た。Comparative Example 2 A comparative composition was obtained in the same manner as in Example 1 except that CH3 was not used.
次に下記に示す試験を行なった。Next, the following tests were conducted.
実施例１〜１０及び比較例１．２の各組成物を乾燥膜厚
１００μ（ただし、耐水性、耐候性は５０μで実験した
。）になるように塗装した後、第１表に記載の乾燥条件
で乾燥して試験に供した。After coating each of the compositions of Examples 1 to 10 and Comparative Example 1.2 to a dry film thickness of 100μ (however, water resistance and weather resistance were tested at 50μ), the drying method described in Table 1 was applied. It was dried under the following conditions and used for testing.
ゲル分率：乾燥させた塗膜をガラス板からはがしとりソ
ックスレー抽出器で還流温度でアセトンを用いて６時間
抽出した後、塗膜の残分を％で表わした。Gel fraction: The dried coating film was peeled off from the glass plate and extracted with acetone at reflux temperature using a Soxhlet extractor for 6 hours, and the remaining content of the coating film was expressed in %.
耐衝撃性：素材は軟鋼板を用いた。デュポン衝撃試験器
を用い、５００ｇのおもりを塗面に落下せしめ、塗膜の
ワレ、ハガレのない最大落下距離（ｃｍ ）を調べた。Impact resistance: The material used is mild steel plate. Using a DuPont impact tester, a 500 g weight was dropped onto the painted surface, and the maximum fall distance (cm 2 ) without cracking or peeling of the paint film was determined.
耐水性：素材は軟鋼板を用いた。試験片を温水（４０℃
）に６０日間浸漬し、その後塗面状態の異常の有無を調
べた。Water resistance: The material used is mild steel plate. Place the test piece in warm water (40℃
) for 60 days, and then the coated surface was examined for abnormalities.
耐候性：素材はアルミ板を用いた。ザＱパネル社製のＱ
ＵＶ式ウェザ−メーター（紫外線蛍光ランプｒＮｏ、Ｑ
Ｆ Ｓ−４０、ＵＶ−ＢＪ 、波長域３２０〜２８０
ｎｍ）を用いて温度４０〜７０℃で照射（１５分）と結
露（１５分）というサイクルを２０００時間繰返した後
塗膜劣化の程度を観察した。Weather resistance: The material used is aluminum plate. Q manufactured by The Q Panel Co., Ltd.
UV weather meter (ultraviolet fluorescent lamp rNo, Q
FS-40, UV-BJ, wavelength range 320-280
After repeating a cycle of irradiation (15 minutes) and dew condensation (15 minutes) at a temperature of 40 to 70° C. for 2000 hours, the degree of deterioration of the coating film was observed.
上塗り適性：塗膜上に「ビニデラックス」 （関西ペイ
ント社製、アクリル樹脂系エマルジョン塗料を４０μ塗
装し、２０℃で２時間乾燥させてから塗面にクロスカッ
トを入れてセロハンテープ剥離試験を行なった後、剥離
の程度を調べた。Suitability for overcoating: Apply 40μ of "Vini Deluxe" (manufactured by Kansai Paint Co., Ltd., acrylic resin emulsion paint) on the paint film, dry it at 20℃ for 2 hours, then make a cross cut on the painted surface and perform a cellophane tape peeling test. After that, the degree of peeling was examined.
試験結果を第１表に示す。The test results are shown in Table 1.
Claims (3)
数式、化学式、表等があります▼を示す。 Ｒ＿１は水素原子又はメチル基を、Ｒ＿２は炭素数１〜
６の２価の脂肪族飽和炭化水素基を、Ｒ＿３及びＲ＿４
は同一又は異なつてフェニル基、炭素数１〜６のアルキ
ル基又は炭素数１〜６のアルコキシ基を、Ｒ＿５は炭素
数１〜６のアルキル基をそれぞれ示す。ｎは１〜１００
の整数を示す。〕 で表わされる化合物であるアルコキシシラン基含有ビニ
ル単量体とオキシラン基含有ビニル単量体とを単量体成
分として含有してなる共重合体に、架橋反応硬化剤とし
てアルミニウムキレート化合物を配合してなることを特
徴とする硬化性組成物。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. Showing ▼. R_1 is a hydrogen atom or a methyl group, R_2 is a carbon number of 1 to
6 divalent aliphatic saturated hydrocarbon groups, R_3 and R_4
are the same or different and each represents a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R_5 represents an alkyl group having 1 to 6 carbon atoms. n is 1 to 100
indicates an integer. ] An aluminum chelate compound is blended as a crosslinking reaction curing agent into a copolymer containing as monomer components an alkoxysilane group-containing vinyl monomer and an oxirane group-containing vinyl monomer, which is a compound represented by A curable composition characterized by:
ラン基含有ビニル単量体である特許請求の範囲第１項に
記載の組成物。(2) The composition according to claim 1, wherein the oxirane group-containing vinyl monomer is an alicyclic oxirane group-containing vinyl monomer.
数式、化学式、表等があります▼を示す。 Ｒ＿１は水素原子又はメチル基を、Ｒ＿２は炭素数１〜
６の２価の脂肪族飽和炭化水素基を、Ｒ＿３及びＲ＿４
は同一又は異なつてフェニル基、炭素数１〜６のアルキ
ル基又は炭素数１〜６のアルコキシ基を、Ｒ＿５は炭素
数１〜６のアルキル基をそれぞれ示す。ｎは１〜１００
の整数を示す。〕 で表わされる化合物であるアルコキシシラン基含有ビニ
ル単量体とオキシラン基含有ビニル単量体とを単量体成
分として含有してなる共重合体に、架橋反応硬化剤とし
てアルミニウムキレート化合物を配合してなる硬化性組
成物を、水分の存在下に１００℃以下で架橋させること
を特徴とする硬化方法。(3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲
There are mathematical formulas, chemical formulas, tables, etc. Showing ▼. R_1 is a hydrogen atom or a methyl group, R_2 is a carbon number of 1 to
6 divalent aliphatic saturated hydrocarbon groups, R_3 and R_4
are the same or different and each represents a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R_5 represents an alkyl group having 1 to 6 carbon atoms. n is 1 to 100
indicates an integer. ] An aluminum chelate compound is blended as a crosslinking reaction curing agent into a copolymer containing as monomer components an alkoxysilane group-containing vinyl monomer and an oxirane group-containing vinyl monomer, which is a compound represented by A curing method comprising crosslinking a curable composition comprising:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11133686 | 1986-05-15 | ||
| JP61-111336 | 1986-05-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63108048A true JPS63108048A (en) | 1988-05-12 |
| JPH0567647B2 JPH0567647B2 (en) | 1993-09-27 |
Family
ID=14558615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62119835A Granted JPS63108048A (en) | 1986-05-15 | 1987-05-15 | Curable composition and curing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63108048A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02160879A (en) * | 1988-09-05 | 1990-06-20 | Kansai Paint Co Ltd | Automotive paint composition |
| JPH0680456U (en) * | 1993-04-30 | 1994-11-15 | 市川 聡 | Hitting head |
| JP2001310943A (en) * | 2000-02-22 | 2001-11-06 | Ube Nitto Kasei Co Ltd | Organic/inorganic functionally gradient material |
| JP2007512402A (en) * | 2003-11-17 | 2007-05-17 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Hydrolyzates and / or condensates of epoxy-functional and silane-functional oligomers and polymers, and their production and use |
| JP2008517008A (en) * | 2004-10-19 | 2008-05-22 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Highly elastic coating agent with high scratch resistance based on alkoxysilane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52112698A (en) * | 1976-03-19 | 1977-09-21 | Toray Ind Inc | Curable resin compositions |
| JPS6067553A (en) * | 1983-09-24 | 1985-04-17 | Kansai Paint Co Ltd | Curable composition |
| JPS61127765A (en) * | 1984-11-26 | 1986-06-16 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
-
1987
- 1987-05-15 JP JP62119835A patent/JPS63108048A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52112698A (en) * | 1976-03-19 | 1977-09-21 | Toray Ind Inc | Curable resin compositions |
| JPS6067553A (en) * | 1983-09-24 | 1985-04-17 | Kansai Paint Co Ltd | Curable composition |
| JPS61127765A (en) * | 1984-11-26 | 1986-06-16 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02160879A (en) * | 1988-09-05 | 1990-06-20 | Kansai Paint Co Ltd | Automotive paint composition |
| JPH0680456U (en) * | 1993-04-30 | 1994-11-15 | 市川 聡 | Hitting head |
| JP2512761Y2 (en) * | 1993-04-30 | 1996-10-02 | 市川 聡 | Pattern head |
| JP2001310943A (en) * | 2000-02-22 | 2001-11-06 | Ube Nitto Kasei Co Ltd | Organic/inorganic functionally gradient material |
| JP2007512402A (en) * | 2003-11-17 | 2007-05-17 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Hydrolyzates and / or condensates of epoxy-functional and silane-functional oligomers and polymers, and their production and use |
| JP4823915B2 (en) * | 2003-11-17 | 2011-11-24 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | Hydrolyzates and / or condensates of epoxy-functional and silane-functional oligomers and polymers, and their production and use |
| JP2008517008A (en) * | 2004-10-19 | 2008-05-22 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Highly elastic coating agent with high scratch resistance based on alkoxysilane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0567647B2 (en) | 1993-09-27 |
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