JP5924815B2 - Low contamination paint composition - Google Patents
Low contamination paint composition Download PDFInfo
- Publication number
- JP5924815B2 JP5924815B2 JP2012100034A JP2012100034A JP5924815B2 JP 5924815 B2 JP5924815 B2 JP 5924815B2 JP 2012100034 A JP2012100034 A JP 2012100034A JP 2012100034 A JP2012100034 A JP 2012100034A JP 5924815 B2 JP5924815 B2 JP 5924815B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerizable unsaturated
- meth
- component
- unsaturated monomer
- acrylate
- 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.)
- Active
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- 239000003973 paint Substances 0.000 title claims description 51
- 238000011109 contamination Methods 0.000 title claims description 48
- 239000000203 mixture Substances 0.000 title claims description 33
- -1 acrylic polyol Chemical class 0.000 claims description 87
- 238000000576 coating method Methods 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 66
- 125000003277 amino group Chemical group 0.000 claims description 38
- 229920005862 polyol Polymers 0.000 claims description 38
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 239000008199 coating composition Substances 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 14
- 239000005056 polyisocyanate Substances 0.000 claims description 14
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 claims description 3
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims description 3
- KZFDTCQVSIKDRH-UHFFFAOYSA-N 3-chloro-n,n-dimethylpropan-1-amine;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CN(C)CCCCl KZFDTCQVSIKDRH-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 67
- 239000011248 coating agent Substances 0.000 description 59
- 239000002904 solvent Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000006224 matting agent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 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 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- 239000005453 ketone based solvent Substances 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000012170 montan wax Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 1
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- GYRLUVSVUQTJAM-UHFFFAOYSA-M 3-aminopropyl-ethyl-dimethylazanium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CC[N+](C)(C)CCCN GYRLUVSVUQTJAM-UHFFFAOYSA-M 0.000 description 1
- QBSUYSSJHXRRIL-UHFFFAOYSA-N 3-chloro-n,n-diethyl-3-phenylpropan-1-amine Chemical compound CCN(CC)CCC(Cl)C1=CC=CC=C1 QBSUYSSJHXRRIL-UHFFFAOYSA-N 0.000 description 1
- NYYRRBOMNHUCLB-UHFFFAOYSA-N 3-chloro-n,n-dimethylpropan-1-amine Chemical class CN(C)CCCCl NYYRRBOMNHUCLB-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
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- PZOOLKGCOFWELU-UHFFFAOYSA-N tributyl propyl silicate Chemical compound CCCCO[Si](OCCC)(OCCCC)OCCCC PZOOLKGCOFWELU-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は低汚染塗料組成物に関する。 The present invention relates to a low contamination coating composition.
従来、建築物に代表される屋外の基材には、装飾又は保護を目的として耐候性に優れた塗料が塗装されている。 2. Description of the Related Art Conventionally, paints having excellent weather resistance are painted on outdoor base materials represented by buildings for the purpose of decoration or protection.
一般に塗膜は屋外で長期間の暴露により、砂塵、鉄粉、雨（酸性雨）、太陽光線などの影響によって塗膜表面が汚れ易くなり塗膜外観が悪くなる。 In general, when a coating film is exposed outdoors for a long period of time, the surface of the coating film tends to become dirty due to the influence of dust, iron powder, rain (acid rain), sunlight, etc., and the appearance of the coating film deteriorates.
かかる問題点に関する建築塗料の分野の市場のひとつの方向性として、雨だれによる汚染防止特性を有する塗料、いわゆる低汚染塗料に対する市場ニーズがある。 As one direction of the market in the field of architectural coatings related to such problems, there is a market need for coatings having anti-pollution properties due to raindrops, so-called low-pollution coatings.
こうした市場ニーズに応えるべく、本出願人は特許文献１において、塗料中に特定のオルガノシリケートおよび／又はその縮合物を配合する技術を提案した。 In order to meet such market needs, the present applicant has proposed a technique for blending a specific organosilicate and / or a condensate thereof into a paint in Patent Document 1.
オルガノシリケートおよび／又はその縮合物を低汚染化剤として使用する技術は、塗膜形成過程でオルガノシリケート縮合物を有効に塗膜表層又はその近傍に配向させる技術である。
そして特許文献１には、記載の塗料から形成された塗膜は、その塗膜表面層又はその近傍に、オルガノシリケート又はその縮合物成分の多い層で形成されかつ該オルガノシリケート又はその縮合物は雨水等により加水分解し、高分子量化（縮合）するので塗膜が形成された初期の段階から油性の汚染物質の付着し難く、付着したとしても雨水などで洗い流してしまうという性質（低汚染性）及び耐久性に優れた効果を発揮することが記載されている。
一方、近年、環境や健康に与える影響を考慮し、トルエンやキシレンなどの溶解力の強い、いわゆる強溶剤を含む強溶剤系塗料から、ミネラルスピリットなどの溶解力の弱い溶剤いわゆる弱溶剤を用いた弱溶剤系塗料への転換が進められている。
The technique of using an organosilicate and / or its condensate as a low contamination agent is a technique for effectively orienting the organosilicate condensate on the surface of the coating film or in the vicinity thereof in the coating film forming process.
And in patent document 1, the coating film formed from the coating material of description is formed in the coating-film surface layer or its vicinity with the layer with many organosilicate or its condensate components, and this organosilicate or its condensate is Since it is hydrolyzed by rainwater, etc., and becomes high molecular weight (condensation), it is difficult for oily contaminants to adhere from the initial stage when the coating film is formed, and even if it adheres, it is washed away with rainwater (low contamination) ) And exhibiting excellent durability.
On the other hand, in recent years, taking into consideration the impact on the environment and health, so-called weak solvents such as mineral spirits were used from strong solvent-based paints containing strong solvents such as toluene and xylene, so-called strong solvents. Conversion to weak solvent paints is underway.
弱溶剤系塗料は、耐溶剤性が不十分な旧塗膜であっても、該旧塗膜を侵さずに建築用塗り替え市場に求められる性能を好適に具備しているために、その需要は近年益々拡大している。 Weak solvent-based paints, even for old paint films with insufficient solvent resistance, have the performance required for the architectural repainting market without damaging the old paint film, so the demand is It has been increasing in recent years.
そのような状況の中、特許文献２においては弱溶剤系の低汚染性を有する塗料組成物が提案されている。 Under such circumstances, Patent Document 2 proposes a coating composition having a weak solvent-based low contamination property.
特許文献２の記載によれば、官能基としてアミノ基及び水酸基を有するシリコーン変性分散型樹脂、イソシアネート化合物及び特定のオルガノシリケート化合物を含むことで、塗装作業性が良好であり、低汚染性塗膜を形成する弱溶剤系の塗料が得られるというものである。 According to the description of Patent Document 2, the coating workability is good by including a silicone-modified dispersed resin having an amino group and a hydroxyl group as a functional group, an isocyanate compound, and a specific organosilicate compound, and a low-fouling coating film. It is said that a weak solvent-based paint that forms can be obtained.
ところで、一般に建築塗料の塗装現場では塗料を一回塗装して乾燥させてからもう一度同じ塗料を塗り重ねる、いわゆる２回塗り塗装が頻繁に行われている。 By the way, in general, at the building paint application site, so-called twice-painting is frequently performed in which the paint is applied once and dried, and then the same paint is applied again.
しかしながら上記特許文献１及び２記載の塗料では、２回塗り塗装した場合に、通常であれば問題とならない場合でも、１回目の塗装と２回目の塗装のインターバル時間が長くなったときに、１回目と２回目の塗装との間でハガレが生じるというような、１層目と２層目との層間付着性が十分ではない場合がある。 However, in the paints described in Patent Documents 1 and 2, when the coating is performed twice, even if there is no problem if it is normal, when the interval time between the first coating and the second coating becomes long, 1 In some cases, the adhesion between the first layer and the second layer, such that peeling occurs between the first and second coatings, is not sufficient.
そもそもオルガノシリケート化合物を含む低汚染塗料は塗膜形成時にオルガノシリケート化合物が表層に移行し、汚れ物質の付着し難い塗膜になると考察されており、低汚染性塗料の層間付着性を改善するのは極めて困難である。 In the first place, it is considered that low-contamination paints containing organosilicate compounds will transfer to the surface layer during coating film formation, resulting in coatings that are difficult to adhere to dirt substances, improving the inter-layer adhesion of low-contamination paints. Is extremely difficult.
本発明は、層間付着性と低汚染性を有する塗膜を形成するのに適する低汚染塗料組成物を提供することにある。 An object of the present invention is to provide a low-contamination coating composition suitable for forming a coating film having interlayer adhesion and low contamination.
本発明者らは上記した課題に対して鋭意検討した結果、低汚染塗料組成物を構成する特定組成の主剤成分に、特定量のアミノ基を含ませることで低汚染性を有し、且つ塗り重ね時の層間付着性が向上することを見出し、本発明に到達した。 As a result of intensive studies on the above-mentioned problems, the inventors of the present invention have a low contamination property by adding a specific amount of amino groups to the main component of a specific composition constituting the low-contamination coating composition. The inventors have found that the adhesion between the layers at the time of stacking is improved, and have reached the present invention.
即ち本発明は、
１．樹脂成分（Ａ）及び有機溶剤（Ｂ）を含む主剤成分（Ｉ）と、ポリイソシアネート化合物（Ｃ）を含む硬化剤成分（II）とを組み合わせてなる２液型の組成物であって、
主剤成分（Ｉ）又は硬化剤成分（II）のいずれか又は双方が顔料分（Ｄ）及び／又はオルガノシリケート化合物（Ｅ）を含むものであり、
樹脂成分（Ａ）がその成分の一部として、アミノ基及び／又は４級アンモニウム基を含有するアクリルポリオール（Ａ−１）並びにアミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）を共に含むものであり、
アクリルポリオール（Ａ−１）が、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノプロピルメタクリレート、ジメチルアミノプロピルアクリルアミド、メタクリル酸ジメチルアミノエチルメチルクロライド塩から選ばれる少なくとも１種のアミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマー、水酸基含有重合性不飽和モノマー並びにその他の重合性不飽和モノマーを共重合成分とするものであり、
これらモノマー合計質量を基準として、アミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマーの使用割合が３〜２５質量％であり、該アミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマーの使用量が、アクリルポリオール（Ａ−１）及びアクリルポリオール（Ａ−２）の固形分合計１００質量部を基準として０．２〜２５質量部の範囲内にある低汚染塗料組成物、
２．アクリルポリオール（Ａ−１）／アクリルポリオール（Ａ−２）固形分質量比が、（Ａ−１）成分と（Ａ−２）成分の質量合計を基準にして、３／９７〜９７／３の範囲内にある１項に記載の低汚染塗料組成物、
３．顔料分（Ｄ）がその成分の一部として酸化ケイ素を含む１項または２項に記載の低汚染塗料組成物、
４．被塗面に、１項ないし３項のいずれか１項に記載の低汚染塗料組成物を塗装する塗装方法、に関する。
That is, the present invention
1. A two-component composition comprising a main component (I) containing a resin component (A) and an organic solvent (B) and a curing agent component (II) containing a polyisocyanate compound (C),
Either or both of the main component (I) and the curing agent component (II) contain the pigment component (D) and / or the organosilicate compound (E),
The resin component (A) includes, as part of the component, an acrylic polyol (A-1) containing an amino group and / or a quaternary ammonium group, and an acrylic polyol (A-2) containing no amino group and quaternary ammonium group. Including both
The acrylic polyol (A-1) is selected from N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, dimethylaminopropylacrylamide, and dimethylaminoethylmethyl chloride methacrylate salt. And at least one amino group-containing polymerizable unsaturated monomer and / or quaternary ammonium group-containing polymerizable unsaturated monomer, hydroxyl group-containing polymerizable unsaturated monomer, and other polymerizable unsaturated monomers as copolymerization components. Yes,
Based on the total mass of these monomers, the proportion of the amino group-containing polymerizable unsaturated monomer and / or quaternary ammonium group-containing polymerizable unsaturated monomer is 3 to 25% by mass, and the amino group-containing polymerizable unsaturated monomer And / or the usage-amount of a quaternary ammonium group containing polymerizable unsaturated monomer is 0.2-25 mass parts on the basis of 100 mass parts of solid content total of acrylic polyol (A-1) and acrylic polyol (A-2). A low-contamination paint composition that is in the range of
2. The acrylic polyol (A-1) / acrylic polyol (A-2) solid content mass ratio is 3/97 to 97/3 based on the total mass of the components (A-1) and (A-2). The low-contamination paint composition according to claim 1, which is in the range,
3. Item 3. The low-contamination paint composition according to Item 1 or 2, wherein the pigment component (D) contains silicon oxide as a part of the component.
4). The present invention relates to a coating method for coating the surface to be coated with the low-contamination paint composition according to any one of items 1 to 3.
本発明の低汚染塗料組成物は、低汚染性を有し、耐水性、耐候性などの塗膜物性に優れている上、各種素材との付着性に非常に優れているので、塗り重ね時に塗装と塗装のインターバル時間が長くなった場合においても良好な層間付着性を有することができるものである。 The low-contamination paint composition of the present invention has low-contamination properties and excellent coating properties such as water resistance and weather resistance, as well as excellent adhesion to various materials. Even when the interval time between coatings becomes long, good interlayer adhesion can be obtained.
本発明は、主剤成分（Ｉ）と硬化剤成分（II）を塗装前に混合して得られる、２液型の低汚染塗料組成物である。 The present invention is a two-component low-contamination paint composition obtained by mixing the main component (I) and the curing agent component (II) before coating.
まず主剤成分（Ｉ）について説明する。 First, the main component (I) will be described.
＜樹脂成分（Ａ）＞
本発明において、主剤成分（Ｉ）に含まれる樹脂成分（Ａ）は、その成分の一部として、アミノ基及び／又は４級アンモニウム基含有アクリルポリオール（Ａ−１）並びにアミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）を共に含む。両者を併用することによって、本発明低汚染塗料組成物を２回塗り塗装したときの層間付着性（以下、２回塗り塗装したときの層間付着性を「塗り重ね時の付着性」と記する場合がある）と低汚染性とを両立することができると共に、本発明の低汚染塗料組成物から形成される塗膜の耐水性、耐候性などの塗膜物性を良好なものとすることができる。
<Resin component (A)>
In the present invention, the resin component (A) contained in the main component (I) includes, as part of the component, an amino group and / or quaternary ammonium group-containing acrylic polyol (A-1) and an amino group and quaternary ammonium. A group-free acrylic polyol (A-2) is included together. By using both in combination, the adhesion between the layers when the low-contamination paint composition of the present invention is applied twice (hereinafter, the adhesion between the layers when applied twice is referred to as “adhesion at the time of recoating”). In some cases, it is possible to achieve both low contamination and low contamination, and to improve the coating properties such as water resistance and weather resistance of the coating formed from the low contamination coating composition of the present invention. it can.
かかるアミノ基及び／又は４級アンモニウム基含有アクリルポリオール（Ａ−１）は、アミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマー、水酸基含有重合性不飽和モノマー並びにその他の重合性不飽和モノマーを共重合成分とするものである。 Such an amino group and / or quaternary ammonium group-containing acrylic polyol (A-1) includes an amino group-containing polymerizable unsaturated monomer and / or a quaternary ammonium group-containing polymerizable unsaturated monomer, a hydroxyl group-containing polymerizable unsaturated monomer, and Another polymerizable unsaturated monomer is used as a copolymerization component.
その製造方法は特に制限されるものではなく、アゾ化合物や過酸化物を開始剤に用いたラジカル重合法など定法により製造してもよいし、又は市販品等を使用することも可能である。 The production method is not particularly limited, and it may be produced by a conventional method such as a radical polymerization method using an azo compound or a peroxide as an initiator, or a commercially available product may be used.
アミノ基含有重合性不飽和モノマーとしては、例えば、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ−ｔ−ブチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノブチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド等が挙げられる。 Examples of the amino group-containing polymerizable unsaturated monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N- Examples thereof include t-butylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide and the like.
４級アンモニウム基含有重合性不飽和モノマーとしては、（メタ）アクリル酸ジメチルアミノエチルメチルクロライド塩、（メタ）アクリル酸ジメチルアミノエチルベンジルクロライド塩、（メタ）アクリル酸ジエチルアミノエチルメチルクロライド塩、（メタ）アクリル酸ジエチルアミノエチルベンジルクロライド塩、（メタ）アクリル酸アミノプロピルジメチルアンモニウムメチルクロライド塩、（メタ）アクリル酸アミノプロピルジメチルアンモニウムベンジルクロライド塩、（メタ）アクリル酸アミノプロピルジエチルアンモニウムメチルクロライド塩、（メタ）アクリル酸アミノプロピルジエチルアンモニウムベンジルクロライド塩、（メタ）アクリル酸トリメチルアンモニウムメチルサルフェート塩、（メタ）アクリル酸トリエチルアンモニウムメチルサルフェート塩、（メタ）アクリル酸アミノプロピルジメチルアンモニウムメチルサルフェート塩、（メタ）アクリル酸アミノプロピルジメチルアンモニウムエチルサルフェート塩、（メタ）アクリル酸トリメチルアミノエチルｐ−トルエンスルホネート塩、（メタ）アクリル酸アミノプロピルジメチルエチルアンモニウムエチルサルフェート塩等の４級アンモニウム基含有重合性不飽和モノマーなどが挙げられる。 Quaternary ammonium group-containing polymerizable unsaturated monomers include (meth) acrylic acid dimethylaminoethyl methyl chloride salt, (meth) acrylic acid dimethylaminoethyl benzyl chloride salt, (meth) acrylic acid diethylaminoethyl methyl chloride salt, (meth ) Diethylaminoethylbenzyl chloride chloride (meth) acrylate, aminopropyldimethylammonium methylchloride (meth) acrylate, aminopropyldimethylammonium benzylchloride (meth) acrylate, aminopropyldiethylammonium methylchloride (meth) acrylate, (meth) ) Aminopropyldiethylammonium benzyl chloride salt of acrylic acid, (meth) acrylic acid trimethylammonium methyl sulfate salt, (meth) acrylic acid trie Luammonium methyl sulfate salt, (meth) acrylic acid aminopropyldimethylammonium methyl sulfate salt, (meth) acrylic acid aminopropyldimethylammonium ethyl sulfate salt, (meth) acrylic acid trimethylaminoethyl p-toluenesulfonate salt, (meth) acrylic And quaternary ammonium group-containing polymerizable unsaturated monomers such as acid aminopropyldimethylethylammonium ethyl sulfate salt.
以上の述べたアミノ基含有重合性不飽和モノマー及び４級アンモニウム基含有重合性不飽和モノマーは単独で使用してもよいし、２種以上組み合わせて使用してもよい。 The amino group-containing polymerizable unsaturated monomer and quaternary ammonium group-containing polymerizable unsaturated monomer described above may be used alone or in combination of two or more.
水酸基含有重合性不飽和モノマーとしては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸と炭素数２〜８の２価アルコールとのモノエステル化物、該（メタ）アクリル酸と炭素数２〜８の２価アルコールとのモノエステル化物のε−カプロラクトン変性体、Ｎ−ヒドロキシメチル（メタ）アクリルアミド、アリルアルコ−ル、分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等が挙げられ、これらは単独で又は２種以上組み合わせて使用することができる。 Examples of the hydroxyl group-containing polymerizable unsaturated monomer include (meth) 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Monoesterified product of acrylic acid and C2-8 dihydric alcohol, ε-caprolactone modified product of monoesterified product of (meth) acrylic acid and C2-8 dihydric alcohol, N-hydroxymethyl Examples include (meth) acrylamide, allyl alcohol, (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end, and these can be used alone or in combination of two or more.
その他の重合性不飽和モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉｓｏ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉｓｏ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート（ラウリル（メタ）アクリレート）、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、ｔ−ブチルシクロヘキシル（メタ）アクリレート、シクロドデシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート等のアルキル又はシクロアルキル（メタ）アクリレート等のアルキル基を有するアルキル（メタ）アクリレート；ベンジル（メタ）アクリレート、スチレン、α−メチルスチレン、ビニルトルエン等の芳香環含有重合性不飽和モノマー；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、γ−（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリエトキシシラン等のアルコキシシリル基を有する重合性不飽和モノマー；パーフルオロブチルエチル（メタ）アクリレート、パーフルオロオクチルエチル（メタ）アクリレート等のパーフルオロアルキル（メタ）アクリレート；フルオロオレフィン等のフッ素化アルキル基を有する重合性不飽和モノマー；マレイミド基等の光重合性官能基を有する重合性不飽和モノマー；Ｎ−ビニルピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニル等のビニル化合物；（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレート等のカルボキシル基含有重合性不飽和モノマー；（メタ）アクリロニトリル、（メタ）アクリルアミド等の含窒素重合性不飽和モノマー；グリシジル（メタ）アクリレート、β−メチルグリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、３，４−エポキシシクロヘキシルエチル（メタ）アクリレート、３，４−エポキシシクロヘキシルプロピル（メタ）アクリレート、アリルグリシジルエーテル等のエポキシ基含有重合性不飽和モノマー；Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、メトキシエチル（メタ）アクリレート、メトキシプロピル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、エトキシプロピル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート、ポリエチレングリコールモノメトキシ（メタ）アクリレート等のポリアルキレングリコールモノアルコキシ（メタ）アクリレート等のアルコキシ基含有重合性不飽和モノマー；アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、４〜７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等のカルボニル基含有重合性不飽和モノマー等が挙げられ、これらは単独で又は２種以上組み合わせて使用することができる。 Other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate ( Lauryl (meth) acrylate), tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate , T-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, alkyl such as tricyclodecanyl (meth) acrylate or alkyl such as cycloalkyl (meth) acrylate Alkyl (meth) acrylate having a group; aromatic ring-containing polymerizable unsaturated monomer such as benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxy) Polymerizable unsaturated monomers having an alkoxysilyl group such as ethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane; Perfluoroalkyl (meth) acrylates such as fluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; polymerizable unsaturated monomers having fluorinated alkyl groups such as fluoroolefins; and photopolymerizable functionalities such as maleimide groups Polymerizable unsaturated monomers having a group; vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate; (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, etc. Carboxyl group-containing polymerizable unsaturated monomers; nitrogen-containing polymerizable unsaturated monomers such as (meth) acrylonitrile and (meth) acrylamide; glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclo Epoxy group-containing polymerizable unsaturated monomers such as xylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether; N-methoxymethyl (meta ) Alkoxyalkyl (meth) acrylates such as acrylamide, N-butoxymethyl (meth) acrylamide, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, polyethylene glycol Polyalkylene glycol monoalkoxy (meth) acrylate and other alkoxy group-containing polymerizable unsaturated monomers such as monomethoxy (meth) acrylate; acrolein, dye Carbonyl group-containing polymerizability such as acetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketone having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) An unsaturated monomer etc. are mentioned, These can be used individually or in combination of 2 or more types.
本発明においては上記アミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマーの使用量が、アクリルポリオール（Ａ−１）及び後述のアミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）の固形分合計１００質量部を基準として０．２〜２５質量部の範囲内にあることを特徴としており、０．５〜２０質量部の範囲内にあるとさらに好ましい。 In the present invention, the amino group-containing polymerizable unsaturated monomer and / or the quaternary ammonium group-containing polymerizable unsaturated monomer is used in an acrylic polyol (A-1) and no amino group and quaternary ammonium group described later. It is characterized by being in the range of 0.2 to 25 parts by mass based on 100 parts by mass of the total solid content of the acrylic polyol (A-2), and more preferably in the range of 0.5 to 20 parts by mass. .
本明細書において固形分とは、不揮発分を意味するものであり、試料から、水、有機溶剤等の揮発する成分を除いた残渣を意味し、試料の質量に固形分濃度を乗じて算出することができる。固形分濃度は、試料約３グラムを、１０５℃、３時間乾燥させた残渣の質量を、乾燥前の質量で除することにより求めることができ、また、１００分率で示す場合もある。 In this specification, solid content means non-volatile content, means a residue obtained by removing volatile components such as water and organic solvent from a sample, and is calculated by multiplying the mass of the sample by the solid content concentration. be able to. The solid content concentration can be obtained by dividing the mass of a residue obtained by drying about 3 grams of a sample at 105 ° C. for 3 hours by the mass before drying, and may be expressed as a 100 fraction.
該アミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマーの使用量が（Ａ−１）及び（Ａ−２）の合計固形分に対して０．２質量部未満では、塗り重ね時付着性が不十分であり、一方２５質量部を超えると耐水性、耐候性などの塗膜物性が不十分となり、好ましくない。 The amount of the amino group-containing polymerizable unsaturated monomer and / or quaternary ammonium group-containing polymerizable unsaturated monomer used is less than 0.2 parts by mass relative to the total solid content of (A-1) and (A-2). Then, the adhesion at the time of recoating is insufficient. On the other hand, if it exceeds 25 parts by mass, the physical properties of the coating film such as water resistance and weather resistance become insufficient, which is not preferable.
本発明において上記アミノ基及び／又は４級アンモニウム基含有アクリルポリオール（Ａ−１）におけるアミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマー、水酸基含有重合性不飽和モノマー並びにその他の重合性不飽和モノマーの使用割合としては一般に、これらの合計質量を基準として、
アミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマーが１〜３０質量％、好ましくは３〜２５質量％、
水酸基含有重合性不飽和モノマーが３〜２０質量％、好ましくは５〜１５質量％、
その他の重合性不飽和モノマーが９６〜５０質量％、好ましくは９２〜６０質量％の範囲内にあることが適している。
In the present invention, the amino group-containing polymerizable unsaturated monomer and / or the quaternary ammonium group-containing polymerizable unsaturated monomer, hydroxyl group-containing polymerizable unsaturated in the amino group and / or quaternary ammonium group-containing acrylic polyol (A-1). The proportion of monomer and other polymerizable unsaturated monomers used is generally based on their total mass,
The amino group-containing polymerizable unsaturated monomer and / or the quaternary ammonium group-containing polymerizable unsaturated monomer is 1 to 30% by mass, preferably 3 to 25% by mass,
3 to 20% by mass of a hydroxyl group-containing polymerizable unsaturated monomer, preferably 5 to 15% by mass,
It is suitable that the other polymerizable unsaturated monomer is in the range of 96 to 50% by mass, preferably 92 to 60% by mass.
アミノ基及び／又は４級アンモニウム基含有アクリルポリオール（Ａ−１）の弱溶剤溶解性及び塗膜の耐候性、耐水性などの塗膜物性の観点から、アミノ基及び／又は４級アンモニウム基含有アクリルポリオール（Ａ−１）の共重合成分としてのその他の重合性不飽和モノマーは、炭素数が４以上のアルキル基を有する（メタ）アクリレートをその他の重合性不飽和モノマー質量を基準として５０質量％以上、好ましくは５０〜９５質量％使用することが適している。 Amino group and / or quaternary ammonium group-containing acrylic group (A-1) from the viewpoint of weak solvent solubility and coating film properties such as weather resistance and water resistance of the coating film. The other polymerizable unsaturated monomer as a copolymerization component of acrylic polyol (A-1) is 50 masses of (meth) acrylate having an alkyl group having 4 or more carbon atoms based on the mass of the other polymerizable unsaturated monomer. % Or more, preferably 50 to 95% by mass is used.
該炭素数が４以上のアルキル基を有する（メタ）アクリレートとしては、例えばｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、「イソステアリルアクリレート」（商品名、大阪有機化学社製）、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリデシル（メタ）アクリレート等の直鎖状、分岐状又は環状アルキル基含有(メタ)アクリレートを挙げることができ、これらは単独でまたは２種以上組み合わせて使用することができる。中でも炭素数が４のアルキル基を有する（メタ）アクリレート、好ましくは炭素数が４のアルキル基を有するメタクリレートを含むことが好ましい。 Examples of the (meth) acrylate having an alkyl group having 4 or more carbon atoms include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n -Octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, "isostearyl acrylate" (trade name, manufactured by Osaka Organic Chemical Co., Ltd.), cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) ) A linear, branched or cyclic alkyl group-containing (meth) acrylate such as acrylate can be mentioned, and these can be used alone or in combination of two or more. Among them, it is preferable to include (meth) acrylate having an alkyl group having 4 carbon atoms, preferably a methacrylate having an alkyl group having 4 carbon atoms.
本明細書中における弱溶剤とは当該分野でよく用いられる用語であって、一般的には溶解力の弱い溶剤を意味するものであり厳密に定義されるものではないが、労働安全衛生法による有機溶剤の分類において、第３種有機溶剤とされているものであることができる。 The weak solvent in this specification is a term often used in the field, and generally means a solvent having a weak dissolving power and is not strictly defined. In the classification of the organic solvent, the organic solvent can be a third type organic solvent.
その具体例としては、例えば、ガソリン、灯油、コールタールナフサ（ソルベントナフサを含む）、石油エーテル、石油ナフサ、石油ベンジン、テレピン油、ミネラルスピリット（ミネラルシンナー、ペトロリウムスピリット、ホワイトスピリットおよびミネラルターペンを含む）を挙げることができ、これらは単独でまたは２種以上組み合わせたものであってもよく、労働安全衛生法における第１種有機溶剤、第２種有機溶剤を５質量％以下で含んだものであっても良い。 Specific examples thereof include gasoline, kerosene, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, mineral spirit (mineral thinner, petrolium spirit, white spirit and mineral turpentine. These may be used singly or in combination of two or more, and contain 5% by mass or less of the first type organic solvent and the second type organic solvent in the Industrial Safety and Health Act. It may be.
なお、第１種有機溶剤とは、クロロホルム、四塩化炭素、１，２−ジクロルエタン、１，２−ジクロルエチレン、１，１，２，２−テトラクロルエタン、トリクロルエタン、二硫化炭素、及び、これらのみからなる混合物等が挙げられ、第２種有機溶剤とは、いわゆる強溶剤と呼ばれるものであり、アセトン、イソブチルアルコール、イソプロピルアルコール、イソペンチルアルコール、エチルアルコール、エチレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ−ｎ−ブチルエーテル、エチレングリコールモノメチルエーテル、オルト−ジクロロベンゼン、キシレン、クレゾール、クロルベンゼン、酢酸イソブチル、酢酸イソプロピル、酢酸イソペンチル、酢酸エチル、酢酸−ｎ−ブチル、酢酸−ｎ−プロピル、酢酸−ｎ−ペンチル、酢酸メチル、シクロヘキサノール、シクロヘキサノン、１，４−ジオキサン、ジクロロメタン、Ｎ，Ｎ−ジメチルホルムアミド、スチレン、テトラクロロエチレン、テトラヒドロフラン、１，１，１−トリクロルエタン、トルエン、ｎ−ヘキサン、１−ブタノール、２−ブタノール、メタノール、メチルイソブチルケトン、メチルエチルケトン、メチルシクロヘキサノール、メチルシクロヘキサノン、メチル−ｎ−ブチルケトン等を挙げることができる。 The first type organic solvent is chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2,2-tetrachloroethane, trichloroethane, carbon disulfide, and The second type organic solvent is a so-called strong solvent, such as acetone, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, ethyl alcohol, ethylene glycol monoethyl ether, ethylene. Glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, ortho-dichlorobenzene, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethyl acetate, acetic acid n-butyl, acetic acid-n-propyl, acetic acid-n-pentyl, methyl acetate, cyclohexanol, cyclohexanone, 1,4-dioxane, dichloromethane, N, N-dimethylformamide, styrene, tetrachloroethylene, tetrahydrofuran, 1,1,1 -Trichloroethane, toluene, n-hexane, 1-butanol, 2-butanol, methanol, methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexanol, methyl cyclohexanone, methyl-n-butyl ketone and the like can be mentioned.
上記弱溶剤としては市販品を使用することもでき、その具体例としては、「スワゾール１０００」、「スワゾール１５００」（以上、丸善石油株式会社製）、「ソルベッソ１５０」、「ソルベッソ２００」、「ＨＡＷＳ」、「ＬＡＷＳ」（以上、シェルジャパン社製）、「エッソナフサＮｏ．６」、「エクソールＤ３０」（商品名、エクソンモービル化学社製）、「ペガゾール３０４０」（商品名、エクソンモービル化学社製）、「Ａソルベント」、「クレンゾル」、「イプゾール１００」（出光興産株式会社製）、「ミネラルスピリットＡ」、「ハイアロム２Ｓ」、「ハイアロム２Ｓ」（以上、新日本石油化学株式会社製）、「リニアレン１０」、「リニアレン１２」（以上、出光石油化学株式会社製）、「リカソルブ９００」、「リカソルブ９１０Ｂ」、「リカソルブ１０００」（以上、新日本理化株式会社製）などを挙げることができ、これらを単独または混合して用いることができる。 Commercially available products may be used as the weak solvent, and specific examples thereof include “Swazole 1000”, “Swazol 1500” (manufactured by Maruzen Petroleum Co., Ltd.), “Solvesso 150”, “Solvesso 200”, “ “HAWS”, “LAWS” (above, manufactured by Shell Japan), “Essonaphtha No. 6”, “Exor D30” (trade name, manufactured by ExxonMobil Chemical), “Pegasol 3040” (trade name, manufactured by ExxonMobil Chemical) ), “A Solvent”, “Clensol”, “Ipsol 100” (manufactured by Idemitsu Kosan Co., Ltd.), “Mineral Spirit A”, “High Alom 2S”, “High Alom 2S” (above, Shin Nippon Petrochemical Co., Ltd.), “Linearene 10”, “Linearene 12” (above, manufactured by Idemitsu Petrochemical Co., Ltd.), “Rikasolve 900”, “Rikaso” Bed 910B "," Rikasorubu 1000 "(or, New Japan Chemical Co., Ltd.) and the like can be illustrated, may be used alone or in combination.
以上で述べたアミノ基及び／又は４級アンモニウム基含有アクリルポリオール（Ａ−１）の重量平均分子量としては、１，０００〜１５０，０００、好ましくは５，０００〜５０，０００の範囲内にあることが形成塗膜の塗り重ね時付着性と耐水性、耐候性、弱溶剤溶解性などの点から好適である。 The weight average molecular weight of the amino group and / or quaternary ammonium group-containing acrylic polyol (A-1) described above is in the range of 1,000 to 150,000, preferably 5,000 to 50,000. This is preferable from the viewpoints of adhesion during recoating of the formed coating film, water resistance, weather resistance, weak solvent solubility, and the like.
本明細書において重量平均分子量はゲルパーミエーションクロマトグラフ（東ソー（株）社製、「ＨＬＣ８１２０ＧＰＣ」）で測定した重量平均分子量をポリスチレンの重量平均分子量を基準にして換算した値である。カラムは、「ＴＳＫｇｅｌＧ−４０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−３０００Ｈ×Ｌ」、「ＴＳＫｇｅｌＧ−２５００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−２０００Ｈ×Ｌ」（いずれも東ソー（株）社製、商品名）の４本を用い、移動相；テトラヒドロフラン、測定温度；４０℃、流速；１ｍｌ／分、検出器；ＲＩの条件で行ったものである。 In the present specification, the weight average molecular weight is a value obtained by converting a weight average molecular weight measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the weight average molecular weight of polystyrene. Columns are “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation, trade name). Four were used, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 ml / min, detector: RI.
本発明においてアミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）は、本発明塗料組成物を用いて形成される塗膜の低汚染性と塗り重ね時付着性を保ちつつ、耐水性、耐候性などの塗膜物性を向上させるために用いられるものであり、アミノ基及び４級アンモニウム基のいずれも有さず、例えば、水酸基含有重合性不飽和モノマー及びその他の重合性不飽和モノマーを共重合成分とする樹脂を挙げることができる。 In the present invention, the amino group and quaternary ammonium group-free acrylic polyol (A-2) is water resistant while maintaining the low contamination of the coating film formed by using the coating composition of the present invention and the adhesion during coating. , Which is used for improving coating film properties such as weather resistance and has neither an amino group nor a quaternary ammonium group, for example, a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers. Can be mentioned as a copolymerization component.
水酸基含有重合性不飽和モノマー及びその他の重合性不飽和モノマーの具体例としては上記アミノ基及び／又は４級アンモニウム基含有アクリルポリオール（Ａ−１）説明で水酸基含有重合性不飽和モノマー及びその他の重合性不飽和モノマーとして例示したものと同様のものを挙げることができる。 Specific examples of the hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers include the hydroxyl group-containing polymerizable unsaturated monomer and the other amino group and / or quaternary ammonium group-containing acrylic polyol (A-1) described above. The thing similar to what was illustrated as a polymerizable unsaturated monomer can be mentioned.
上記アミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）において、水酸基含有重合性不飽和モノマー及びその他の重合性不飽和モノマーの使用割合としては一般に、これらの合計量を基準として
水酸基含有重合性不飽和モノマーが１〜２０質量％、好ましくは５〜１５質量％、
その他の重合性不飽和モノマーが９９〜８０質量％、好ましくは９５〜８５質量％の範囲内にあることが適している。
In the above amino group and quaternary ammonium group-free acrylic polyol (A-2), the hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers are generally used in proportions based on the total amount thereof. 1 to 20% by weight of polymerizable unsaturated monomer, preferably 5 to 15% by weight,
It is suitable that the other polymerizable unsaturated monomer is in the range of 99 to 80% by mass, preferably 95 to 85% by mass.
また、アミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）も弱溶剤に溶解可能であることが適しており、アクリルポリオール（Ａ−２）の製造に使用されるその他の重合性不飽和モノマーが、炭素数が４以上のアルキル基を有する（メタ）アクリレートを５０質量％以上、好ましくは６０〜９９質量％含むことが適している。 In addition, it is suitable that the amino group and quaternary ammonium group-free acrylic polyol (A-2) is also soluble in a weak solvent, and other polymerizable substances used for the production of the acrylic polyol (A-2). It is suitable that the saturated monomer contains 50% by mass or more, preferably 60 to 99% by mass of (meth) acrylate having an alkyl group having 4 or more carbon atoms.
上記アミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）の重量平均分子量としては、１，０００〜１５０，０００、好ましくは５，０００〜５０，０００の範囲内にあることが形成塗膜の耐水性、耐候性、弱溶剤溶解性などの点から好適である。 The weight average molecular weight of the amino group and quaternary ammonium group-free acrylic polyol (A-2) is 1,000 to 150,000, preferably 5,000 to 50,000. This is preferable from the viewpoint of the water resistance, weather resistance, weak solvent solubility and the like of the film.
本発明において、主剤成分（Ｉ）に含まれる樹脂成分（Ａ）は、アミノ基及び／又は４級アンモニウム塩基含有アクリルポリオール（Ａ−１）並びにアミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）を共に含むものであり、その使用割合としては、（Ａ−１）成分と（Ａ−２）成分の合計質量を基準にして、アクリルポリオール（Ａ−１）／アクリルポリオール（Ａ−２）固形分質量比が３／９７〜９７／３、好ましくは５／９５〜９５／５の範囲内にあることが塗り重ね時付着性、耐水性、耐候性などの塗膜物性の点から適している。 In the present invention, the resin component (A) contained in the main component (I) is an amino group and / or quaternary ammonium base-containing acrylic polyol (A-1) and an amino group and quaternary ammonium group-free acrylic polyol (A). -2), and the use ratio thereof is acrylic polyol (A-1) / acrylic polyol (A-) based on the total mass of component (A-1) and component (A-2). 2) From the viewpoint of the physical properties of the coating film such as adhesion, water resistance, weather resistance, etc., when the solid content is in the range of 3/97 to 97/3, preferably 5/95 to 95/5. Is suitable.
本発明において樹脂成分（Ａ）はアミノ基及び／又は４級アンモニウム基含有アクリルポリオール（Ａ−１）、アミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）に加えて、（Ａ−１）及び（Ａ−２）以外のアクリル樹脂、アルキド樹脂、ウレタン樹脂、シリコン樹脂等の併用樹脂を必要に応じて含むことができる。樹脂成分（Ａ）が、（Ａ−１）及び（Ａ−２）以外の上記例示したごとき併用樹脂を含む場合、その場合の併用樹脂の含有量としては樹脂成分（Ａ）固形分質量を基準として４０質量％以下、好ましくは３０質量％以下の範囲内とすることができる。 In the present invention, in addition to the amino group and / or quaternary ammonium group-containing acrylic polyol (A-1), the amino group and quaternary ammonium group-free acrylic polyol (A-2), A combination resin such as an acrylic resin other than 1) and (A-2), an alkyd resin, a urethane resin, and a silicone resin can be included as necessary. When the resin component (A) includes a combination resin as exemplified above other than (A-1) and (A-2), the content of the combination resin in that case is based on the solid content of the resin component (A). As 40 mass% or less, Preferably it can be in the range of 30 mass% or less.
＜有機溶剤（Ｂ）＞
本発明の低汚染塗料組成物に使用するに好ましい有機溶剤（Ｂ）としては上述の弱溶剤を挙げることができる。また、弱溶剤以外の有機溶剤を使用することもできる。
<Organic solvent (B)>
Examples of the organic solvent (B) preferable for use in the low-contamination paint composition of the present invention include the above-mentioned weak solvents. Moreover, organic solvents other than a weak solvent can also be used.
かかる弱溶剤以外の有機溶剤としては、例えばｎ−ブタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、シクロペンタン、シクロヘキサン、シクロブタンなどの炭化水素溶剤；トルエン、キシレン等の芳香族系溶剤；メチルイソブチルケトン等のケトン系溶剤；ｎ−ブチルエーテル、ジオキサンなどのエーテル系溶剤；酢酸エチル、酢酸ｎ−ブチル、酢酸イソブチル、エチレングリコールモノメチルエーテルアセテート、ブチルカルビトールアセテート等のエステル系溶剤；メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン等のケトン系溶剤等の従来公知の溶剤を挙げることができる。 Examples of organic solvents other than such weak solvents include hydrocarbon solvents such as n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and cyclobutane; aromatic solvents such as toluene and xylene; methyl Ketone solvents such as isobutyl ketone; ether solvents such as n-butyl ether and dioxane; ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate and butyl carbitol acetate; methyl ethyl ketone and methyl isobutyl Conventionally known solvents such as ketone solvents such as ketone and diisobutyl ketone can be exemplified.
本発明の低汚染塗料組成物はポリウレタン系塗料であるので、水酸基含有有機溶剤の使用は好ましくはないが、該水酸基含有有機溶剤は必要に応じて含ませることもでき、その使用を排除するものではない。 Since the low-contamination paint composition of the present invention is a polyurethane-based paint, the use of a hydroxyl group-containing organic solvent is not preferable, but the hydroxyl group-containing organic solvent can be included as necessary, and its use is excluded. is not.
［主剤成分（Ｉ）］
本発明において主剤成分（Ｉ）は、前記樹脂成分（Ａ）及び有機溶剤（Ｂ）を含むものであり、貯蔵段階（封缶状態）におけるそれぞれの使用割合としては一般に、樹脂成分（Ａ）固形分質量１００質量部を基準として、有機溶剤（Ｂ）が５〜１００質量部、好ましくは１０〜７０質量部の範囲内にあることができる。
[Main ingredient component (I)]
In the present invention, the main component (I) contains the resin component (A) and the organic solvent (B), and generally the resin component (A) solid is used as the respective use ratio in the storage stage (sealed state). The organic solvent (B) can be in the range of 5 to 100 parts by mass, preferably 10 to 70 parts by mass, based on the partial mass of 100 parts by mass.
次に硬化剤成分（II）について説明する。 Next, the curing agent component (II) will be described.
＜ポリイソシアネート化合物（Ｃ）＞
本発明において硬化剤成分（II）に含まれるポリイソシアネート化合物（Ｃ）としては、１分子中に遊離のイソシアネート基を２個以上有する化合物であり、従来公知のものを制限なく使用することができる。例えば、脂肪族ポリイソシアネート化合物、脂環族ポリイソシアネート化合物、芳香脂肪族ポリイソシアネート化合物、芳香族ポリイソシアネート化合物及びこれらポリイソシアネート化合物の誘導体等を挙げることができる。
<Polyisocyanate compound (C)>
In the present invention, the polyisocyanate compound (C) contained in the curing agent component (II) is a compound having two or more free isocyanate groups in one molecule, and any conventionally known one can be used without limitation. . Examples include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, araliphatic polyisocyanate compounds, aromatic polyisocyanate compounds, and derivatives of these polyisocyanate compounds.
ポリイソシアネート化合物の誘導体としては、例えば、上記したポリイソシアネート化合物のダイマー、トリマー、ビュウレット、アロファネート、カルボジイミド、ウレトジオン、ウレトイミン、イソシアヌレート、オキサジアジントリオン、ポリメチレンポリフェニルポリイソシアネート（クルードＭＤＩ、ポリメリックＭＤＩ）、クルードＴＤＩ等を挙げることができる。これらポリイソシアネート化合物及びその誘導体は単独で使用してもよいし、２種以上組み合わせたものであってもよい。 Examples of the polyisocyanate compound derivative include dimer, trimer, burette, allophanate, carbodiimide, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). ), Crude TDI and the like. These polyisocyanate compounds and derivatives thereof may be used alone or in combination of two or more.
＜低汚染塗料組成物＞
本発明の低汚染塗料組成物において、上記主剤成分（Ｉ）及び硬化剤成分（II）は別個に保管され、両者を塗装業者が塗装前に混合して得られるものである。
<Low contamination paint composition>
In the low-contamination paint composition of the present invention, the main component (I) and the curing agent component (II) are stored separately, and both are obtained by a painter mixing them before painting.
主剤成分（Ｉ）及び硬化剤成分（II）の使用割合は、適宜調整されるものであるが、主剤成分（Ｉ）に含まれる樹脂成分（Ａ）の水酸基１当量に対し、硬化剤成分（II）に含まれるポリイソシアネート化合物（Ｄ）のイソシアネート基の当量比が０．３〜２．０、好ましくは０．５〜１．５の範囲内にあることが望ましい。 The proportions of the main agent component (I) and the curing agent component (II) are adjusted as appropriate, but the curing agent component (I) is equivalent to 1 equivalent of the hydroxyl group of the resin component (A) contained in the main agent component (I). It is desirable that the equivalent ratio of isocyanate groups of the polyisocyanate compound (D) contained in II) is in the range of 0.3 to 2.0, preferably 0.5 to 1.5.
また、本発明の低汚染塗料組成物は顔料分（Ｄ）及びオルガノシリケート化合物（Ｅ）を含む。 The low-contamination coating composition of the present invention contains a pigment component (D) and an organosilicate compound (E).
顔料分（Ｄ）及びオルガノシリケート化合物（Ｅ）はそれぞれ、主剤成分（Ｉ）及び硬化剤成分（Ｅ）のいずれ又は双方に含ませることができるが、主剤成分（Ｉ）が顔料分（Ｄ）を含み、硬化剤成分（II）がオルガノシリケート化合物（Ｅ）を含むことが各成分の貯蔵安定性や形成塗膜の仕上がり外観の点から適している。 The pigment component (D) and the organosilicate compound (E) can be contained in either or both of the main component (I) and the curing agent component (E), respectively, but the main component (I) is the pigment component (D). It is suitable that the curing agent component (II) contains the organosilicate compound (E) from the viewpoint of the storage stability of each component and the finished appearance of the formed coating film.
＜顔料分（Ｄ）＞
本発明の低汚染塗料組成物に用いられる顔料分（Ｄ）としては、従来公知のものを制限なく使用することができ、例えば、チタン白、亜鉛華などの白色顔料；シアニンブルー、インダスレンブルーなどの青色顔料；シアニングリーン、緑青などの緑色顔料；アゾ系やキナクリドン系などの有機赤色顔料、ベンガラなどの赤色顔料；ベンツイミダゾロン系、イソインドリノン系、イソインドリン系及びキノフタロン系などの有機黄色顔料、チタンイエロー、黄鉛などの黄色顔料；カーボンブラック、黒鉛、松煙などの黒色顔料；アルミニウム粉、銅粉、ニッケル粉、酸化チタン被覆マイカ粉、酸化鉄被覆マイカ粉及び光輝性グラファイトなどの光輝性顔料；タルク、クレー、カオリン、バリタ、硫酸バリウム、炭酸バリウム、炭酸カルシウム、アルミナホワイト等の体質顔料などを挙げることができ、目的の塗色に応じて適宜１種又は２種以上を組み合わせて使用することができる。
<Pigment content (D)>
As the pigment component (D) used in the low-contamination paint composition of the present invention, conventionally known pigment components can be used without limitation, for example, white pigments such as titanium white and zinc white; cyanine blue, and induslen blue Blue pigments such as cyanine green, green blue, etc .; organic red pigments such as azo and quinacridone; red pigments such as Bengala; organics such as benzimidazolone, isoindolinone, isoindoline, and quinophthalone Yellow pigments, yellow pigments such as titanium yellow and yellow lead; black pigments such as carbon black, graphite and pine smoke; aluminum powder, copper powder, nickel powder, titanium oxide-coated mica powder, iron oxide-coated mica powder and glittering graphite Glitter pigments of talc, clay, kaolin, barita, barium sulfate, barium carbonate, calcium carbonate, Lumina such extender pigments can be exemplified such as white, it can be used in combination of two or more appropriately in accordance with the paint color of interest.
かかる顔料分（Ｄ）の使用量としては顔料の種類に応じて適宜調整できるが一般に、樹脂成分（Ａ）固形分質量１００質量部を基準として、顔料分（Ｂ）の質量が３０〜２００質量部、好ましくは５０〜１５０質量部の範囲内にあることが望ましい。 The amount of the pigment component (D) can be appropriately adjusted according to the type of pigment, but generally, the pigment component (B) has a mass of 30 to 200 masses based on 100 mass parts of the solid content of the resin component (A). Part, preferably 50 to 150 parts by weight.
また、本発明の低汚染塗料組成物を艶消し塗膜にする場合には、必要に応じて、顔料分（Ｄ）に艶消し剤を含ませることができる。 Moreover, when making the low-pollution coating composition of this invention into a matte coating film, a matting agent can be included in a pigment part (D) as needed.
艶消し剤としては特に制限なく従来公知のものが使用でき、例えば酸化ケイ素、セラミック粉、石灰等の無機粉末；アクリルビーズ、ポリエチレンビーズ、ウレタンビーズ等の樹脂ビーズ；ポリオレフィンワックス及びその誘導体、モンタンワックス及びその誘導体、パラフィンワックス及びその誘導体等のワックス類が挙げられる。 As the matting agent, conventionally known matting agents can be used without limitation, for example, inorganic powders such as silicon oxide, ceramic powder and lime; resin beads such as acrylic beads, polyethylene beads and urethane beads; polyolefin wax and derivatives thereof, montan wax And waxes such as paraffin wax and derivatives thereof.
これらの中でも塗り重ね時付着性と低汚染性が低下することなく、かつ塗装方法や膜厚によって光沢度合いの差が生じにくく、さらに塗膜の艶消し感が良好で低光沢度を容易に得られることから、艶消し剤として酸化ケイ素を使用することが適している。 Among these, the adhesion and low contamination during coating are not reduced, the difference in glossiness is unlikely to occur depending on the coating method and film thickness, and the glossiness of the coating film is good and low glossiness is easily obtained. Therefore, it is suitable to use silicon oxide as a matting agent.
本発明塗料組成物が艶消しタイプの塗料組成物の場合、その場合の艶消し剤の含有量としては、主剤成分（Ｉ）に含まれる樹脂固形分１００質量部を基準として、艶消し剤の量が３〜３０質量部、好ましくは５〜２５質量部の範囲内にあることが艶消し感と塗り重ね時付着性の点から適している。 When the coating composition of the present invention is a matte type coating composition, the content of the matting agent in that case is based on 100 parts by mass of the resin solid content contained in the main component (I). It is suitable that the amount is in the range of 3 to 30 parts by mass, preferably 5 to 25 parts by mass, in terms of matte feeling and adhesion at the time of coating.
＜オルガノシリケート化合物（Ｅ）＞
本発明の低汚染塗料組成物は形成塗膜に低汚染性を付与するためにオルガノシリケート化合物（Ｅ）を含む。かかるオルガノシリケート化合物（Ｅ）としては、低汚染塗料として公知の低汚染化剤を使用することができ、例えば下記一般式で示される化合物又はその部分分解縮合物を挙げることができる。
Ｓｉ（−ＯＲ１）４
（式中Ｒ１は同一又は相異なってもよい、アルキル基、アリール基およびアラルキル基から選ばれた１価の炭化水素基である。）
Ｒ１としては同一又は異なって炭素数１〜４のアルキル基が好ましく、オルガノシリケート化合物の具体例としては、テトラメトキシシラン、テトラエトキシシラン、テトラ−ｎ−プロポキシシラン、テトラ−ｉ−プロポキシシラン、テトラ−ｎ−ブトキシシラン、テトラ−ｉ−ブトキシシラン、テトラ−ｔ−ブトキシシラン等のテトラアルコキシシラン；モノメトキシトリエトキシシラン、モノメトキシトリプロポキシシラン、モノエトキシトリプロポキシシラン、モノメトキシトリブトキシシラン、モノエトキシトリブトキシシラン、及びモノプロポキシトリブトキシシラン；ジメトキシジエトキシシラン、ジメトキシジプロポキシシラン、ジエトキシジプロポキシシラン、ジメトキシジブトキシシラン、及びジエトキシジブトキシシラン等及びそれらの部分加水分解・縮合物が例示できる。
<Organosilicate compound (E)>
The low-contamination paint composition of the present invention contains an organosilicate compound (E) in order to impart low-contamination properties to the formed coating film. As such an organosilicate compound (E), a known low-fouling agent can be used as a low-fouling paint, and examples thereof include compounds represented by the following general formula or partially decomposed condensates thereof.
Si (—OR 1 ) 4
(In the formula, R 1 may be the same or different and is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group.)
R 1 is the same or different and preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the organosilicate compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, Tetraalkoxysilanes such as tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane; monomethoxytriethoxysilane, monomethoxytripropoxysilane, monoethoxytripropoxysilane, monomethoxytributoxysilane, Monoethoxytributoxysilane and monopropoxytributoxysilane; dimethoxydiethoxysilane, dimethoxydipropoxysilane, diethoxydipropoxysilane, dimethoxydibutoxysilane, and diethoxydibutoxysilane And their partial hydrolysis / condensation products.
上記オルガノシリケート化合物（Ｅ）の市販品としては、「エチルシリケート４５」、「エチルシリケート４０」、「エチルシリケート４８」「エチルシリケートＥＭＡ４８５」（以上、コルコート社製）、「シリケート４５」、「シリケート４０」（以上、多摩化学工業社製）、「ＴＥＳ４０ＷＮ」、（以上、旭化成ワッカーシリコーン社製）等を挙げることができる。 Commercially available products of the organosilicate compound (E) include "ethyl silicate 45", "ethyl silicate 40", "ethyl silicate 48", "ethyl silicate EMA 485" (manufactured by Colcoat Co.), "silicate 45", "silicate" 40 ”(manufactured by Tama Chemical Industry Co., Ltd.),“ TES40WN ”(manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), and the like.
オルガノシリケート化合物（Ｅ）の含有量としては、主剤成分（I）に含まれる樹脂成分（Ａ）固形分質量１００質量部を基準として、０．１〜３０質量部、好ましくは１．０〜２０質量部の範囲内に調整されることが、低汚染性と塗り重ね時の付着性を両立させると共に、耐水性及び耐候性などの塗膜物性の観点からも適している。 The content of the organosilicate compound (E) is 0.1 to 30 parts by mass, preferably 1.0 to 20 based on 100 parts by mass of the solid content of the resin component (A) contained in the main component (I). Adjustment within the range of parts by mass is suitable from the viewpoint of coating properties such as water resistance and weather resistance as well as achieving both low contamination and adhesion during coating.
本発明の低汚染塗料組成物は、以上に述べた樹脂成分（Ａ）、有機溶剤（Ｂ）、ポリイソシアネート化合物（Ｃ）、顔料分（Ｄ）及びオルガノシリケート化合物（Ｅ）を含むものであり、それ以外に、塗料分野で使用できる硬化触媒、防カビ剤、沈降防止剤、顔料分散剤、消泡剤、塗面調整剤の添加剤等を必要に応じて主剤成分（Ｉ）及び／又は硬化剤成分（II）に配合することができる。 The low-contamination paint composition of the present invention comprises the resin component (A), organic solvent (B), polyisocyanate compound (C), pigment component (D) and organosilicate compound (E) described above. In addition to this, the main component (I) and / or the additives such as a curing catalyst, an antifungal agent, an anti-settling agent, a pigment dispersant, an antifoaming agent, and a coating surface conditioner that can be used in the paint field are used. It can mix | blend with hardening | curing agent component (II).
上記の如きして得られる本発明の低汚染塗料組成物は、塗装業者が主剤成分（Ｉ）及び硬化剤成分(II)を混合してから２４時間以内、好ましくは１２時間以内、さらに好ましくは３時間以内に塗装を行うことが適している。 The low-contamination paint composition of the present invention obtained as described above is preferably within 24 hours, preferably within 12 hours, more preferably after the painter has mixed the main component (I) and the curing agent component (II). It is suitable to paint within 3 hours.
また、本発明の低汚染塗料組成物は弱溶剤型であることができる。このことから、貯蔵段階（封缶状態）における主剤成分（Ｉ）又は硬化剤成分（II）に含まれる弱溶剤含有量としては、全有機溶剤を基準として５０質量％以上、特に７０質量％以上の範囲内にあることができる。弱溶剤型であることで、本発明塗料組成物を旧塗膜の上に塗装したときのチヂミの発生などの塗膜欠陥を抑制することができ、また、塗装による環境への負荷が比較的少ない利点を有する。 Moreover, the low-contamination coating composition of the present invention can be a weak solvent type. From this, the weak solvent content contained in the main component (I) or the curing agent component (II) in the storage stage (sealed state) is 50% by mass or more, particularly 70% by mass or more, based on the total organic solvent. Can be in the range of By being a weak solvent type, it is possible to suppress coating film defects such as generation of scratches when the coating composition of the present invention is applied on an old coating film, and the environmental impact due to coating is relatively low. Has few advantages.
本発明の低汚染塗料組成物は常温で硬化することができ、その硬化物である塗膜は塗り重ね時の付着性と低汚染性を両立でき、且つ耐水性や耐候性などの塗膜物性にも優れた性能を発揮するものであるが、強制乾燥や加熱硬化させても良い。 The low-contamination paint composition of the present invention can be cured at room temperature, and the coating film that is a cured product can achieve both adhesion and low-contamination properties during recoating, and physical properties such as water resistance and weather resistance. However, it may be forced-dried or heat-cured.
本発明の低汚染塗料組成物が適用される被塗面としては、必要に応じて下地処理した金属素材面、例えば鉄、鋼板面や亜鉛めっき面、ステンレス面、アルミニウム面、それらに塗装されてなる旧塗膜面などが挙げられるが、コンクリート、モルタル、スレート、スレート瓦等のアルカリ性を有する基材、窯業系建材、プラスチックなどの素材面やそれらに塗装されてなる旧塗膜面などにも塗装が可能である。 As the coated surface to which the low-contamination coating composition of the present invention is applied, it is coated on a metal material surface, for example, iron, steel plate surface, galvanized surface, stainless steel surface, aluminum surface, as necessary. Old paint film surface, etc., but also on the base material surface such as concrete, mortar, slate, slate tile, etc., ceramic building materials, plastic etc. and the old paint film surface coated on them Can be painted.
塗装物の用途としては特に制限されるものではないが、建築物、構造物の外壁に適している。 Although it does not restrict | limit especially as a use of a coated object, It is suitable for the outer wall of a building and a structure.
本発明の低汚染塗料組成物の塗装は、適正粘度に希釈した後、スプレー塗り、ローラー塗り、刷毛塗り、流し塗り等の公知の手段で行うことができ、一般に３０〜４００ｇ／ｍ２、好ましくは５０〜２５０ｇ／ｍ２の塗布量で塗装することができる。 Application of the low-contamination paint composition of the present invention can be carried out by a known means such as spray coating, roller coating, brush coating, flow coating, etc. after dilution to an appropriate viscosity, generally 30 to 400 g / m 2 , preferably Can be applied at a coating amount of 50 to 250 g / m 2 .
以下、本発明を実施例によりさらに具体的に説明する。ただし、本発明はこれらの実施例のみに限定されるものではない。なお、下記例中の「部」および「％」はそれぞれ「質量部」および「質量％」を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.
＜アクリルポリオールの製造＞
製造例１
温度計、サーモスタット、攪拌装置、還流冷却器及び滴下装置を備えた製造フラスコに「スワゾール１５００」（注１）３０部を仕込み、１１５℃まで昇温し、窒素気流中攪拌混合しながら下記組成のモノマー組成物を３時間かけて滴下した。
＜モノマー組成物＞
ヒドロキシエチルメタクリレート １０部、
メタクリル酸 ２部、
ｎ−ブチルメタクリレート ８３部、
Ｎ，Ｎ−ジエチルアミノエチルメタクリレート ５部、
ｔ−ブチルパーオキシ−２−エチルヘキサノエート １．２部、
＜触媒混合液＞
「スワゾール１５００」（注１） ３０部、
２，２´−アゾビス（２，４−ジメチルバレロニトリル） ０．５部、
次いで上記触媒混合液を同温度で１時間かけて滴下し、１１５℃で１時間熟成した後、固形分が５０％となるように「スワゾール１５００」（注１）を添加して、３級アミノ基含有アクリルポリオール１を得た。
（注１）「スワゾール１５００」：商品名、丸善石油（株）社製、芳香族系混合溶剤、沸点１８３〜２０８℃。
<Manufacture of acrylic polyol>
Production Example 1
A production flask equipped with a thermometer, thermostat, stirring device, reflux condenser and dropping device was charged with 30 parts of “Swazol 1500” (Note 1), heated to 115 ° C. and stirred and mixed in a nitrogen stream with the following composition: The monomer composition was added dropwise over 3 hours.
<Monomer composition>
10 parts hydroxyethyl methacrylate,
2 parts methacrylic acid,
83 parts of n-butyl methacrylate,
5 parts of N, N-diethylaminoethyl methacrylate,
1.2 parts t-butylperoxy-2-ethylhexanoate,
<Catalyst mixture>
"Swazole 1500" (Note 1) 30 parts,
0.5 part of 2,2′-azobis (2,4-dimethylvaleronitrile),
Next, the above catalyst mixture was added dropwise at the same temperature over 1 hour, and after aging at 115 ° C. for 1 hour, “Swazol 1500” (Note 1) was added so that the solid content was 50%. A group-containing acrylic polyol 1 was obtained.
(Note 1) “Swazole 1500”: trade name, manufactured by Maruzen Petroleum Corporation, aromatic mixed solvent, boiling point 183 to 208 ° C.
製造例２〜９
上記製造例１において、滴下するモノマー組成物を下記表１とする以外は上記製造例１と同様にしてアミノ基又は４級アンモニウム基含有アクリルポリオール２〜８及びアミノ基及び４級アンモニウム基非含有アクリルポリオールを得た。
Production Examples 2-9
In the above Production Example 1, the amino group or quaternary ammonium group-containing acrylic polyols 2 to 8 and the amino group and quaternary ammonium group are not contained in the same manner as in Production Example 1 except that the monomer composition to be dropped is shown in Table 1 below. An acrylic polyol was obtained.
表中略号の説明は下記通りである。
Ｓｔ：スチレン
ｉＢＭＡ：ｉ−ブチルメタクリレート
２ＥＨＡ：アクリル酸２エチルヘキシル
ＨＥＭＡ：２−ヒドロキシエチルメタクリレート
ＭＡＡ：メタクリル酸
ｎＢＭＡ：ｎ−ブチルメタクリレート
ＤＥＡＥＭＡ：Ｎ，Ｎ−ジエチルアミノエチルメタクリレート
ＤＭＡＥＭＡ：Ｎ，Ｎ−ジメチルアミノエチルメタクリレート
ＤＭＡＰＭＡ：Ｎ，Ｎ−ジメチルアミノプロピルメタクリレート
ＤＭＡＰＡＡ：ジメチルアミノプロピルアクリルアミド
ＤＭＣ：メタクリル酸ジメチルアミノエチルメチルクロライド塩
Ｍｗ：重量平均分子量
Ｎ．Ｖ．（％）：固形分質量濃度（％）
ＯＨ価：固形分あたりの水酸基価（ｍｇＫＯＨ／ｇ）。
The abbreviations in the table are explained as follows.
St: Styrene iBMA: i-butyl methacrylate 2EHA: 2-ethylhexyl acrylate HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid nBMA: n-butyl methacrylate DEAEMA: N, N-diethylaminoethyl methacrylate DMAEMA: N, N-dimethylaminoethyl Methacrylate DMAPMA: N, N-dimethylaminopropyl methacrylate DMAPAA: Dimethylaminopropylacrylamide DMC: Dimethylaminoethylmethyl chloride salt of methacrylate Mw: Weight average molecular weight V. (%): Solid content mass concentration (%)
OH value: hydroxyl value per solid content (mgKOH / g).
＜低汚染塗料の製造＞
実施例１〜１５及び比較例１〜７
下記配合組成でベース塗料を製造し、表１記載の硬化剤成分を混合して、艶有り塗膜が得られる低汚染塗料、及び艶消し塗膜が得られる低汚染塗料をそれぞれ製造し、下記評価に供した。
尚、表中の数値は実配合表示である。
<Manufacture of low contamination paint>
Examples 1-15 and Comparative Examples 1-7
A base paint is produced with the following composition, and the curing agent components shown in Table 1 are mixed to produce a low-contamination paint from which a glossy paint film is obtained and a low-contamination paint from which a matte paint film is obtained. It used for evaluation.
In addition, the numerical value in a table | surface is an actual compounding display.
注２）チタン白：二酸化チタン、比重４．１、
注３）「デュラネートＴＳＳ１００」：商品名、旭化成ケミカルズ株式会社製ＮＣＯ含量：１７．６質量％、
注４)「エチルシリケート４０」：商品名、コルコート株式会社製、エチルシリケート誘導体、有効成分９４％、
注５）「エチルシリケート４８」：商品名、コルコート株式会社製、エチルシリケート誘導体、有効成分９５％、
注６）「エチルシリケートＥＭＳ４８５」：コルコート株式会社製、エチルシリケート誘導体、有効成分９４％。
Note 2) Titanium white: Titanium dioxide, specific gravity 4.1,
Note 3) “Duranate TSS100”: trade name, NCO content manufactured by Asahi Kasei Chemicals Corporation: 17.6% by mass,
Note 4) “Ethyl silicate 40”: trade name, manufactured by Colcoat Co., Ltd., ethyl silicate derivative, 94% active ingredient,
Note 5) “Ethyl silicate 48”: trade name, manufactured by Colcoat Co., Ltd., ethyl silicate derivative, active ingredient 95%,
Note 6) “Ethyl silicate EMS485”: manufactured by Colcoat Co., Ltd., ethyl silicate derivative, active ingredient 94%.
＜試験塗板の作成＞
ボンデ鋼板（７０×１５０×０．８ｍｍ）に、「ザウルスＥＸ２」（商品名、関西ペイント社製、一液弱溶剤形エポキシさび止め塗料）をミネラルスピリットで１５％希釈したものをウェット膜厚７５ミクロンになるようにスプレー塗装した。翌日、該塗面上に上塗り１回目塗装として、表２記載の各塗料組成物を表２記載のベース塗料／硬化剤比率で混合し、更に、ミネラルスピリットで１０％希釈し、刷毛塗りで塗付量１００ｇ／ｍ２となるように塗装した。
<Creation of test coating plate>
Bonded steel plate (70 x 150 x 0.8 mm), "Zaurus EX2" (trade name, manufactured by Kansai Paint Co., Ltd., one-part weak solvent type epoxy rust-preventing paint) diluted 15% with mineral spirits, wet film thickness 75 It was spray-painted to become a micron. On the next day, each coating composition shown in Table 2 is mixed at the base paint / curing agent ratio shown in Table 2 as the first overcoating on the coated surface, and further diluted by 10% with mineral spirit and applied by brush coating. The coating amount was 100 g / m 2 .
上塗り塗料１回目と２回目の塗装間隔（インターバル）として、２３℃／湿度５０％環境下で７日間養生した。 As the coating interval (interval) for the first and second top coats, curing was performed for 7 days in an environment of 23 ° C./50% humidity.
上塗り１回目塗装後、上塗り２回目塗装として１回目に用いた塗料と同じ塗料を刷毛塗りで塗布量１００ｇ／ｍ２となるように塗装した。 After the first top coating, the same paint as the first coating was applied as a second top coating by brushing to a coating amount of 100 g / m 2 .
＜評価試験＞
（＊１）初期の付着性
２回目塗装後、２３℃/湿度５０％環境下で７日間養生後、初期の付着試験を行った。
<Evaluation test>
(* 1) Initial adhesion After the second coating, after curing for 7 days in an environment of 23 ° C./50% humidity, an initial adhesion test was conducted.
カッターナイフを用いて、互いに３０度の角度で交差する素地に達する長さ４０ｍｍの切り傷をつけ、次いでカット部上に粘着テープ（ＪＩＳ Ｚ１５２２に規定する幅１８ｍｍのもの）を貼り付け、該粘着テープを密着させてから、瞬間的に引き剥がし、ハガレ程度を下記基準にて評価を行った。
◎：ハガレなし、
○：カット部周囲に一部ハガレあり、
△：粘着テープを貼り付けた部分に対して、半分程度ハガレあり、
×：全面ハガレ。
（＊２）没水後の二次付着性
上記養生を行った試験板を水道水に２３℃で７日間浸漬させた。
塗板を引上げた後、軟らかい布およびウエスなどで水分を拭き取り、初期の付着試験と同じ条件で没水後の付着試験を行った。
◎：ハガレなし、
○：カット部周囲に一部ハガレあり
△：粘着テープを貼り付けた部分に対して、半分程度ハガレあり、
×：全面ハガレ。
（＊３）耐水性
各試験塗板を上水に２３℃で７日間浸漬した後、塗面状態を観察し、下記基準にて評価した。
○：良好、
△：塗膜の一部ブリスター発生、
×：塗膜の全面にブリスター発生。
（＊４）耐湿潤冷熱繰り返し性
各試験塗板を、ＪＩＳ Ｋ ５６００−７−４（耐湿潤冷熱繰り返し性）に準じ、２３℃の水に１８時間浸水後、−２０℃で３時間、さらに５０℃で３時間試験に供した。
この繰り返しを１０サイクル行い、試験終了後の塗膜の状態を目視により評価した。
○：ワレが認められない、
△：塗膜にややワレが認められる、
×：塗膜に著しいワレが認められる。
（＊５）耐汚染性
各試験塗板を、東京都大田区において試験面が南面を向き水平面に対し３０度の角度となるように固定し、６ヵ月間ばくろした後の汚染状態を、下記基準により、目視で評価した。また、ばくろ前後の色差△Ｅを、色彩色差計「ＣＲ−３１０」（商品名、ミノルタ（株）製）で評価した。
○：△Ｅが５より小さい（汚れはそれほど目立たない）、
△：△Ｅが５〜１０（汚れがやや目立つ）、
×：△Ｅが１０を越える（汚れが目立つ）。
Using a cutter knife, make a cut of 40 mm in length to reach the substrate intersecting at an angle of 30 degrees, and then stick an adhesive tape (with a width of 18 mm as defined in JIS Z1522) on the cut part. Then, the film was peeled off instantaneously, and the degree of peeling was evaluated according to the following criteria.
◎: No peeling
○: Some peeling occurs around the cut part.
Δ: About half of the adhesive tape is attached.
X: Full face peeling.
(* 2) Secondary adhesion after submerging The test plate subjected to the above curing was immersed in tap water at 23 ° C. for 7 days.
After pulling up the coated plate, moisture was wiped off with a soft cloth and waste cloth, and an adhesion test after submerging was performed under the same conditions as the initial adhesion test.
◎: No peeling
○: Partial peeling around the cut part △: About half peeling relative to the part where the adhesive tape is pasted,
X: Full face peeling.
(* 3) Water resistance Each test coated plate was immersed in clean water at 23 ° C for 7 days, and then the coated surface state was observed and evaluated according to the following criteria.
○: Good,
Δ: Partial blistering of the coating,
X: Blister occurs on the entire surface of the coating film.
(* 4) Wet cold / heat repeatability Each test coated plate was immersed in 23 ° C. water for 18 hours in accordance with JIS K 5600-7-4 (wet cold / heat repeatability), then at −20 ° C. for 3 hours, and further 50 It was subjected to the test at 3 ° C. for 3 hours.
This cycle was repeated for 10 cycles, and the state of the coating film after the test was visually evaluated.
○: crack is not recognized,
Δ: Slight cracking is observed in the coating film,
X: A remarkable crack is recognized by the coating film.
(* 5) Contamination resistance Each test coating plate was fixed in Ota-ku, Tokyo, with the test surface facing the south surface at an angle of 30 degrees with respect to the horizontal surface. Visual evaluation was made according to the criteria. Further, the color difference ΔE before and after exposure was evaluated with a color difference meter “CR-310” (trade name, manufactured by Minolta Co., Ltd.).
○: ΔE is smaller than 5 (dirt is not so noticeable),
Δ: ΔE is 5 to 10 (dirt is slightly noticeable),
X: ΔE exceeds 10 (dirt is noticeable).
Claims (4)
主剤成分（Ｉ）又は硬化剤成分（II）のいずれか又は双方が顔料分（Ｄ）及び／又はオルガノシリケート化合物（Ｅ）を含むものであり、
樹脂成分（Ａ）がその成分の一部として、アミノ基及び／又は４級アンモニウム基を含有するアクリルポリオール（Ａ−１）並びにアミノ基及び４級アンモニウム基非含有アクリルポリオール（Ａ−２）を共に含むものであり、
アクリルポリオール（Ａ−１）が、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノプロピルメタクリレート、ジメチルアミノプロピルアクリルアミド、メタクリル酸ジメチルアミノエチルメチルクロライド塩から選ばれる少なくとも１種のアミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマー、水酸基含有重合性不飽和モノマー並びにその他の重合性不飽和モノマーを共重合成分とするものであり、
これらモノマー合計質量を基準として、アミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマーの使用割合が３〜２５質量％であり、該アミノ基含有重合性不飽和モノマー及び／又は４級アンモニウム基含有重合性不飽和モノマーの使用量が、アクリルポリオール（Ａ−１）及びアクリルポリオール（Ａ−２）の固形分合計１００質量部を基準として０．２〜２５質量部の範囲内にある低汚染塗料組成物。 A two-component composition comprising a main component (I) containing a resin component (A) and an organic solvent (B) and a curing agent component (II) containing a polyisocyanate compound (C),
Either or both of the main component (I) and the curing agent component (II) contain the pigment component (D) and / or the organosilicate compound (E),
The resin component (A) includes, as part of the component, an acrylic polyol (A-1) containing an amino group and / or a quaternary ammonium group, and an acrylic polyol (A-2) containing no amino group and quaternary ammonium group. Including both
The acrylic polyol (A-1) is selected from N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, dimethylaminopropylacrylamide, and dimethylaminoethylmethyl chloride methacrylate salt. And at least one amino group-containing polymerizable unsaturated monomer and / or quaternary ammonium group-containing polymerizable unsaturated monomer, hydroxyl group-containing polymerizable unsaturated monomer, and other polymerizable unsaturated monomers as copolymerization components. Yes,
Based on the total mass of these monomers, the proportion of the amino group-containing polymerizable unsaturated monomer and / or quaternary ammonium group-containing polymerizable unsaturated monomer is 3 to 25% by mass, and the amino group-containing polymerizable unsaturated monomer And / or the usage-amount of a quaternary ammonium group containing polymerizable unsaturated monomer is 0.2-25 mass parts on the basis of 100 mass parts of solid content total of acrylic polyol (A-1) and acrylic polyol (A-2). A low-contamination paint composition in the range of
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