JPH0253880A - Resin composition for coating excellent in low-temperature curability - Google Patents
Resin composition for coating excellent in low-temperature curabilityInfo
- Publication number
- JPH0253880A JPH0253880A JP20461988A JP20461988A JPH0253880A JP H0253880 A JPH0253880 A JP H0253880A JP 20461988 A JP20461988 A JP 20461988A JP 20461988 A JP20461988 A JP 20461988A JP H0253880 A JPH0253880 A JP H0253880A
- Authority
- JP
- Japan
- Prior art keywords
- group
- meth
- weight
- acrylate
- monomer
- 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
- 238000000576 coating method Methods 0.000 title claims description 21
- 239000011342 resin composition Substances 0.000 title claims description 11
- 239000011248 coating agent Substances 0.000 title description 17
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 229920000768 polyamine Polymers 0.000 claims abstract description 27
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- -1 nitrogen-containing compound Chemical class 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical group [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- 238000001723 curing Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003973 paint Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229920006163 vinyl copolymer Polymers 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- FKKZGQXMWVGPMH-UHFFFAOYSA-N (2-hydroxyphenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].OC1=CC=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 FKKZGQXMWVGPMH-UHFFFAOYSA-N 0.000 description 1
- BGUPWTFDMHDYIR-UHFFFAOYSA-N (3-methylphenyl)-diphenylphosphane Chemical compound CC1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BGUPWTFDMHDYIR-UHFFFAOYSA-N 0.000 description 1
- MZBKKJRCQNVENM-UHFFFAOYSA-M (4-ethoxyphenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].C1=CC(OCC)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MZBKKJRCQNVENM-UHFFFAOYSA-M 0.000 description 1
- MUAHCGHHMGUQRW-UHFFFAOYSA-M (4-ethoxyphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].C1=CC(OCC)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MUAHCGHHMGUQRW-UHFFFAOYSA-M 0.000 description 1
- UJIHVZPVGXBWJZ-AATRIKPKSA-N (E)-4-(6-hydroxyhexoxy)-4-oxobut-2-enoic acid Chemical compound OCCCCCCOC(=O)\C=C\C(O)=O UJIHVZPVGXBWJZ-AATRIKPKSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- XETDBHNHTOJWPZ-UHFFFAOYSA-M 2-(1,3-dioxan-2-yl)ethyl-triphenylphosphanium;bromide Chemical compound [Br-].O1CCCOC1CC[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XETDBHNHTOJWPZ-UHFFFAOYSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OSMIKBUMHDSMJT-UHFFFAOYSA-M 2-(dimethylamino)ethyl-triphenylphosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCN(C)C)C1=CC=CC=C1 OSMIKBUMHDSMJT-UHFFFAOYSA-M 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- KZBWHCFTAAHIJJ-UHFFFAOYSA-M 2-oxopropyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)C)C1=CC=CC=C1 KZBWHCFTAAHIJJ-UHFFFAOYSA-M 0.000 description 1
- XAMZZEBAJZJERT-UHFFFAOYSA-M 2-oxopropyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)C)C1=CC=CC=C1 XAMZZEBAJZJERT-UHFFFAOYSA-M 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- HMJBXEZHJUYJQY-UHFFFAOYSA-N 4-(aminomethyl)octane-1,8-diamine Chemical compound NCCCCC(CN)CCCN HMJBXEZHJUYJQY-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- MLOSJPZSZWUDSK-UHFFFAOYSA-N 4-carboxybutyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCC(=O)O)C1=CC=CC=C1 MLOSJPZSZWUDSK-UHFFFAOYSA-N 0.000 description 1
- RDVQCZWYQQOQOC-UHFFFAOYSA-N 4-carboxybutyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCC(=O)O)C1=CC=CC=C1 RDVQCZWYQQOQOC-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical class Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 description 1
- 125000000174 L-prolyl group Chemical group [H]N1C([H])([H])C([H])([H])C([H])([H])[C@@]1([H])C(*)=O 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000005700 Putrescine Substances 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NCKJIJSEWKIXAT-DQRAZIAOSA-N [(z)-2-diphenylphosphanylethenyl]-diphenylphosphane Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)/C=C\P(C=1C=CC=CC=1)C1=CC=CC=C1 NCKJIJSEWKIXAT-DQRAZIAOSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- VUJGHKLQWVJKNL-UHFFFAOYSA-N [4-diphenoxyphosphorylbutyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)CCCCP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 VUJGHKLQWVJKNL-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- CAKCTOSIPXLHDW-UHFFFAOYSA-M [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=C)C1=CC=CC=C1 Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=C)C1=CC=CC=C1 CAKCTOSIPXLHDW-UHFFFAOYSA-M 0.000 description 1
- OMLMIKWOLVLSAZ-UHFFFAOYSA-N [Cl-].OC1=C(C[P+](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2)C=CC=C1 Chemical compound [Cl-].OC1=C(C[P+](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2)C=CC=C1 OMLMIKWOLVLSAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WTEPWWCRWNCUNA-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 WTEPWWCRWNCUNA-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- YFTMLUSIDVFTKU-UHFFFAOYSA-M bromomethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CBr)C1=CC=CC=C1 YFTMLUSIDVFTKU-UHFFFAOYSA-M 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 1
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- SXYFAZGVNNYGJQ-UHFFFAOYSA-M chloromethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCl)C1=CC=CC=C1 SXYFAZGVNNYGJQ-UHFFFAOYSA-M 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- ZXKWUYWWVSKKQZ-UHFFFAOYSA-N cyclohexyl(diphenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZXKWUYWWVSKKQZ-UHFFFAOYSA-N 0.000 description 1
- KUIAJKPVKOXUQO-UHFFFAOYSA-N cyclohexyl(phenyl)phosphane Chemical compound C1CCCCC1PC1=CC=CC=C1 KUIAJKPVKOXUQO-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- ORICWOYODJGJMY-UHFFFAOYSA-N dibutyl(phenyl)phosphane Chemical compound CCCCP(CCCC)C1=CC=CC=C1 ORICWOYODJGJMY-UHFFFAOYSA-N 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- LVTCZSBUROAWTE-UHFFFAOYSA-N diethyl(phenyl)phosphane Chemical compound CCP(CC)C1=CC=CC=C1 LVTCZSBUROAWTE-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NOCGROPYCGRERZ-UHFFFAOYSA-M methoxymethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(COC)C1=CC=CC=C1 NOCGROPYCGRERZ-UHFFFAOYSA-M 0.000 description 1
- SJFNDMHZXCUXSA-UHFFFAOYSA-M methoxymethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(COC)C1=CC=CC=C1 SJFNDMHZXCUXSA-UHFFFAOYSA-M 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- ODBJKENDOPPIFT-UHFFFAOYSA-N n,n'-bis(2-aminoethyl)butane-1,4-diamine Chemical compound NCCNCCCCNCCN ODBJKENDOPPIFT-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- AEHDSYHVTDJGDN-UHFFFAOYSA-M phenacyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1C(=O)C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AEHDSYHVTDJGDN-UHFFFAOYSA-M 0.000 description 1
- OSRKWUXYLYWDOH-UHFFFAOYSA-N phenyl(dipropyl)phosphane Chemical compound CCCP(CCC)C1=CC=CC=C1 OSRKWUXYLYWDOH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- MOSFSEPBWRXKJZ-UHFFFAOYSA-N tridecylphosphane Chemical compound CCCCCCCCCCCCCP MOSFSEPBWRXKJZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- FPZZZGJWXOHLDJ-UHFFFAOYSA-N trihexylphosphane Chemical compound CCCCCCP(CCCCCC)CCCCCC FPZZZGJWXOHLDJ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- IWPNEBZUNGZQQQ-UHFFFAOYSA-N tripentylphosphane Chemical compound CCCCCP(CCCCC)CCCCC IWPNEBZUNGZQQQ-UHFFFAOYSA-N 0.000 description 1
- FWYKRJUVEOBFGH-UHFFFAOYSA-M triphenyl(prop-2-enyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FWYKRJUVEOBFGH-UHFFFAOYSA-M 0.000 description 1
- FKMJROWWQOJRJX-UHFFFAOYSA-M triphenyl(prop-2-enyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FKMJROWWQOJRJX-UHFFFAOYSA-M 0.000 description 1
- XMQSELBBYSAURN-UHFFFAOYSA-M triphenyl(propyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 XMQSELBBYSAURN-UHFFFAOYSA-M 0.000 description 1
- IUNJPQCPINLADS-UHFFFAOYSA-L triphenyl-[[4-(triphenylphosphaniumylmethyl)phenyl]methyl]phosphanium;dichloride Chemical compound [Cl-].[Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC(C=C1)=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 IUNJPQCPINLADS-UHFFFAOYSA-L 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 1
- DSROZUMNVRXZNO-UHFFFAOYSA-K tris[(1-naphthalen-1-yl-3-phenylnaphthalen-2-yl)oxy]alumane Chemical compound C=1C=CC=CC=1C=1C=C2C=CC=CC2=C(C=2C3=CC=CC=C3C=CC=2)C=1O[Al](OC=1C(=C2C=CC=CC2=CC=1C=1C=CC=CC=1)C=1C2=CC=CC=C2C=CC=1)OC(C(=C1C=CC=CC1=C1)C=2C3=CC=CC=C3C=CC=2)=C1C1=CC=CC=C1 DSROZUMNVRXZNO-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規にして有用なる塗料用樹脂組成物に関し、
さらに詳細に、特定のカーブネート基含有共重合体と、
ポリアミン化合物と、特定の硬化助剤とを必須の成分と
して含んで成る、とりわけ、低温硬化性と、ポリアミン
化合物との相溶性にすぐれ、しかもポットライフも長い
という特定のカーブネート基含有共重合体を用いた塗料
用樹脂組成物に関す、る。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new and useful resin composition for coatings,
More specifically, a specific carnate group-containing copolymer,
A specific carnate group-containing copolymer that contains a polyamine compound and a specific curing aid as essential components, and has particularly excellent low-temperature curability and compatibility with the polyamine compound, as well as a long pot life. Relating to a resin composition for paint using.
従来の二液ウレタン硬化型アクリル樹脂組成物にあって
は、架橋剤として、ポリイソシアネート化合物が用いら
れてきたが、かかるポリイソシアネート化合物中に含ま
れるフリーのイソシアネト・モノマーの毒性が問題とな
っている。In conventional two-component urethane curable acrylic resin compositions, polyisocyanate compounds have been used as crosslinking agents, but the toxicity of free isocyanate monomers contained in such polyisocyanate compounds has become a problem. There is.
そうした中で、これまでにも、側鎖にカーブネト基を有
する重合体とポリアミン化合物とを組み合わせることに
より、ウレタン結合を介して架橋させるという、インシ
アネートフリーの二液ウレタン硬化型の樹脂組成物は知
られている。Under these circumstances, inocyanate-free two-component urethane curable resin compositions have been developed, which are crosslinked via urethane bonds by combining a polymer having a carbeneto group in the side chain and a polyamine compound. Are known.
しかしながら、こうした従来のイソシアネートフリーの
塗料用硬化型樹脂に用いられるカーボネート基含有重合
体は、硬化剤としてのポリアミン化合物との相溶性が著
しく悪く、そのため両者を混合せしめたさいに濁りを生
じ、塗膜を形成せしめてもクリアリティーが劣るという
欠点がある。However, carbonate group-containing polymers used in conventional isocyanate-free curable resins for paints have extremely poor compatibility with polyamine compounds as curing agents, resulting in turbidity and coating when mixed. Even if a film is formed, the problem is that the clarity is poor.
さらに、かかる相溶性の悪さに起因してカーボネート基
とポリアミン化合物との反応性も十分でなく硬化塗膜の
諸物性が劣るという欠点がある。Furthermore, due to such poor compatibility, the reactivity between the carbonate group and the polyamine compound is also insufficient, resulting in poor physical properties of the cured coating film.
しかるに、本発明者らは上述した如き従来技術における
種々の欠点の存在に鑑みて、ポリアミン化合物との相溶
性が良好な新だなカーボネート基含有共重合体を開発す
るべく鋭意検討を重ねた結果、かかるカーボネート基含
有共重合体の必須単量体成分として、後掲する如きカー
ボネート基含有重合性単量体とカルボキシル基含有重合
性単量体とを、それぞれ、特定の使用量で用いることに
より、まず、ポリアミン化合物との相溶性が良好なるカ
ーボネート基含有共重合体が得られること、しかも、当
該カーボネート基含有共重合体とチリアミン化合物とか
ら成る組成物に、さらに硬化助剤としての、含燐化合物
および/または含窒素化合物をも添加配合せしめること
によシ、とりわけ、低温硬化性のすぐれた塗料用樹脂組
成物が得られることをも見い出すに及んで、本発明を完
成させるに到った。However, in view of the various shortcomings in the prior art as described above, the present inventors have conducted intensive studies to develop a new carbonate group-containing copolymer that has good compatibility with polyamine compounds. , by using specific amounts of a carbonate group-containing polymerizable monomer and a carboxyl group-containing polymerizable monomer as described below as essential monomer components of such a carbonate group-containing copolymer. First, a carbonate group-containing copolymer having good compatibility with a polyamine compound can be obtained, and furthermore, a composition comprising the carbonate group-containing copolymer and a thiamine compound may further contain a curing aid. The present invention was completed by discovering that a resin composition for coatings with particularly excellent low-temperature curability can be obtained by adding and blending a phosphorus compound and/or a nitrogen-containing compound. Ta.
すなわち、本発明は必須の成分として、一般式で示され
る重合性単量体(a−’1)C以下、カーゼネート基含
有重合性単量体(a−1)と略記する。〕の00.2〜
90重量と、カルボキシル基含有重合性単量体(a−2
)の0.01〜30重量%と、これら上記の重合性単量
体(a−1)および(a−2)と共重合可能なモノエチ
レン性不飽和単量体(a −3)とを、全単量体の合計
が100重量%となるように共重合させて得られるカー
ブネート基含有共重合体囚と、ポリアミン化合物(B)
と、該カーボネート基含有共重合体(4)に対して0.
0001〜20重量%なる範囲内の、含燐化合物(e
−L)および含窒素化合物(c−2)よりなる群から選
ばれる少なくとも1種の硬化助剤(C)とを含んで成る
、とりわけ低温硬化性にすぐれた塗料用樹脂組成物を提
供しようとするものである。That is, in the present invention, as an essential component, a polymerizable monomer (a-'1) represented by the general formula C is hereinafter abbreviated as a carzenate group-containing polymerizable monomer (a-1). ]00.2~
90 weight and carboxyl group-containing polymerizable monomer (a-2
) and a monoethylenically unsaturated monomer (a-3) copolymerizable with the above polymerizable monomers (a-1) and (a-2). , a carnate group-containing copolymer obtained by copolymerizing so that the total of all monomers is 100% by weight, and a polyamine compound (B)
and 0.0% for the carbonate group-containing copolymer (4).
0001 to 20% by weight of phosphorus-containing compounds (e
-L) and at least one curing aid (C) selected from the group consisting of a nitrogen-containing compound (c-2), and has particularly excellent low-temperature curability. It is something to do.
ここにおいて、まず、前記カーゼネート基含有重合性単
量体(a−1)として代表的なものには、2゜3−カー
ボネートプロピル(メタ)アクリレート、3.4−カー
ブネートブチル(メタ)アクリレート、4.5−カーゼ
ネートペンチル(メタ)アクリレート、5,6−カー?
ネートヘキシル(メタ)アクリレートまたは6,7−カ
ーブネートヘキシル(メタ)アクリレートなどがある。Here, first, typical examples of the carzenate group-containing polymerizable monomer (a-1) include 2゜3-carbonate propyl (meth)acrylate, 3.4-carnate butyl (meth)acrylate, 4.5-carzenate pentyl (meth)acrylate, 5,6-car?
Examples include natehexyl (meth)acrylate and 6,7-carnatehexyl (meth)acrylate.
これらの使用量としては0.2〜90重量%、好ましく
は2〜45重量%なる範囲内が適切である。The appropriate amount of these to be used is 0.2 to 90% by weight, preferably 2 to 45% by weight.
次に、前記(a−2)たるカルボキシル基含有重合性単
量体の代表的なものを挙げれば、(メタ)アクリル酸、
クロトン酸、イタコン酸、マレイン酸、フマル酸、イタ
コン酸モノアルキルエステル、マレイン酸モノアルキル
エステルもしくハフマル酸モノアルキルエステル、また
はβ−ヒドロキシエチル(メタ)アクリレートの如き水
酸基含有ビニル単量体と無水こはく酸もしくは無水トリ
メリット酸の如き酸無水物との付加物などである。そし
て、かかるカルブキシル基含有重合性単量体(a−2)
の使用量としては、後掲する如きポリアミン化合物(B
)との相溶性や、このぼりアミン(B)の混合時におけ
る粘度などの面から、0.01〜30重量%、好ましく
は0.1〜10重量%なる範囲内が適切である。Next, typical examples of the carboxyl group-containing polymerizable monomer (a-2) include (meth)acrylic acid,
Hydroxyl group-containing vinyl monomers such as crotonic acid, itaconic acid, maleic acid, fumaric acid, itaconic acid monoalkyl ester, maleic acid monoalkyl ester or hafumaric acid monoalkyl ester, or β-hydroxyethyl (meth)acrylate and anhydride. These include adducts with acid anhydrides such as succinic acid or trimellitic anhydride. And such carboxyl group-containing polymerizable monomer (a-2)
The amount of polyamine compound (B
) and the viscosity when mixed with the amine (B), a suitable range is 0.01 to 30% by weight, preferably 0.1 to 10% by weight.
また、前記(a−3)たる共重合性モノエチレン性不飽
和単量体としては、前掲された如き、それぞれ、重合性
単量体(a−1)および(a−2)と共重合可能なもの
であれば、いずれも使用できるが、そのうちでも特に代
表的なものを例示するのみに止めれば、(メタ)アクリ
ル酸メチル、(メタ)アクリル酸エチル、(メタ)アク
リル酸プロピル、(メタ)アクリル酸ブチル、(メタ)
アクリル酸−2−エチルヘキシル、(メタ)アクリル酸
ラウリル;スチレン、α−メチルスチレン、p −te
rt−ブチルスチレン、ジメチルスチレン、ビニルトル
エン;(メタ)アクリルアミド、N−メチロール(メタ
)アクリルアミド、ブトキシ(メタ)アクリルアミド;
2−ヒドロキシエチル(メタ)アクリレート、2−ヒド
ロキシプロぎル(メタ)アクリレート、3−ヒドロキシ
ブチル(メタ)アクリレート、4−ヒドロキシブチル(
メタ)アクリレート、3−クロロ−2−ヒドロキシプロ
ピル(メタ)アクリレート、ジー2−ヒドロキシエチル
フマレート、モノ−2−ヒドロキシエチル−モノブチル
フマレート、ポリエチレングリコールモノ(メタ)アク
リレート、ポリゾロ2レンゲリコールモノ(メタ)アク
リレート、「プラクセルFMないしはFAモノマー」〔
ダイセル化学(株)興のカプロラクトン付加モノマー〕
;ジメチルアミノエチル(メタ)アクリレート、ジエチ
ルアミノエチル(メタ)アクリレート;さらには(メタ
)アクリロニトリル、酢酸ビニル、マレイン酸ジエチル
、マレイン酸ジブチル、フマル酸、シブチル、イタコン
酸ジエチ/I/またはイタコン酸ジブチルなどである。In addition, the copolymerizable monoethylenically unsaturated monomer (a-3) can be copolymerized with the polymerizable monomers (a-1) and (a-2), respectively, as listed above. Any of them can be used, but the most representative ones are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. ) Butyl acrylate, (meth)
2-ethylhexyl acrylate, lauryl (meth)acrylate; styrene, α-methylstyrene, p-te
rt-butylstyrene, dimethylstyrene, vinyltoluene; (meth)acrylamide, N-methylol (meth)acrylamide, butoxy (meth)acrylamide;
2-hydroxyethyl (meth)acrylate, 2-hydroxyprogyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (
meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate, polyethylene glycol mono(meth)acrylate, polyzolo 2-hydroxypropyl mono(meth)acrylate (meth)acrylate, "Plaxel FM or FA monomer" [
Caprolactone addition monomer from Daicel Chemical Co., Ltd.]
; dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; further (meth)acrylonitrile, vinyl acetate, diethyl maleate, dibutyl maleate, fumaric acid, sibutyl, diethyl itaconate/I/or dibutyl itaconate, etc. It is.
以上に掲げられた如き各種の単量体を用いて前記カーは
ネート基含有共重合体(4)を調製するには、公知慣用
のいずれの方法によっても可能であるが、そのうち、特
に溶液ラジカル重合法によるのが最も簡便である。In order to prepare the above-mentioned nate group-containing copolymer (4) using the various monomers listed above, it is possible to use any known and commonly used method. The simplest method is the polymerization method.
そのさいには、トルエンやキシレンの如き芳香族炭化水
素系溶剤;ペンタン、ヘキサンもしくはシクロヘキサン
の如き(環状)脂肪族炭化水素系溶剤;酢酸エチル、酢
酸−n−ブチルもしくはエチレングリコールモノメチル
エーテルアセテートの如きエステル系溶剤;アセトン、
メチルエチルケトン、メチルインブチルケトンもしくは
シクロヘキサノンの如きケトン系溶剤;イソプロ・やノ
ール、n−ブタノールもしくはイソブタノールの如きア
ルコール系溶剤などの溶剤類と、アゾ系まだは過酸化物
系の如き公知慣用の重合開始剤とを用いて常法によシ重
合を行々えばよい。In this case, aromatic hydrocarbon solvents such as toluene or xylene; (cyclo)aliphatic hydrocarbon solvents such as pentane, hexane or cyclohexane; such as ethyl acetate, n-butyl acetate or ethylene glycol monomethyl ether acetate are used. Ester solvent; acetone,
Ketone solvents such as methyl ethyl ketone, methyl imbutyl ketone or cyclohexanone; solvents such as alcohol solvents such as isopro-, n-butanol or isobutanol, and known and commonly used polymerizations such as azo-based and peroxide-based solvents. Polymerization may be carried out in a conventional manner using an initiator.
また、重合に際してtert−ドデシルメルカプタン、
ラウリルメルカプタン、チオグリコール酸アルキルエス
テルもしくはβ−メルカプトプロピオン酸の如きメルカ
プタン類やα−メチルスチレンダイマーなどの分子量調
節剤を用いて重合を行うこともできる。In addition, during polymerization, tert-dodecyl mercaptan,
Polymerization can also be carried out using mercaptans such as lauryl mercaptan, thioglycolic acid alkyl ester or β-mercaptopropionic acid, and molecular weight regulators such as α-methylstyrene dimer.
次に、本発明の塗料用樹脂組成物を構成するポリアミン
化合物(B)成分について説明する。Next, the polyamine compound (B) component constituting the coating resin composition of the present invention will be explained.
前記のようにして調製されたカーブネート基含有共重合
体(4)なるペース樹脂成分は、硬化剤成分たる当該ポ
リアミン化合物(B)と混合される。The paste resin component, which is the carnate group-containing copolymer (4) prepared as described above, is mixed with the polyamine compound (B), which is the curing agent component.
かかるポリアミン化合物(B)としては、脂肪族ポリア
ミン、芳香族ポリアミン、複合ポリアミン、変性脂肪族
ぼりアミンまたは複素環式ポリアミンなどの公知慣用の
ポリアミン類から少なくとも1種が適宜選択される。As the polyamine compound (B), at least one kind is appropriately selected from known and commonly used polyamines such as aliphatic polyamines, aromatic polyamines, composite polyamines, modified aliphatic polyamines, and heterocyclic polyamines.
そのうちでも、特に代表的なものを例示するに止めるな
らば、エチレンジアミン、1,2−ジアミノプロパン、
1.3−−/アミノプロノやン、1,4−ジアミノブタ
ン、1,5−ジアミノ4ンタン、1,6.−ジアミノヘ
キサン、■、7−ジアミンへブタン、1゜8−シアミン
オクタン、1,9−ジアミノノナン、■、10−ノアミ
ノデカン、1,2−ノアミノシクロへキサン、1,4−
ビス(3−アミノプロピル)ビベブタン、3,9−ビス
(3−アミノプロピル)−2゜4,8.10−テトラオ
キサスを口[5,5]ウンデカン、ジエチレントリアミ
ン、トリエチレンテトラミン、テトラエチレンペンタミ
ン、ペンタエチレンへキサパン、N、N’−ビス(2−
アミノメチル)エチレンジアミン、 N、N’−ビス(
2−アミノエチル)−エチレンジアミン、N、N’−ビ
ス(3−アミノプロピル)エチレン・シアミン、N、N
′−ヒス(2−アミノメチル)−1,3−ゾロパンジア
ミン、N、N’−ビス(2−アミノエチル) −1,3
−プロノクンノアミン、N、v−ビス(3−アミノゾロ
ビル) −L3−ゾロパンジアミン、N、N−ビス(2
−アミノメチル) −1,4−ブタンジアミン、N、N
’−ビス(2−アミノエチル) −1,4−ブタンジア
ミン、 N、N’−ビス(3−アミノゾロピル) −1
,4−ブタンジアミン、ビス(4−アミノシクロヘキシ
ル)メタンもしくは1,3−ビス(アミノメチル)シク
ロヘキサンまたは[ジェファーミン D−230もしく
はD−400J [三片テキサコケミカル(株)製品〕
の如き三官能1級アミン化合物、あるいはトリスアミノ
エチルアミンもしくは4−アミノメチル−1,8−ジア
ミノオクタンまたは「ジェファーミンT−403J (
同上社製品)の如き三官能1級アミン化合物をはじめ、
酸基含有アクリル樹脂−ゾロピレンイミン付加物、ポリ
エポキシ化合物−ポリアミン付加物、
あるいはオリゴエステル(メタ)アクリレートと前掲
された如き各種ポリアミン化合物との付加物などである
。Among them, ethylenediamine, 1,2-diaminopropane,
1.3--/aminopronoyan, 1,4-diaminobutane, 1,5-diaminobutane, 1,6. -diaminohexane, ■, 7-diaminehebutane, 1°8-cyamine octane, 1,9-diaminonane, ■, 10-noaminodecane, 1,2-noaminocyclohexane, 1,4-
Bis(3-aminopropyl)bibebutane, 3,9-bis(3-aminopropyl)-2゜4,8.10-tetraoxas, [5,5]undecane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, Pentaethylene hexapane, N,N'-bis(2-
aminomethyl)ethylenediamine, N,N'-bis(
2-aminoethyl)-ethylenediamine, N,N'-bis(3-aminopropyl)ethylene cyamine, N,N
'-His(2-aminomethyl)-1,3-zolopanediamine, N,N'-bis(2-aminoethyl)-1,3
-pronocunnnoamine, N,v-bis(3-aminozorobyl) -L3-zolopanediamine, N,N-bis(2
-aminomethyl) -1,4-butanediamine, N,N
'-bis(2-aminoethyl)-1,4-butanediamine, N,N'-bis(3-aminozolopyl)-1
, 4-butanediamine, bis(4-aminocyclohexyl)methane or 1,3-bis(aminomethyl)cyclohexane or [Jeffamine D-230 or D-400J [Mikata Texaco Chemical Co., Ltd. product]
or trisaminoethylamine or 4-aminomethyl-1,8-diaminooctane or "Jeffamine T-403J (
Including trifunctional primary amine compounds such as
Acid group-containing acrylic resin-zolopyreneimine adduct, polyepoxy compound-polyamine adduct,
Alternatively, they are adducts of oligoester (meth)acrylate and various polyamine compounds as listed above.
また、ポリアミド樹脂も使用することができるのは勿論
であシ、公知慣用のものであれば、いずれのs9リアミ
ド樹脂も使用できるが、そのうちでも代表的なものとし
ては、「ラッカマイト」〔犬日本インキ化学工業(株)
製品〕、「トーマイド」〔富士化成工業(株)製品〕ま
たは「サンマイド」〔三和化学工業(株)製品〕の如き
ポリアミドアミン系樹脂などが挙げられる。Of course, polyamide resins can also be used, and any known and commonly used S9 lyamide resins can be used, but the representative one is ``laccamite'' [Inu Nippon Ink Chemical Industry Co., Ltd.
Examples include polyamide amine resins such as "Tomide" (product of Fuji Kasei Kogyo Co., Ltd.) and "Sanmide" (product of Sanwa Kagaku Kogyo Co., Ltd.).
そして、当該ポリアミン化合物(B)と前掲のカーブネ
ート基含有共重合体(4)との配合比としては、カーボ
ネート基/1級アミン基なる当量比が05〜2、好まし
くは0.8〜1゜2なる範囲内にあるのが適切であり、
良好な塗膜性能を与える。The blending ratio of the polyamine compound (B) and the above-mentioned carnate group-containing copolymer (4) is such that the equivalent ratio of carbonate group/primary amine group is 05 to 2, preferably 0.8 to 1. It is appropriate that it is within the range of ゜2,
Gives good coating performance.
この場合において、2を超える場合には、どうしても硬
化が不十分となり、塗膜性能が劣るようになるし、一方
、0.5未満の場合には、カーブネート基含有共重合体
(A)とポリアミン化合物(B)との相溶性が劣るよう
になり、これらの混合物が白濁し易くなるので、いずれ
も好ましくない。In this case, if it exceeds 2, curing will inevitably be insufficient and the coating performance will deteriorate, while if it is less than 0.5, the carnate group-containing copolymer (A) Both are unfavorable because the compatibility with the polyamine compound (B) becomes poor and the mixture thereof tends to become cloudy.
また、本発明の塗料用樹脂組成物を構成する、さらにも
う一つの必須成分たる、前記した含燐化合物(e−1)
と含窒素化合物(e−2)なる硬化助剤(Cりについて
説明することにする。Further, the above-mentioned phosphorus-containing compound (e-1) is another essential component constituting the coating resin composition of the present invention.
The hardening aid (C), which is a nitrogen-containing compound (e-2), will be explained below.
そのうちのまず、含燐化合物(c−1)として代表的な
ものを挙げれば、トリエチルホスフィン、トリエチルホ
スフィン、トリブチルホスフィン、トリペンチルホスフ
ィン、トリへキシルホスフィン、トリへブチルホスフィ
ン、トリオクチルホスフィン、トリノニルホスフィン、
トリデシルホスフィン、トリシクロへキシルホスフィン
、ジメチルフェニルホスフィン、ジエチルフェニルホス
フィン、ジプロピルフェニルホスフィン、ジブチルフェ
ニルホスフィン、・クシクロヘキシルフェニルホスフィ
ン、メチルジフェニルホスフィン、エチルジフェニルホ
スフィン、プロピルジフェニルホスフィン、ブチルジフ
ェニルホスフィン、シクロヘキシルジフェニルホスフィ
ン、ビス(ジフェニルホスフィン)メタン、1,2−ビ
ス(、ジフェニルホスフィノ)エタン、1,2−ビス(
ジフェニルホスフィノ)エチレン、1.4−ビス(ジフ
ェニルホスフォノ)ブタン、トリフェニルホスフィン、
トリー〇−)リルホスフィン、トリーm−)リルホスフ
ィン、トリーp−)リルホスフィン、ジフェニル(0−
トリル)ホスフィン、ジフェニル(m−トリル)ホスフ
ィンまたはジフェニル(p−)リル)ホスフィンの如き
3配位の有機燐化合物などであるし、さらにはテトラブ
チルホスホニウムブロマイド、テトラブチルホスホニウ
ムクロライド、テトラブチルホスホニウムノ1イドロオ
キサイド、メチルトリフェニルブロマイド、メチルトリ
フェニルクロライド、メチルトリフェニルアイオダイド
、ブロモメチルトリフェニルホスホニウムブロマイド、
クロロメチルトリフェニルホスホニウムクロライド、ビ
ニルトリフェニルホスホニウムクロライド、エチルトリ
フェニルホスホニウムブロマイド、2−ヒドロキシエチ
ルブロマイド、2−ヒドロキシエチルクロライド、メト
キシメチルトリフェニルホスホニウムブロマイド、メト
キシメチルトリフェニルホスホニウムクロライド、プロ
/4′ゾルトリフエニルホスホニウムブロマイド、プロ
パジルトリフェニルホスホニウムクロライド、カルがメ
トキシメチルトリフェニルホスホニウムブロマイド、カ
ルデメトキシメチルトリフェニルホスホニウムクロライ
ド、アリルトリフェニルホスホニウムブロマイド、アリ
ルトリフェニルホスホニウムクロライド、シクロゾロぎ
ルトリフェニルホスホニウムブロマイド、シクロゾロぎ
ルトリフェニルクロライド、アセトニルトリフェニルホ
スホニウムブロマイド、アセトニルトリフェニルホスホ
ニウムクロライド、プロピルトリフェニルホスホニウム
ブロマイド、ブロールトリフェニルホスホニウムクロラ
イド、(カルベトキシメチル)トリフェニルホスホニウ
ムブロマイド、(カルベトキシメチル)トリフェニルホ
スホニウムクロライド、1.3−・ジオキソラン−2−
イル−メチルトリフェニルホスホニウムブロマイド、1
.3−ジオキソラン−2−イル−メチルトリフェニルホ
スホニウムクロライド、ブチルトリフェニルホスホニウ
ムブロマイド、ブチルトリフェニルホスホニウムクロラ
イr1 (2−ツメチルアミノエチル)トリフェニルホ
スホニウムブロマイド、(2−ジメチルアミノエチル)
トリフェニルホスホニウムクロライド、(4−カルボキ
シブチル)トリフェニルホスホニウムブロマイド、(4
−カルボキシブチル)トリフェニルホスホニウムクロラ
イド、(2−(1,3−ジオキサン−2−イル)−エチ
ルトリフェニルホスホニウムブロマイド、[2−(1,
3−ジオキサン−2−イル)−エチル〕トリノェニルホ
スホニウムクロライ)’ 、2− ヒトo キシベンジ
ルトリフェニルホスホニウムブロマイド、2−ヒドロキ
シベンジルトリフェニルホスホニウムクロライド、ベン
ジルトリフェニルホスホニウムブロマイド、ベンジルト
リフェニルホスホニウムクロライド、フェナシルトリフ
ェニルホスホニウムブロマイド、フェナシルトリフェニ
ルホスホニウムクロライド、(4−エトキシベンジル)
トリフェニルホスホニウムブロマイド、(4−エトキシ
ベンジル)トリフェニルホスホニウムクロライド、p−
キシリレンビス(トリフェニルホスホニウムブロマイド
>−thはp−キシリレンビス(トリフェニルホスホニ
ウムクロライド)の如キ4配位の有機燐化合物などであ
る。First of all, typical phosphorus-containing compounds (c-1) include triethylphosphine, triethylphosphine, tributylphosphine, tripentylphosphine, trihexylphosphine, trihebutylphosphine, trioctylphosphine, and trinonyl. phosphine,
Tridecylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, diethylphenylphosphine, dipropylphenylphosphine, dibutylphenylphosphine, cyclohexylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, propyldiphenylphosphine, butyldiphenylphosphine, cyclohexyldiphenyl Phosphine, bis(diphenylphosphine)methane, 1,2-bis(,diphenylphosphino)ethane, 1,2-bis(
diphenylphosphino)ethylene, 1,4-bis(diphenylphosphono)butane, triphenylphosphine,
tri〇-)lylphosphine, tri-m-)lylphosphine, tri-p-)lylphosphine, diphenyl(0-
These include three-coordinated organic phosphorus compounds such as tolyl)phosphine, diphenyl(m-tolyl)phosphine, and diphenyl(p-)lyl)phosphine, as well as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, and tetrabutylphosphonium bromide. 1hydroxide, methyltriphenyl bromide, methyltriphenyl chloride, methyltriphenyl iodide, bromomethyltriphenylphosphonium bromide,
Chloromethyltriphenylphosphonium chloride, vinyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, 2-hydroxyethyl bromide, 2-hydroxyethyl chloride, methoxymethyltriphenylphosphonium bromide, methoxymethyltriphenylphosphonium chloride, pro/4' sol Triphenylphosphonium bromide, propadyltriphenylphosphonium chloride, calmethoxymethyltriphenylphosphonium bromide, caldemethoxymethyltriphenylphosphonium chloride, allyltriphenylphosphonium bromide, allyltriphenylphosphonium chloride, cyclozologyltriphenylphosphonium bromide, cyclozologyl triphenyl chloride, acetonyltriphenylphosphonium bromide, acetonyltriphenylphosphonium chloride, propyltriphenylphosphonium bromide, brorotriphenylphosphonium chloride, (carbetoxymethyl)triphenylphosphonium bromide, (carbetoxymethyl)triphenylphosphonium chloride, 1.3-・dioxolane-2-
yl-methyltriphenylphosphonium bromide, 1
.. 3-dioxolan-2-yl-methyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium chloride r1 (2-trimethylaminoethyl)triphenylphosphonium bromide, (2-dimethylaminoethyl)
Triphenylphosphonium chloride, (4-carboxybutyl)triphenylphosphonium bromide, (4
-carboxybutyl)triphenylphosphonium chloride, (2-(1,3-dioxan-2-yl)-ethyltriphenylphosphonium bromide, [2-(1,
3-Dioxan-2-yl)-ethyl trinoenylphosphonium chloride)', 2-hydroxybenzyltriphenylphosphonium bromide, 2-hydroxybenzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride , phenacyltriphenylphosphonium bromide, phenacyltriphenylphosphonium chloride, (4-ethoxybenzyl)
Triphenylphosphonium bromide, (4-ethoxybenzyl)triphenylphosphonium chloride, p-
Xylylene bis(triphenylphosphonium bromide>-th) is a four-coordinated organic phosphorus compound such as p-xylylene bis(triphenylphosphonium chloride).
次いで、前記した含窒素化合物(c−2)として代表的
なものを挙げればビリジ/、2−ヒドロキシピリジン、
1,5−ジアザビシクロ[3,4,0]ノネン−5,1
,8−ジアザビシクロ[5,4,O]ラウンセン−7ま
たは1,4−ジアザビシクロ(2,2,2]オクタンな
どである。Next, typical examples of the nitrogen-containing compound (c-2) include pyridine/, 2-hydroxypyridine,
1,5-diazabicyclo[3,4,0]nonene-5,1
, 8-diazabicyclo[5,4,O]laurensen-7 or 1,4-diazabicyclo(2,2,2]octane.
止揚された如き含燐化合物および/まだは含窒素化合物
たる硬化助剤(C)の使用量としては、前記カー?ネー
ト基含有共重合体(4)に対して0.0001〜20重
量%、好ましくはo、o o i〜10重量%なる範囲
内が適切である。The amount of the curing aid (C) which is a phosphorus-containing compound and/or a nitrogen-containing compound that has been submerged is as follows: A suitable range is from 0.0001 to 20% by weight, preferably from o, o oi to 10% by weight, based on the nate group-containing copolymer (4).
0.0001未満では、硬化助剤としての効果が、どう
しても期待し得なく々るし、一方、20重量%を超える
場合には、どうしても、黄変性や耐薬品性などの塗膜性
能が劣るように寿るので、いずれも好ましくない。If it is less than 0.0001, the effect as a curing aid cannot be expected. On the other hand, if it exceeds 20% by weight, the coating film performance such as yellowing and chemical resistance will inevitably deteriorate. Both are undesirable because they last for a long time.
かくして得られる本発明の塗料用樹脂組成物は、その−
itクリヤー塗料として使用することもできるし、さら
に顔料を混合することによシエナメル塗料として使用す
ることもできる。The coating resin composition of the present invention thus obtained has -
It can be used as a clear paint, or by mixing pigments, it can be used as a enamel paint.
また、本発明組成物には、さらに必要に応じて、レベリ
ング剤、紫外線吸収剤まだは顔料分散剤などの各種の慣
用の添加剤を配合することもできるし、また、ケトン系
の溶剤を希釈シンナーとして用いることにより、ポット
ライフを長することもできるし、塗膜外観を向上させる
こともできるし、さらには公知慣用のセルロース系化合
物、可塑剤、まだはポリエステル樹脂の如き他の樹脂成
分をも併用することができる。Furthermore, the composition of the present invention may further contain various conventional additives such as leveling agents, ultraviolet absorbers, pigment dispersants, etc., as required, and may also be used to dilute ketone solvents. By using it as a thinner, it is possible to extend the pot life, improve the appearance of the coating film, and also add other resin components such as well-known and commonly used cellulose compounds, plasticizers, and even polyester resins. can also be used together.
かくして得られる本発明の低温硬化性にすぐれる塗料用
樹脂組成物は、ゾラスチックス、金属、木材、建材また
は無機質基材などといっだ多岐に亘る素材ないしは加工
品の塗装に極めて有用なものである。The thus obtained coating resin composition of the present invention with excellent low-temperature curability is extremely useful for coating a wide variety of materials or processed products such as Zolastics, metals, wood, building materials, and inorganic base materials. .
また、塗装方法としては、刷毛塗り、スプレ塗装または
ロール塗装などの如き常用の方法が採用でき、硬化方法
としては、常温乾燥から加熱乾燥までの幅広い範囲で、
本発明の塗料用樹脂組成物を構成する共重合体成分(A
)と架橋剤成分(B)との組合わせに応じた最適の硬化
条件が設計できる。In addition, as a coating method, commonly used methods such as brush coating, spray coating, or roll coating can be adopted, and as a curing method, a wide range of methods can be used, from drying at room temperature to drying with heat.
The copolymer component (A
) and crosslinking agent component (B) can be designed to suit the combination.
次に、本発明を参考例、実施例および比較例によシー層
具体的に説明するが、以下において特に断シのない限シ
、部および饅はすべて重量基準であるものとする。Next, the present invention will be explained in detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, unless otherwise specified, all terms, parts, and parts are based on weight.
参考例1〔カーブネート基含有共重合体(4)の調製例
〕
温度計、攪拌機、滴下漏斗、窒素導入管および冷却器を
備えた反応器に、トルエン700部を仕込んで窒素界囲
気中で110℃に昇温し、次いでことにスチレン300
部、メチルメタクリレート200部、n−ブチルアクリ
レート95部、アクリル酸5部、2,3−カーぜネート
プロピルメタクリレート400部、アゾビスイソブチロ
ニドIJ /l/(ATBN)の10部、tert−ブ
チルパーオキシオクトエ−)(TBPO)の10部、t
art−ブチルパーオキシベンゾエート(TBPB )
の5部およびトルエン300部からなる混合物を3時間
に亘って滴下し、しかるのち同温度に15時間保持して
反応を進行させた。これにより不揮発分(NV)が50
.2%で、かつ数平均分子量(扁)が13,700なる
カーボネト基を有するビニル共重合体の溶液を得た。以
下これをビニル共重合体(A−1)と略記する。Reference Example 1 [Example of Preparation of Carnate Group-Containing Copolymer (4)] 700 parts of toluene was charged into a reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a condenser, and the mixture was heated in a nitrogen atmosphere. The temperature was raised to 110°C, and then the styrene was heated to 300°C.
parts, 200 parts of methyl methacrylate, 95 parts of n-butyl acrylate, 5 parts of acrylic acid, 400 parts of 2,3-carzenatopropyl methacrylate, 10 parts of azobisisobutyronide IJ/l/(ATBN), tert- 10 parts of butyl peroxyoctoate (TBPO), t
art-butyl peroxybenzoate (TBPB)
A mixture consisting of 5 parts of and 300 parts of toluene was added dropwise over 3 hours, and the reaction was then maintained at the same temperature for 15 hours to allow the reaction to proceed. This results in a non-volatile content (NV) of 50
.. A solution of a vinyl copolymer having carbonate groups with a concentration of 2% and a number average molecular weight (diameter) of 13,700 was obtained. Hereinafter, this will be abbreviated as vinyl copolymer (A-1).
参考例2〜4(同上)
第1表に示されるような単量体混合物を用いる以外は、
参考例1と同様の操作を繰シ返して各種ビニル共重合体
の溶液(A−2)〜(A−4)を得た。Reference Examples 2 to 4 (same as above) Except for using a monomer mixture as shown in Table 1,
The same operation as in Reference Example 1 was repeated to obtain various vinyl copolymer solutions (A-2) to (A-4).
参考例5(比較対照用のビニル共重合体の調製例)第1
表に示されるような単量体混合物を用いるように変更し
た以外は、参考例1と同様にして対照用のビニル共重合
体溶液を得だ。以下、これをビニル共重合体(A’−1
)と略記する。Reference example 5 (preparation example of vinyl copolymer for comparison) 1st
A control vinyl copolymer solution was obtained in the same manner as in Reference Example 1, except that a monomer mixture as shown in the table was used. Hereinafter, this will be referred to as vinyl copolymer (A'-1
).
それぞれの樹脂溶液の性状値(不揮発分、粘度およびM
n )を第1表にまとめて示す。Properties of each resin solution (non-volatile content, viscosity and M
n) are summarized in Table 1.
実施例1〜5および比較例1〜9
各参考例で得られたそれぞれのビニル共重合体溶液をペ
ース樹脂成分として用い、かつ、第2表(1)に示され
るような配合比でクリヤー塗料を得た。Examples 1 to 5 and Comparative Examples 1 to 9 Each vinyl copolymer solution obtained in each reference example was used as a paste resin component, and a clear paint was prepared at the compounding ratio shown in Table 2 (1). I got it.
ただし、同表中の希釈溶剤の欄における各溶剤の略号は
、それぞれ次の通りである。However, the abbreviations for each solvent in the column of diluting solvent in the same table are as follows.
MEK・・・メチルエチルケトン、 n−BuOH
・・・n−ブタノール次いで、それぞれの塗料を希釈溶
剤を用いてスプレー粘度にまで希釈した。それぞれの希
釈塗料について保存安定性の評価を行なうと共に、これ
らの各希釈塗料から経時的に得られる乾燥硬化塗膜につ
いて、その都度、ダル分率を測定して、低温硬化性の評
価をも行ない、両性能の結果を同表にまとめて示した。MEK...methyl ethyl ketone, n-BuOH
... n-Butanol Each paint was then diluted to spray viscosity using a diluting solvent. In addition to evaluating the storage stability of each diluted paint, we also evaluated the low-temperature curability by measuring the dull fraction of each dry-cured film obtained from each diluted paint over time. The results of both performances are summarized in the same table.
引き続いて、上記各希釈塗料をガラス板およびポリプロ
ピレン板に、各別に、スプレー塗装し、しかるのち、室
温(25℃)で7日間かけて乾燥硬化せしめた。Subsequently, each of the above-mentioned diluted paints was spray-coated on a glass plate and a polypropylene plate, respectively, and then dried and cured at room temperature (25°C) for 7 days.
かくして得られた各硬化塗膜について性能評価を行なっ
た処、第2表(2)に示すような結果が得られた。Performance evaluation was performed on each cured coating film thus obtained, and the results shown in Table 2 (2) were obtained.
/
/
第2表(2)の結果より明らか々ように、本発明で使用
されるカーボネート基含有共重合体は硬化剤である。3
9 リアミン化合物と相溶性が良く、かつ優れた硬化物
を与えるものであることが知れる。とくに、本発明組成
物は低温硬化性にすぐれるほか、透明性が良好で、かつ
外観にもすぐれた塗膜を付与するものであることが知れ
る。/ / As is clear from the results in Table 2 (2), the carbonate group-containing copolymer used in the present invention is a curing agent. 3
9 It is known that it has good compatibility with lyamine compounds and provides an excellent cured product. In particular, it is known that the composition of the present invention not only has excellent low-temperature curability, but also provides a coating film with good transparency and excellent appearance.
本発明の塗料用樹脂組成物は、そのベース樹脂成分とし
て用いられている、それぞれ、カーボネート基含有重合
性単量体とカル?キシル基含有重合性単量体とを必須の
共重合成分として調製されたカーボネート基含有共重合
樹脂それ自体が、硬化剤としてのポリアミン化合物と極
めて良い相溶性を示すものである処から、こうした良好
な相溶性に起因して、すぐれた硬化物を与えることがで
きるものである。The coating resin composition of the present invention has a carbonate group-containing polymerizable monomer and a carbonate group-containing polymerizable monomer, which are used as base resin components, respectively. This favorable result is due to the fact that the carbonate group-containing copolymer resin itself, prepared with a xyl group-containing polymerizable monomer as an essential copolymerization component, exhibits extremely good compatibility with the polyamine compound as a curing agent. Due to their excellent compatibility, they can provide excellent cured products.
本発明にあっては、カーボネート基含有共重合樹脂とポ
リアミン硬化剤とから成る組成物それ自体でも、低温硬
化性にすぐれている処から、各種基材に対し、かかる低
温硬化によってすぐれた物性の硬化被膜を形成すること
ができるのは勿論、さらに硬化助剤をも含んで成る組成
物は、とりわけ、−層すぐれた低温硬化性を発揮するも
のである。In the present invention, since the composition itself consisting of a carbonate group-containing copolymer resin and a polyamine curing agent has excellent low-temperature curability, it can be applied to various substrates with excellent physical properties by such low-temperature curing. A composition that not only can form a cured film but also contains a curing aid exhibits particularly excellent low-temperature curability.
代理人 弁理士 高 橋 勝 利Agent: Patent Attorney Katsutoshi Takahashi
Claims (1)
とし、またnは1から4までの整数であるものとする。 で示される重合性単量体(a−1)の0.2〜90重量
%と、カルボキシル基含有重合性単量体(a−2)の0
.01〜30重量%と、 上記重合性単量体(a−1)および(a−2)と共重合
可能な他のモノエチレン性不飽和単量体(a−3)とを
、全単量体の総量が100重量%となるように共重合さ
せて得られるカーボネート基含有共重合体(A)と、ポ
リアミン化合物(B)と、上記カーボネート基含有共重
合体(A)に対して0.0001〜20重量%なる範囲
内の、含燐化合物(c−1)および含窒素化合物(c−
2)よりなる群から選ばれる少なくとも1種の硬化助剤
(C)とを必須成分として含んで成る、低温硬化性にす
ぐれた塗料用樹脂組成物。[Claims] (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] However, R in the formula represents a hydrogen atom or a methyl group, and n is an integer from 1 to 4. shall be. 0.2 to 90% by weight of the polymerizable monomer (a-1) represented by
.. 01 to 30% by weight and another monoethylenically unsaturated monomer (a-3) copolymerizable with the polymerizable monomers (a-1) and (a-2), based on the total monomer content. A carbonate group-containing copolymer (A) obtained by copolymerizing so that the total amount of the carbonate group-containing copolymer (A) is 100% by weight, and a polyamine compound (B). 0001 to 20% by weight of phosphorus-containing compound (c-1) and nitrogen-containing compound (c-
2) A resin composition for coatings with excellent low temperature curability, which comprises as an essential component at least one curing aid (C) selected from the group consisting of:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20461988A JP2705131B2 (en) | 1988-08-19 | 1988-08-19 | Resin composition for coatings with excellent low-temperature curability |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20461988A JP2705131B2 (en) | 1988-08-19 | 1988-08-19 | Resin composition for coatings with excellent low-temperature curability |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0253880A true JPH0253880A (en) | 1990-02-22 |
JP2705131B2 JP2705131B2 (en) | 1998-01-26 |
Family
ID=16493477
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20461988A Expired - Fee Related JP2705131B2 (en) | 1988-08-19 | 1988-08-19 | Resin composition for coatings with excellent low-temperature curability |
Country Status (1)
Country | Link |
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JP (1) | JP2705131B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5712363A (en) * | 1993-01-06 | 1998-01-27 | Akzo Nobel Nv | Oligomeric sterically hindered polyamine crosslinkers and coating compositions containing the same |
CN103459481A (en) * | 2011-03-31 | 2013-12-18 | 巴斯夫欧洲公司 | Two-component coating compositions |
JP2016507608A (en) * | 2012-12-19 | 2016-03-10 | アルケマ フランス | Organic resins having cyclic carbonate groups and aqueous dispersions for crosslinked polyurethanes |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9238764B2 (en) * | 2011-03-31 | 2016-01-19 | Basf Se | Two-component coating compositions |
-
1988
- 1988-08-19 JP JP20461988A patent/JP2705131B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5712363A (en) * | 1993-01-06 | 1998-01-27 | Akzo Nobel Nv | Oligomeric sterically hindered polyamine crosslinkers and coating compositions containing the same |
CN103459481A (en) * | 2011-03-31 | 2013-12-18 | 巴斯夫欧洲公司 | Two-component coating compositions |
JP2016507608A (en) * | 2012-12-19 | 2016-03-10 | アルケマ フランス | Organic resins having cyclic carbonate groups and aqueous dispersions for crosslinked polyurethanes |
Also Published As
Publication number | Publication date |
---|---|
JP2705131B2 (en) | 1998-01-26 |
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