JP4521169B2 - Water-based paint composition for outer surface of seamless metal can, and seamless metal can having cured coating layer of the paint composition - Google Patents
Water-based paint composition for outer surface of seamless metal can, and seamless metal can having cured coating layer of the paint composition Download PDFInfo
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- JP4521169B2 JP4521169B2 JP2003291911A JP2003291911A JP4521169B2 JP 4521169 B2 JP4521169 B2 JP 4521169B2 JP 2003291911 A JP2003291911 A JP 2003291911A JP 2003291911 A JP2003291911 A JP 2003291911A JP 4521169 B2 JP4521169 B2 JP 4521169B2
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- seamless metal
- metal
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- 229910052751 metal Inorganic materials 0.000 title claims description 53
- 239000002184 metal Substances 0.000 title claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 38
- 239000003973 paint Substances 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 title claims description 11
- 239000011247 coating layer Substances 0.000 title description 4
- 239000011248 coating agent Substances 0.000 claims description 55
- 238000000576 coating method Methods 0.000 claims description 55
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 239000008199 coating composition Substances 0.000 claims description 33
- 239000000049 pigment Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229920003180 amino resin Polymers 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 amino compound Chemical class 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 229920000178 Acrylic resin Polymers 0.000 description 12
- 239000004925 Acrylic resin Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 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
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- FNNFAYGKUXMHSH-UHFFFAOYSA-N 6-[2-(4,6-diamino-1,3,5-triazin-2-yl)phenyl]-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C(=CC=CC=2)C=2N=C(N)N=C(N)N=2)=N1 FNNFAYGKUXMHSH-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005010 epoxy-amino resin Substances 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Rigid Containers With Two Or More Constituent Elements (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本発明は、シームレス金属缶の外表面にカラーフリップフロップ性と耐レトルト性を有する塗膜層を形成するためのシームレス金属缶外面用水性塗料組成物、及び該塗料組成物の乾燥硬化塗膜層を有するシームレス金属缶に関する。 The present invention relates to an aqueous coating composition for the outer surface of a seamless metal can for forming a coating layer having color flip-flop properties and retort resistance on the outer surface of the seamless metal can, and a dry-cured coating layer of the coating composition. The present invention relates to a seamless metal can.
近年、化粧品用、飲食物用等に使用される金属缶の意匠性を高めるために、パール系顔料を含有するワニスや、光干渉性顔料を添加した塗料により、金属缶表面に塗膜を形成することが提案されている。(例えば、特許文献1及び2参照)
また、自動車車体等の高い意匠性が必要とされる物品に、光源の位置や見る人の位置によって、塗膜の色調が2色以上に変化するカラーフリップフロップ性を付与する塗料組成物も提案されている。(特許文献3及び4参照)
In recent years, in order to enhance the design of metal cans used for cosmetics, food and drinks, etc., a coating film is formed on the surface of metal cans with varnishes containing pearl pigments and paints with added light interference pigments. It has been proposed to do. (For example, see Patent Documents 1 and 2)
We also propose a coating composition that gives color flip-flop properties that change the color tone of the coating film to two or more colors depending on the position of the light source or the position of the viewer on articles that require high design, such as automobile bodies. Has been. (See Patent Documents 3 and 4)
飲料や食料を収納した金属缶では、内容物を充填密封した後に内容物を殺菌するために、例えば120℃30分間といった条件で加圧水蒸気処理(レトルト処理)が行われる。したがって、金属缶表面に形成する塗膜にはこのようなレトルト処理に対する耐性が必要とされ、このような観点から、従来の金属缶用塗料としては、エポキシ−アミノ系樹脂、アクリル−アミノ系樹脂、ポリエステル−アミノ系樹脂を有機溶剤に溶解した溶剤型塗料が使用されている。しかしながら、溶剤型塗料を使用した場合には、塗膜の乾燥時に多量の溶剤が揮散し大気汚染の原因となり、また資源の浪費を招くものであった。 In metal cans containing beverages and foods, pressurized water vapor treatment (retort treatment) is performed under conditions such as 120 ° C. for 30 minutes in order to sterilize the contents after filling and sealing the contents. Therefore, the coating film formed on the surface of the metal can needs to have resistance to such retort treatment. From such a viewpoint, as a conventional paint for metal can, epoxy-amino resin, acrylic-amino resin A solvent-type paint in which a polyester-amino resin is dissolved in an organic solvent is used. However, when a solvent-type paint is used, a large amount of solvent is volatilized when the coating film is dried, which causes air pollution and wastes resources.
このような溶剤型塗料の欠点を解消するために、例えばアクリル系樹脂やポリエステル系樹脂等の水性皮膜形成樹脂とアミノ系樹脂を主成分とする種々の水性塗料が提案されているが、これらの水性塗料を使用した場合には塗膜の耐水性が劣ったものとなり、レトルト処理に耐える塗膜を得ることはできなかった。
特に塗膜の意匠性を高めるために、パール系顔料や光干渉性顔料を添加した真珠光沢やカラーフリップフロップ性を有する塗料では、これらの顔料を水性塗料に配合することによって、得られる塗膜の耐レトルト性が一段と低下する傾向がみられ、耐レトルト性と意匠性を両立させた金属缶外面用水性塗料組成物を製造することは、きわめて困難であった。特に、塗装方法や塗装工程に制約のある、金属を絞りしごき成形したシームレス缶(DI缶、薄肉化深絞り缶等)にも適用可能な、水性塗料組成物を得ることは、実質的に不可能であった。
In order to eliminate the disadvantages of such solvent-based paints, various water-based paints mainly composed of an aqueous film-forming resin such as an acrylic resin or a polyester resin and an amino resin have been proposed. When a water-based paint was used, the water resistance of the coating film was inferior, and a coating film that could withstand retort treatment could not be obtained.
Especially for paints with pearl luster and color flip-flop properties to which pearl pigments and light interference pigments are added in order to improve the design of the paint film, the paint film obtained by blending these pigments in the aqueous paint However, it was extremely difficult to produce a water-based paint composition for the outer surface of a metal can that has both retort resistance and design properties. In particular, it is substantially impossible to obtain an aqueous coating composition that can be applied to seamless cans (DI cans, thin-walled deep-drawn cans, etc.) that are formed by squeezing and squeezing metal, which have restrictions on the painting method and process. It was possible.
したがって、本発明は上記従来技術の問題点を解消して、シームレス金属缶外面に塗装した際に、光源の位置や見る角度によって塗膜の色調が大きく変化するカラーフリップフロップ性を付与するとともに、レトルト処理に耐える耐熱性、耐水性及び密着・加工性を有し、しかも環境負荷の少ないシームレス金属缶外面用水性塗料組成物、及び該塗料組成物の硬化乾燥塗膜層を有するシームレス金属缶を提供することを目的とする。 Therefore, the present invention solves the above-mentioned problems of the prior art, and when coated on the outer surface of the seamless metal can, while giving a color flip-flop property that the color tone of the coating film changes greatly depending on the position of the light source and the viewing angle, A water-based coating composition for the outer surface of a seamless metal can that has heat resistance, water resistance, adhesion and processability to withstand retort treatment, and has a low environmental load, and a seamless metal can having a cured and dried coating film layer of the coating composition The purpose is to provide.
本発明者等は鋭意検討した結果、(A)顔料成分として特定のカラーフリップフロップ顔料を選択し、(B)バインダー樹脂成分として、(a)特定の構造を有するアクリル系水性樹脂と(b)特定の構造を有するアミノ樹脂を含有する水性樹脂を使用することによって、上記課題が解決されることを発見し、本発明を完成した。 As a result of intensive studies, the present inventors have selected (A) a specific color flip-flop pigment as the pigment component, (B) (a) an acrylic aqueous resin having a specific structure as the binder resin component, and (b) The present invention has been completed by discovering that the above problems can be solved by using an aqueous resin containing an amino resin having a specific structure.
すなわち、本発明は次のような構成をとるものである。
1.(A)顔料成分、及び(B)バインダー樹脂成分を含有するシームレス金属缶外面用水性塗料組成物において、
(A)顔料成分が、
二酸化ケイ素フレーク表面に金属酸化物を被覆し、さらにシランカップリング剤及びジルコニウム酸化物で表面処理を施したカラーフリップフロップ顔料を含有し、
(B)バインダー樹脂成分が、
(a)α、β−モノエチレン性不飽和カルボン酸(I)、炭素数1〜4のアルコキシ基を含有するN−アルコキシメチル(メタ)アクリルアミド(II)、及び芳香族ビニルモノマー又はアルキル(メタ)アクリレート(III)、を共重合させてなる水性樹脂、及び
(b)活性水素を有するアミノ化合物、ホルムアルデヒド、及び炭素数1〜4のアルコールの反応生成物であり、アミノ化合物の1構造単位当たり1以上のイミノ基を有するアミノ樹脂、
を含有する水性樹脂である、ことを特徴とするシームレス金属缶外面用水性塗料組成物。
2.二酸化ケイ素フレーク表面に被覆する金属酸化物が、二酸化錫、二酸化チタン及び酸化鉄から選択された1種以上の金属酸化物であることを特徴とする1に記載のシームレス金属缶外面用水性塗料組成物。
3.(B)バインダー樹脂成分の固形分100質量部に対して、(A)顔料成分を1〜30質量部含有することを特徴とする1又は2に記載のシームレス金属缶外面用水性塗料組成物。
4.シームレス金属缶の側壁外面に、1〜3のいずれかに記載されたシームレス金属缶外面用水性塗料組成物の乾燥硬化塗膜層を有することを特徴とするシームレス金属缶。
5.シームレス金属缶外面用水性塗料組成物層の乾燥塗膜量が30〜70mg/100cm2であることを特徴とする4に記載のシームレス金属缶。
6.シームレス金属缶の側壁外面に、所望の印刷層を有することを特徴とする4又は5に記載のシームレス金属缶。
That is, the present invention has the following configuration.
1. In the water-based coating composition for the outer surface of a seamless metal can containing (A) a pigment component and (B) a binder resin component,
(A) The pigment component is
It contains a color flip-flop pigment that is coated with a metal oxide on the surface of silicon dioxide flakes and further surface-treated with a silane coupling agent and zirconium oxide,
(B) the binder resin component is
(A) α, β-monoethylenically unsaturated carboxylic acid (I), N-alkoxymethyl (meth) acrylamide (II) containing an alkoxy group having 1 to 4 carbon atoms, and an aromatic vinyl monomer or alkyl (meta An aqueous resin obtained by copolymerization of acrylate (III), and (b) a reaction product of an amino compound having active hydrogen, formaldehyde, and an alcohol having 1 to 4 carbon atoms, per structural unit of the amino compound An amino resin having one or more imino groups,
An aqueous coating composition for an outer surface of a seamless metal can, characterized in that the aqueous coating composition contains an aqueous resin.
2. 2. The aqueous coating composition for an outer surface of a seamless metal can according to 1, wherein the metal oxide coated on the surface of the silicon dioxide flake is one or more metal oxides selected from tin dioxide, titanium dioxide and iron oxide. object.
3. (B) The water-based coating composition for a seamless metal can outer surface according to 1 or 2, comprising 1 to 30 parts by mass of the pigment component (A) with respect to 100 parts by mass of the solid content of the binder resin component.
4). A seamless metal can having a dry-cured coating film layer of the aqueous coating composition for a seamless metal can outer surface described in any one of 1 to 3 on an outer surface of a side wall of the seamless metal can.
5). 5. The seamless metal can according to 4, wherein the amount of the dried coating film of the aqueous coating composition layer for the outer surface of the seamless metal can is 30 to 70 mg / 100 cm 2 .
6). The seamless metal can according to 4 or 5, wherein a desired printed layer is provided on the outer surface of the side wall of the seamless metal can.
本発明によれば、シームレス金属缶外面に塗布した際に、光源の位置や見る角度によって塗膜の色調が、例えば紫色から緑色まで、或いは赤色から緑色まで大きく変化して意匠性を高めることが可能で、しかもレトルト処理に耐える塗膜を形成することができる、環境負荷の少ないシームレス金属缶外面用水性塗料組成物、ならびに該塗料組成物による硬化塗膜層を有する意匠性の高いレトルト処理耐性を有するシームレス金属缶を得ることができる。 According to the present invention, when applied to the outer surface of a seamless metal can, the color tone of the coating film changes greatly, for example, from purple to green, or from red to green, depending on the position of the light source and the viewing angle, thereby enhancing the design. A water-based coating composition for the outer surface of a seamless metal can that can form a coating film that can withstand the retort treatment and has a low environmental impact, and a highly retort-resistant resist having a hard coating layer formed from the coating composition. A seamless metal can having the following can be obtained.
本発明のシームレス金属缶外面用水性塗料組成物では、(A)顔料成分として、二酸化ケイ素フレーク表面に金属酸化物を被覆し、さらにシランカップリング剤及びジルコニウム酸化物で表面処理を施したカラーフリップフロップ顔料を使用する。
金属酸化物としては、二酸化錫、二酸化チタン及び酸化鉄から選択された1種以上の金属酸化物を使用することが好ましく、例えば、二酸化ケイ素フレーク表面に二酸化錫を被覆しさらに二酸化チタンを被覆することにより、塗膜の色調が紫色から緑色まで変化するカラーフリップフロップ顔料を得ることができる。また、二酸化ケイ素フレーク表面に酸化鉄を被覆し、酸化鉄の膜厚をコントロールすることによって、塗膜の色調が赤色から緑色まで変化するカラーフリップフロップ顔料を得ることができる。
In the aqueous coating composition for the outer surface of a seamless metal can according to the present invention, (A) a color flip-flop in which a metal oxide is coated on a silicon dioxide flake surface as a pigment component, and surface treatment is performed with a silane coupling agent and zirconium oxide Use pigments.
As the metal oxide, it is preferable to use one or more metal oxides selected from tin dioxide, titanium dioxide and iron oxide. For example, the surface of silicon dioxide flakes is coated with tin dioxide and further coated with titanium dioxide. As a result, a color flip-flop pigment whose color tone changes from purple to green can be obtained. Further, by coating iron oxide on the surface of silicon dioxide flakes and controlling the film thickness of the iron oxide, a color flip-flop pigment in which the color tone of the coating film changes from red to green can be obtained.
金属酸化物で表面を被覆した二酸化ケイ素フレークは、さらにシランカップリング剤及びジルコニウム酸化物で表面処理を施すことによって、シームレス金属缶外面に形成する塗膜の耐レトルト性を向上させることができる。シランカップリング剤としては特に制限はなく、通常のシランカップリング剤はいずれも使用することができる。 The silicon dioxide flake whose surface is coated with a metal oxide can further improve the retort resistance of the coating film formed on the outer surface of the seamless metal can by further surface treatment with a silane coupling agent and zirconium oxide. There is no restriction | limiting in particular as a silane coupling agent, Any normal silane coupling agent can be used.
本発明の水性塗料組成物に使用するカラーフリップフロップ顔料の平均粒径分布は、5〜40μmの範囲であることが好ましい。この場合における平均粒径分布とは、顔料の90質量%以上が上記粒径範囲に入ることを意味する。
本発明で使用するカラーフリップフロップ顔料は、市販品として入手することが可能であり、例えば酸化鉄被覆タイプとしては、メルク社製「Color stream T20−01 WNT Viola Fantasy」が、また酸化チタン被覆タイプとしては、メルク社製「Color stream F20−00 WNT Autumn Mystery」が挙げられる。また、強いカラーフリップフロップ性を呈する顔料として、ワッカーケミー社製の「HELICONE HC」、「HELICONE HC XL」が挙げられる。これらのカラーフリップフロップ顔料は、単独で又は2種以上を組み合わせて使用することができる。また、カラーフリップフロップ性を有しない通常の顔料と組み合わせて使用することもできる。
The average particle size distribution of the color flip-flop pigment used in the aqueous coating composition of the present invention is preferably in the range of 5 to 40 μm. The average particle size distribution in this case means that 90% by mass or more of the pigment falls within the above particle size range.
The color flip-flop pigment used in the present invention can be obtained as a commercial product. For example, as an iron oxide coating type, “Color stream T20-01 WNT Via Fantasy” manufactured by Merck Ltd., or a titanium oxide coating type is available. Examples thereof include “Color stream F20-00 WNT Automatic Mystery” manufactured by Merck & Co., Inc. Examples of pigments exhibiting a strong color flip-flop include “HELICONE HC” and “HELICONE HC XL” manufactured by Wacker Chemie. These color flip-flop pigments can be used alone or in combination of two or more. Further, it can be used in combination with an ordinary pigment having no color flip-flop property.
水性塗料組成物中のカラーフリップフロップ顔料の含有量は、(B)バインダー樹脂成分の固形分100質量部に対して1〜30質量部、特に1.5〜20質量部とすることが好ましい。カラーフリップフロップ顔料の含有量が1質量部より少ない場合には、シームレス金属缶外面に形成した塗膜にカラーフリップフロップ性を付与することが困難になる。一方、含有量が30質量部を超えると、塗膜の耐レトルト性が低下する。 The content of the color flip-flop pigment in the aqueous coating composition is preferably 1 to 30 parts by mass, particularly 1.5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the (B) binder resin component. When the content of the color flip-flop pigment is less than 1 part by mass, it becomes difficult to impart color flip-flop properties to the coating film formed on the outer surface of the seamless metal can. On the other hand, when content exceeds 30 mass parts, the retort resistance of a coating film will fall.
本発明のシームレス金属缶外面用水性塗料組成物では、(B)バインダー樹脂成分として、(a)α、β−モノエチレン性不飽和カルボン酸(I)、炭素数1〜4のアルコキシ基を含有するN−アルコキシメチル(メタ)アクリルアミド(II)、及び芳香族ビニルモノマー又はアルキル(メタ)アクリレート(III)、を共重合させてなる水性樹脂、及び
(b)活性水素を有するアミノ化合物、ホルムアルデヒド、及び炭素数1〜4のアルコールの反応生成物であり、アミノ化合物の1構造単位当たり1以上のイミノ基を有するアミノ樹脂を含有する水性樹脂を使用する。
なお、本出願においては、アクリル酸及びメタアクリル酸の両者或いはそれらの誘導体を表す記載として、(メタ)アクリルアミドのように表記するものとする。
In the water-based paint composition for the outer surface of the seamless metal can of the present invention, (B) the binder resin component contains (a) α, β-monoethylenically unsaturated carboxylic acid (I), and an alkoxy group having 1 to 4 carbon atoms. N-alkoxymethyl (meth) acrylamide (II) and an aqueous resin obtained by copolymerizing an aromatic vinyl monomer or alkyl (meth) acrylate (III), and (b) an amino compound having active hydrogen, formaldehyde, And an aqueous resin containing an amino resin that is a reaction product of an alcohol having 1 to 4 carbon atoms and having one or more imino groups per structural unit of the amino compound.
In addition, in this application, it shall describe like (meth) acrylamide as description showing both acrylic acid and methacrylic acid, or those derivatives.
この(a)アクリル系水性樹脂は、例えば次の方法により製造することができる。
(I)α、β−モノエチレン性不飽和カルボン酸、(II)N−アルコキシメチル(メタ)アクリルアミド、及び(III)上記(I)及び(II)と共重合可能なビニルモノマーを含有するビニルモノマー混合物を、有機溶剤中でラジカル重合せしめることにより得られる共重合体溶液から余剰の有機溶剤を減圧溜去した後、アンモニア、有機アミン等の揮発性塩基で水性化する方法、もしくは該共重合体溶液に揮発性塩基及び水を添加した後余剰の有機溶剤を水と共に減圧溜去する方法等。
This (a) acrylic water-based resin can be produced, for example, by the following method.
(I) Vinyl containing α, β-monoethylenically unsaturated carboxylic acid, (II) N-alkoxymethyl (meth) acrylamide, and (III) vinyl monomer copolymerizable with (I) and (II) above A method in which an excess organic solvent is distilled off from a copolymer solution obtained by radical polymerization of a monomer mixture in an organic solvent under reduced pressure, and then made aqueous with a volatile base such as ammonia or organic amine, or the copolymer A method in which a volatile base and water are added to a combined solution, and then an excess organic solvent is distilled off together with water under reduced pressure.
(I)α、β−モノエチレン性不活性カルボン酸としては、例えばアクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸等が挙げられるが、アクリル酸、メタクリル酸が好ましい。これらの使用量は、モノマー全体の5〜20質量%の範囲とすることが好ましい。これらの使用量が5質量%未満では生成樹脂の水性化が困難であり、20質量%を超えると塗膜の耐水性が低下する。 Examples of (I) α, β-monoethylenically inert carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and the like, and acrylic acid and methacrylic acid are preferable. The amount of these used is preferably in the range of 5 to 20% by mass of the whole monomer. If the amount used is less than 5% by mass, it is difficult to make the resulting resin water-based, and if it exceeds 20% by mass, the water resistance of the coating film decreases.
(II)N−アルコキシメチル(メタ)アクリルアミドとしては、例えばメトキシメチル(メタ)アクリルアミド、エトキシメチル(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、イソブトキシメチル(メタ)アクリルアミド等が挙げられる。これらの使用量は、モノマー全体の5〜40質量%の範囲が好ましい。これらの使用量が5質量%未満では硬化不足によって塗膜の耐レトルト性が不充分であり、40質量%を超えると硬化しすぎて塗膜の下地密着性、加工性が損なわれる。 Examples of (II) N-alkoxymethyl (meth) acrylamide include methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, n-butoxymethyl (meth) acrylamide, and isobutoxymethyl (meth) acrylamide. The amount of these used is preferably in the range of 5 to 40% by mass of the whole monomer. If the amount used is less than 5% by mass, the retort resistance of the coating film is insufficient due to insufficient curing, and if it exceeds 40% by mass, it is cured too much and the base adhesion and workability of the coating film are impaired.
(III)上記(I)及び(II)と共重合可能な芳香族ビニルモノマーとしては、例えば、スチレン、p−メチルスチレン、α−メチルスチレン、ビニルトルエン等が挙げられる。また、アルキル(メタ)アクリレートとしては、アクリル酸エチル、アクリル酸ブチル、アクリル酸2−エチルヘキシル、アクリル酸シクロヘキシル、メタクリル酸メチル、メタクリル酸ブチル、メタクリル酸ステアリル、メタクリル酸シクロヘキシル等が例示できる。これらのモノマーは、その使用量がモノマー全体の40〜90質量%の範囲で、塗膜の硬度と可とう性を勘案して種類及び共重合量を選択することが出来る。
(a)アクリル系水性樹脂としては、分子量が5,000〜30,000程度、特に10,000〜25,000程度のものを使用することが好ましい。
(III) Examples of the aromatic vinyl monomer copolymerizable with the above (I) and (II) include styrene, p-methylstyrene, α-methylstyrene, vinyltoluene and the like. Examples of the alkyl (meth) acrylate include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl methacrylate, butyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, and the like. These monomers can be used in an amount of 40 to 90% by mass of the whole monomer, and the type and copolymerization amount can be selected in consideration of the hardness and flexibility of the coating film.
(A) It is preferable to use an acrylic aqueous resin having a molecular weight of about 5,000 to 30,000, particularly about 10,000 to 25,000.
本発明の水性塗料組成物に用いる(a)アクリル系水性樹脂に必須のモノマーは、上記(I)、(II)、(III)であるが、これらのモノマー以外にヒドロキシアルキル(メタ)アクリレート、カルボン酸ビニル、ビニルアルキルエーテル等の(I)、(II)と共重合可能なモノマーも使用することができる。
重合時に用いる溶剤としては、イソプロピルアルコール、n−ブチルアルコール、イソブチルアルコールのようなアルコール系溶剤、エチレングリコールモノメチルエーテル、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プロピルエーテル、エチレングリコールモノブチルエーテルのようなセロソルブ系溶剤、3−メトキシブタノール、3−メチル3−メトキシブタノール等が挙げられる。
Monomers essential for the (a) acrylic aqueous resin used in the aqueous coating composition of the present invention are the above (I), (II), and (III), but in addition to these monomers, hydroxyalkyl (meth) acrylate, Monomers copolymerizable with (I) and (II) such as vinyl carboxylate and vinyl alkyl ether can also be used.
Solvents used in the polymerization include alcohol solvents such as isopropyl alcohol, n-butyl alcohol and isobutyl alcohol, cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether. A solvent, 3-methoxybutanol, 3-methyl 3-methoxybutanol, etc. are mentioned.
本発明の水性塗料組成物に用いる(b)アミノ樹脂は、活性水素を有するアミノ化合物とホルムアルデヒド及び炭素数1〜4のアルコールの反応生成物であって、分子構造中に官能基として、アルコキシ基、メチロール基とともに、アミノ化合物の1構造単位当たり1以上のイミノ基(N−H)を含有することを特徴とする。
上記アミノ化合物としては、例えばメラミン、ベンゾクアナミン、尿素、エチレン尿素、アセトグアナミン、テトラメチレンジグアナミン、フタログアナミン、スピログアナミン等の化合物が挙げられる。また、炭素数1〜4のアルコールとしては、メチルアルコール、エチルアルコール、n−プロピルアルコール、イソプロピルアルコール、n−ブチルアルコール、イソブチルアルコール、sec−ブチルアルコール、t−ブチルアルコール等が挙げられる。
(b)アミノ樹脂としては、分子量が400〜2,000程度、特に500〜1,500程度のものを使用することが好ましい。分子量が400未満では低分子量のアミノ樹脂成分が塗料の焼付時に飛散して焼付オーブンを汚染する原因となり、一方2,000を超えると水性塗料化が困難となる。
The (b) amino resin used in the aqueous coating composition of the present invention is a reaction product of an amino compound having active hydrogen, formaldehyde, and an alcohol having 1 to 4 carbon atoms, and has an alkoxy group as a functional group in the molecular structure. And one or more imino groups (NH) per structural unit of an amino compound together with a methylol group.
Examples of the amino compound include compounds such as melamine, benzoguanamine, urea, ethylene urea, acetoguanamine, tetramethylene diguanamine, phthaloguanamine, and spiroguanamine. Examples of the alcohol having 1 to 4 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, and t-butyl alcohol.
(B) It is preferable to use an amino resin having a molecular weight of about 400 to 2,000, particularly about 500 to 1,500. When the molecular weight is less than 400, the low molecular weight amino resin component is scattered when the paint is baked and contaminates the baking oven. On the other hand, when the molecular weight exceeds 2,000, it becomes difficult to make an aqueous paint.
(B)バインダー樹脂を構成する(a)アクリル系水性樹脂と、(b)イミノ基を有するアミノ樹脂との好ましい使用割合は、樹脂固形分比で、(a)40〜80質量%:(b)20〜60質量%である。(b)の使用量が20質量%未満では塗膜の硬度、耐水性が不充分であり、一方、60質量%を超えると加工性が低下する。 (B) A preferred use ratio of (a) an acrylic aqueous resin constituting the binder resin and (b) an amino resin having an imino group is a resin solid content ratio, and (a) 40 to 80% by mass: (b ) 20 to 60% by mass. When the amount of (b) used is less than 20% by mass, the hardness and water resistance of the coating film are insufficient. On the other hand, when it exceeds 60% by mass, the workability decreases.
本発明の水性塗料組成物において使用し得る溶剤としては、水を主体として、必要に応じて上記(a)アクリル系水性樹脂の重合時に使用した溶剤を併用することができる。 As a solvent that can be used in the water-based coating composition of the present invention, water as a main component can be used together with the solvent used at the time of polymerization of the above (a) acrylic water-based resin, if necessary.
(B)バインダー樹脂には、塗料粘度低下或いは塗膜の下地密着性の向上を目的として、ポリエーテルポリオール、ポリエステルポリオール、ポリウレタンポリオール、或いはビスフェノールAのエチレンオキサイド若しくはプロピレンオキサイド付加物等の低分子ポリオール類を、第3の樹脂成分として上記(a)、(b)に加えて使用することも出来る。この場合、低分子ポリオール類の使用量は、全樹脂固形分中の30質量%以下とすることが、塗膜の耐水性維持の面から好ましい。 (B) The binder resin is a low molecular polyol such as polyether polyol, polyester polyol, polyurethane polyol, or bisphenol A ethylene oxide or propylene oxide adduct for the purpose of lowering the viscosity of the paint or improving the adhesion of the undercoat of the coating film. Can be used as the third resin component in addition to the above (a) and (b). In this case, the amount of the low-molecular polyols used is preferably 30% by mass or less in the total resin solid content from the viewpoint of maintaining the water resistance of the coating film.
本発明の水性塗料組成物を調製するには、上記(a)、(b)及び、所望によりポリオール類を混合し、更に必要に応じて、p−トルエンスルフォン酸、ドデシルベンゼンスルフォン酸、ジノニルジナフタレンジスルフォン酸、或いはこれらのアミン塩を硬化触媒として樹脂固形分100質量部に対し、0.02〜0.2質量部添加すればよい。
本発明の水性塗料組成物には、従来公知の消泡剤、レベリング剤、滑剤、紫外線吸収剤等を添加することができる。
In order to prepare the aqueous coating composition of the present invention, the above (a), (b) and, if necessary, polyols are mixed, and if necessary, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonyl. What is necessary is just to add 0.02-0.2 mass part with respect to 100 mass parts of resin solid content by using dinaphthalenedisulfonic acid or these amine salts as a curing catalyst.
Conventionally known antifoaming agents, leveling agents, lubricants, ultraviolet absorbers and the like can be added to the aqueous coating composition of the present invention.
本発明の水性塗料組成物は、以下の方法で効率よく調製することができる。
(B)バインダー樹脂成分に(A)カラーフリップフロップ顔料を加えて、分散攪拌機で攪拌・混合する。カラーフリップフロップ顔料は、練肉せず攪拌のみで分散させるのが望ましい。
The aqueous coating composition of the present invention can be efficiently prepared by the following method.
(B) Add the color flip-flop pigment (A) to the binder resin component, and stir and mix with a dispersion stirrer. It is desirable to disperse the color flip-flop pigment only by stirring without kneading.
本発明の水性塗料組成物は、ロールコート、スプレーコート、刷毛塗り等公知の手段により電気錫メッキ鋼板、クロム処理鋼板、アルミニウム板等の金属基材から絞りしごき成形等により作製されたシームレス金属缶外面に塗装することが出来る。
好ましい例としては、例えば2ピースコーターにてアルミニウム製DI缶に塗装することにより、アルミニウム下地の光沢、平滑性を活かし強いカラーフリップフロップ性を呈する塗膜を形成することができる。
The aqueous coating composition of the present invention is a seamless metal can produced by drawing and ironing from a metal substrate such as an electrotin-plated steel plate, a chrome-treated steel plate, and an aluminum plate by known means such as roll coating, spray coating, brush coating, etc. Can be painted on the outside.
As a preferred example, a coating film exhibiting strong color flip-flop properties can be formed by applying the gloss and smoothness of the aluminum base by, for example, coating on an aluminum DI can with a two-piece coater.
本発明の水性塗料組成物は、シームレス金属缶外面に塗付した後に、150〜200℃−10分程度の条件から250℃−10秒程度の高温短時間条件までの広範な乾燥条件に於いて、性能良好な硬化塗膜を形成することが出来る。好ましい乾燥条件としては、例えばアルミニウム製DI缶の場合には、一般的な焼付条件である200℃−15秒である。 The water-based coating composition of the present invention can be applied to a wide range of drying conditions from 150 to 200 ° C. for about 10 minutes to 250 ° C. for about 10 seconds after being applied to the outer surface of a seamless metal can. A cured coating film with good performance can be formed. As a preferable drying condition, for example, in the case of an aluminum DI can, a general baking condition is 200 ° C. for 15 seconds.
本発明の水性塗料組成物は、シームレス金属缶外面に形成する塗膜の乾燥質量が30〜70mg/100cm2、特に35〜60mg/100cm2となるようにシームレス金属缶外面に塗布することが好ましい。乾燥質量が30mg/100cm2未満の場合には、カラーフリップフロップ性が低下する傾向があり、一方乾燥質量が70mg/100cm2を超えた場合には、耐レトルト性が低下する傾向が認められる。
この塗膜は、シームレス金属缶の側壁外面にベースコート層又はトップコート層として形成することができる。また、この塗膜は外面全面に形成する以外に、ロゴマーク等の印刷模様を形成するために使用してもよい。そして、この塗膜の下地として、濃色又は不透明なインキ層を設けた場合には、下地層により光が反射されて、カラーフリップフロップ効果が一段と高められたものとなる。
The aqueous coating composition of the present invention is preferably applied to the outer surface of the seamless metal can so that the dry mass of the coating film formed on the outer surface of the seamless metal can is 30 to 70 mg / 100 cm 2 , particularly 35 to 60 mg / 100 cm 2. . When the dry mass is less than 30 mg / 100 cm 2 , the color flip-flop property tends to be reduced. On the other hand, when the dry mass exceeds 70 mg / 100 cm 2 , the tendency to decrease the retort resistance is recognized.
This coating film can be formed on the outer surface of the side wall of the seamless metal can as a base coat layer or a top coat layer. In addition to forming this coating film on the entire outer surface, it may be used for forming a printed pattern such as a logo mark. When a dark or opaque ink layer is provided as the base of this coating film, light is reflected by the base layer, and the color flip-flop effect is further enhanced.
以下、実施例により、本発明を具体的に説明するが、以下の具体例は本発明を限定するものではない。なお、特に指定のない限り、実施例中の、部、%は質量部、質量%を表す。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the following specific examples do not limit this invention. Unless otherwise specified, parts and% in the examples represent parts by mass and% by mass.
〔合成例1:水性アクリル樹脂溶液a−1の合成〕
攪拌機、環流冷却器、滴下ロート、窒素ガス導入管、温度計を具備した容量1リットルの四ツ口フラスコ反応容器に、エチレングリコールモノイソプロピルエーテル420部を仕込み、120℃迄昇温した。同温度を保持しつつ、滴下ロートからアクリル酸40部、n−ブトキシメチルアクリルアミド160部、メタアクリル酸メチル120部、アクリル酸エチル80部、アゾビスイソブチルニトリル16部の混合物を4時間に亘って連続滴下した。滴下終了1時間後にジ−t−ブチルパーオキサイド3部を添加し、更に2時間反応を行った。生成溶液を80℃まで冷却し、減圧下に合成溶剤300部を留去した後、ジメチルアミノエタノール40部、水252部を添加混合して、不揮発分50%、残留有機溶剤14.6%の透明粘稠なアクリル樹脂水溶液a−1を得た。
[Synthesis Example 1: Synthesis of aqueous acrylic resin solution a-1]
To a 1-liter four-necked flask reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen gas inlet tube, and a thermometer, 420 parts of ethylene glycol monoisopropyl ether was charged and heated to 120 ° C. While maintaining the same temperature, a mixture of 40 parts of acrylic acid, 160 parts of n-butoxymethylacrylamide, 120 parts of methyl methacrylate, 80 parts of ethyl acrylate, and 16 parts of azobisisobutylnitrile is added over 4 hours from the dropping funnel. Continuous dripping. One hour after the completion of dropping, 3 parts of di-t-butyl peroxide was added, and the reaction was further performed for 2 hours. The resulting solution was cooled to 80 ° C., and 300 parts of the synthetic solvent was distilled off under reduced pressure. Then, 40 parts of dimethylaminoethanol and 252 parts of water were added and mixed to obtain a non-volatile content of 50% and a residual organic solvent of 14.6%. A transparent viscous acrylic resin aqueous solution a-1 was obtained.
〔合成例2:水性アクリル樹脂溶液a−2の合成〕
攪拌機、環流冷却器、滴下ロート、窒素ガス導入管、温度計を具備した容量1リットルの四ツ口フラスコ反応容器に、エチレングリコールモノイソプロピルエーテル420部を仕込み、120℃迄昇温した。同温度を保持しつつ、滴下ロートからアクリル酸40部、n−ブトキシメチルアクリルアミド80部、メタアクリル酸メチル120部、アクリル酸エチル80部、アクリル酸ブチル80部、アゾビスイソブチルニトリル16部の混合物を4時間に亘って連続滴下した。滴下終了1時間後にジ−t−ブチルパーオキサイド3部を添加し、更に2時間反応を行った。生成溶液を80℃まで冷却し、減圧下に合成溶剤300部を留去した後、ジメチルアミノエタノール40部、水252部を添加混合して、不揮発分50%、残留有機溶剤14.6%の透明粘稠なアクリル樹脂水溶液a−2を得た。
[Synthesis Example 2: Synthesis of aqueous acrylic resin solution a-2]
To a 1-liter four-necked flask reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen gas inlet tube, and a thermometer, 420 parts of ethylene glycol monoisopropyl ether was charged and heated to 120 ° C. While maintaining the same temperature, a mixture of 40 parts of acrylic acid, 80 parts of n-butoxymethylacrylamide, 120 parts of methyl methacrylate, 80 parts of ethyl acrylate, 80 parts of butyl acrylate and 16 parts of azobisisobutylnitrile from the dropping funnel Was continuously added dropwise over 4 hours. One hour after the completion of dropping, 3 parts of di-t-butyl peroxide was added, and the reaction was further performed for 2 hours. The resulting solution was cooled to 80 ° C., and 300 parts of the synthetic solvent was distilled off under reduced pressure. Then, 40 parts of dimethylaminoethanol and 252 parts of water were added and mixed to obtain a non-volatile content of 50% and a residual organic solvent of 14.6%. A transparent viscous acrylic resin aqueous solution a-2 was obtained.
〔比較合成例1:水性アクリル樹脂溶液a−3の合成〕
攪拌機、環流冷却器、滴下ロート、窒素ガス導入管、温度計を具備した容量1リットルの四ツ口フラスコ反応容器に、エチレングリコールモノイソプロピルエーテル420部を仕込み、120℃迄昇温した。同温度を保持しつつ、滴下ロートからアクリル酸60部、メタアクリル酸メチル120部、アクリル酸エチル112部、アクリル酸ブチル108部、アゾビスイソブチルニトリル16部の混合物を4時間に亘って連続滴下した。滴下終了1時間後にジ−t−ブチルパーオキサイド3部を添加し、更に2時間反応を行った。生成溶液を80℃まで冷却し、減圧下に合成溶剤300部を留去した後、ジメチルアミノエタノール60部、水232部を添加混合して、不揮発分50%、残留有機溶剤14.6%の透明粘稠なアクリル樹脂水溶液a−3を得た。
[Comparative Synthesis Example 1: Synthesis of aqueous acrylic resin solution a-3]
To a 1-liter four-necked flask reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a nitrogen gas inlet tube, and a thermometer, 420 parts of ethylene glycol monoisopropyl ether was charged and heated to 120 ° C. While maintaining the same temperature, a mixture of 60 parts of acrylic acid, 120 parts of methyl methacrylate, 112 parts of ethyl acrylate, 108 parts of butyl acrylate, and 16 parts of azobisisobutylnitrile was continuously dropped over 4 hours from the dropping funnel. did. One hour after the completion of dropping, 3 parts of di-t-butyl peroxide was added, and the reaction was further performed for 2 hours. The resulting solution was cooled to 80 ° C., and 300 parts of the synthetic solvent was distilled off under reduced pressure. Then, 60 parts of dimethylaminoethanol and 232 parts of water were added and mixed to obtain a non-volatile content of 50% and a residual organic solvent of 14.6%. A transparent viscous acrylic resin aqueous solution a-3 was obtained.
〔合成例3:イミノ基含有メチルエーテル化ベンゾグアナミン樹脂b−1の合成〕
攪拌機、環流冷却器、滴下ロート、温度計、窒素ガス導入管を具備した容量2リットルの四ツ口フラスコにメタノール640部(20モル)、92%パラホルムアルデヒド130.4部(4モル)、ベンゾグアナミン374部(1モル)、10%水酸化ナトリウム水溶液0.3部を仕込み、70℃まで昇温した。同温度で1時間反応を行った後、30℃まで降温し、36%塩酸にてPHを3.0に調整して2時間反応させた。次いで、50%水酸化ナトリウムにてPHを8.0に調整した後、未反応メタノール、ホルムアルデヒドを加熱減圧下に留去し、エチレングリコールモノブチルエーテルで希釈した。生成物は不揮発分80.1%、ガードナー粘度Z7であった。
[Synthesis Example 3: Synthesis of imino group-containing methyl etherified benzoguanamine resin b-1]
640 parts (20 moles) of methanol, 130.4 parts (4 moles) of 92% paraformaldehyde, 4 parts of benzoguanamine in a 2-liter four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen gas inlet tube 374 parts (1 mole) and 0.3 part of a 10% aqueous sodium hydroxide solution were charged, and the temperature was raised to 70 ° C. After carrying out the reaction at the same temperature for 1 hour, the temperature was lowered to 30 ° C., the pH was adjusted to 3.0 with 36% hydrochloric acid, and the reaction was carried out for 2 hours. Next, after adjusting the pH to 8.0 with 50% sodium hydroxide, unreacted methanol and formaldehyde were distilled off under heating and reduced pressure, and diluted with ethylene glycol monobutyl ether. The product had a non-volatile content of 80.1% and a Gardner viscosity of Z7.
〔合成例4:イミノ基含有メチルエーテル化ベンゾクアナミン樹脂b−2の合成〕
92%パラホルムアルデヒドの仕込み量を195.7部(6モル)とした以外は、合成例3と同様の操作を行い、不揮発分80.3%、ガードナー粘度Z4の生成物を得た。
[Synthesis Example 4: Synthesis of imino group-containing methyl etherified benzoguanamine resin b-2]
The same operation as in Synthesis Example 3 was carried out except that the amount of 92% paraformaldehyde was 195.7 parts (6 moles) to obtain a product having a nonvolatile content of 80.3% and a Gardner viscosity Z4.
〔比較合成例2:メチルエーテル化ベンゾグアナミン樹脂b−3の合成〕
92%パラホルムアルデヒドの仕込み量を391.3部(12モル)とした以外は、合成例3と同様の操作を行い、不揮発分79.9%、ガードナー粘度Zの生成物を得た。
[Comparative Synthesis Example 2: Synthesis of methyl etherified benzoguanamine resin b-3]
A product having a nonvolatile content of 79.9% and a Gardner viscosity Z was obtained by performing the same operation as in Synthesis Example 3, except that the amount of 92% paraformaldehyde was 391.3 parts (12 mol).
(実施例1〜4)
上記の合成例1〜4ならびに比較合成例1、2で得た水性アクリル樹脂溶液、アミノ樹脂溶液、及びBA−8グリコール(日本乳化剤社製、ビスフェノールA−エチレンオキサイド付加物)を、各成分の固形分比が表1に示したように調整し、これにエチレングリコールモノイソプロピレンエーテル、水、及びp−トルエンスルフォン酸、更にはカラーフリップフロップ顔料(メルク社製Color stream T20−01WNT)を添加混合して、不揮発分40%、有機溶剤含有量15%、触媒量0.2PHRの塗料を調製した。
(Examples 1-4)
The aqueous acrylic resin solution, amino resin solution, and BA-8 glycol (manufactured by Nippon Emulsifier Co., Ltd., bisphenol A-ethylene oxide adduct) obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2 were used for each component. The solid content ratio was adjusted as shown in Table 1, and ethylene glycol monoisopropylene ether, water, p-toluenesulfonic acid, and color flip-flop pigment (Color stream T20-01WNT manufactured by Merck) were added thereto. By mixing, a paint having a nonvolatile content of 40%, an organic solvent content of 15%, and a catalyst amount of 0.2 PHR was prepared.
(比較例1〜5)
上記実施例と同様の方法で、水性アクリル樹脂、アミノ樹脂、BA−8グリコールの固形分比が、表1のようになるように塗料を調製した。
(Comparative Examples 1-5)
In the same manner as in the above Examples, a coating material was prepared so that the solid content ratio of the aqueous acrylic resin, amino resin, and BA-8 glycol was as shown in Table 1.
実施例1〜4及び比較例1〜5で得られた塗料について、以下の塗膜物性試験を行い、その結果を表2に示した。
(塗膜物性試験)
アルミニウム製DI缶の側壁外面に、9インチテストコーターとマンドレルを用いて乾燥後の塗膜質量が50mg/100cm2となるように塗料を塗布し、200℃の熱風循環式ガスオーブンで15秒+60秒間乾燥させてテスト缶を作製した。このテスト缶を切り開きパネルとしたものを次の試験に供した。
About the coating material obtained in Examples 1-4 and Comparative Examples 1-5, the following coating-film physical property tests were done, and the result was shown in Table 2.
(Film properties test)
A 9-inch test coater and mandrel were used to coat the outer surface of the aluminum DI can so that the coating weight after drying would be 50 mg / 100 cm 2, and then for 15 seconds +60 in a 200 ° C. hot-air circulating gas oven. Test cans were prepared by drying for 2 seconds. The test can was cut and used as a panel for the next test.
(耐煮沸水性試験)
テストパネルを煮沸水中に30分間浸漬した後、塗膜の状態を評価した。塗膜の白化・浮きがないものを○、塗膜の白化・浮きがわずかに発生したものを△、塗膜の白化・浮きが著しいものを×で示した。
(Boiling water resistance test)
After immersing the test panel in boiling water for 30 minutes, the state of the coating film was evaluated. A case where the coating film was not whitened or floated was indicated by ○, a case where the coating film was slightly whitened or lifted was indicated by Δ, and a case where the coating film was markedly whitened or floated was indicated by ×.
(耐レトルト性試験)
加圧容器中でテストパネルを130℃の水蒸気に30分間曝した後、塗膜の状態を評価した。評価結果は、耐煮沸水性試験と同様にして示した。
(Retort resistance test)
After the test panel was exposed to water vapor at 130 ° C. for 30 minutes in a pressurized container, the state of the coating film was evaluated. The evaluation results were shown in the same manner as in the boiling water resistance test.
(加工密着性試験)
エリクセン試験を行った。塗膜の割れが発生しないものを○、塗膜の割れがわずかに発生したものを△、塗膜の割れが著しく発生したものを×で示した。
(Processing adhesion test)
The Eriksen test was performed. The case where the crack of the coating film did not occur was indicated by ○, the case where the crack of the coating film slightly occurred was indicated by Δ, and the case where the crack of the coating film occurred significantly was indicated by ×.
(衝撃加工耐性試験)
デュポン衝撃試験、500g−10cm、20cm、30cmの条件で加工後の塗膜の状態を評価した。評価結果は、加工密着性試験と同様にして示した。
(Shock resistance test)
The state of the coating film after processing was evaluated under the conditions of a DuPont impact test, 500 g-10 cm, 20 cm, and 30 cm. The evaluation results were shown in the same manner as in the work adhesion test.
(塗膜硬度試験)
テストパネルを室温、ならびに80℃の湯中に浸漬し、常法により鉛筆硬度を測定した。 室温鉛筆硬度は、2H以上を○、HB〜Hを△、B以下を×で示した。
一方、湯中鉛筆硬度は、2B以上を○、2B〜4Bを△、5B以下を×で示した。
(Coating hardness test)
The test panel was immersed in hot water at room temperature and 80 ° C., and the pencil hardness was measured by a conventional method. The room temperature pencil hardness was indicated by ◯ for 2H or more, Δ for HB to H, and x for B or less.
On the other hand, the pencil hardness in hot water is indicated by ◯ for 2B or more, Δ for 2B to 4B, and x for 5B or less.
(カラーフリップフロップ性)
塗膜物性試験で作製したテスト缶を目視により観察し、意匠性を示す色変化が十分であるものを○、意匠性を示す色変化が認められるものを△、色変化が不十分又は発生しないものを×で示した。
(Color flip-flop property)
Test cans prepared by coating film physical property test are visually observed, ◯ when the color change indicating the design property is sufficient, △ when the color change indicating the design property is recognized, △, insufficient or no color change The thing was shown by x.
(実施例5〜10)
合成例1で得た水性アクリル樹脂溶液、合成例3で得たアミノ樹脂溶液、及びBA−8グリコール(日本乳化剤社製、ビスフェノールA−エチレンオキサイド付加物)を、各成分の固形分比が表3に示したように調整し、これにエチレングリコールモノイソプロピレンエーテル、水、及びp−トルエンスルフォン酸、更にはカラーフリップフロップ顔料(メルク社製、Color stream T20−01WNT)の添加量を各々変動させ混合して、表3に記載の塗料(不揮発分40%、有機溶剤含有量15%、触媒量0.2PHR)を調製した。
(Examples 5 to 10)
The aqueous acrylic resin solution obtained in Synthesis Example 1, the amino resin solution obtained in Synthesis Example 3, and BA-8 glycol (manufactured by Nippon Emulsifier Co., Ltd., bisphenol A-ethylene oxide adduct) The amount of ethylene glycol monoisopropylene ether, water, p-toluenesulfonic acid, and color flip-flop pigment (Merck, Color stream T20-01WNT) was varied. The paints shown in Table 3 (non-volatile content 40%, organic solvent content 15%, catalyst amount 0.2 PHR) were prepared.
実施例5〜10で得られた塗料について、上記の塗膜物性試験を行い、その結果を表4に示した。 About the coating material obtained in Examples 5-10, said coating-film physical property test was done and the result was shown in Table 4.
(実施例11〜16)
合成例1で得た水性アクリル樹脂溶液、合成例3で得たアミノ樹脂溶液、及びBA−8グリコール(日本乳化剤社製、ビスフェノールA−エチレンオキサイド付加物)を、一定の固形分比に調整し、これにエチレングリコールモノイソプロピレンエーテル、水、及びp−トルエンスルフォン酸、更にはカラーフリップフロップ顔料(メルク社製、Color stream T20−01WNT)の添加量を5質量部とした塗料(不揮発分40%、有機溶剤含有量15%、触媒量0.2PHR)を調製した。
得られた塗料を、アルミニウム製DI缶の側壁外面に、9インチテストコーターとマンドレルを使用して塗布することにより、乾燥後の塗膜質量が表5に記載したものとなる塗装板を作製した。
(Examples 11 to 16)
The aqueous acrylic resin solution obtained in Synthesis Example 1, the amino resin solution obtained in Synthesis Example 3, and BA-8 glycol (Nippon Emulsifier Co., Ltd., bisphenol A-ethylene oxide adduct) were adjusted to a certain solid content ratio. In addition, a coating material (nonvolatile content 40) containing 5 parts by mass of ethylene glycol monoisopropylene ether, water, p-toluenesulfonic acid, and further color flip-flop pigment (Merck, Color stream T20-01WNT). %, Organic solvent content 15%, catalyst amount 0.2 PHR).
The obtained paint was applied to the outer surface of the side wall of an aluminum DI can by using a 9 inch test coater and a mandrel to prepare a coated plate having the coating film mass after drying described in Table 5. .
実施例11〜16で作製した塗装板について、上記の塗膜物性試験を行ない、その結果を表6に記載した。 About the coating board produced in Examples 11-16, said coating-film physical property test was done, and the result was described in Table 6.
上記各例にみられるように、本発明のシームレス金属外面用水性塗料組成物からなるベースコート層又はトップコート層を有するシームレス金属缶は、光源の位置や見る角度により反射光の色調が大きく変化する強いカラーフリップフロップ性を呈する真珠光沢様の高められた意匠性を有し、(a)アクリル樹脂中のN−アルコキシメチル基と(b)アミノ樹脂中のイミノ基の架橋反応により、飲料缶・食品缶殺菌処理の加圧蒸気処理工程に耐えうる耐熱性、耐水性ならびに各種缶形態に加工し得る密着性・加工性を有する。
As seen in each of the above examples, the seamless metal can having the base coat layer or the top coat layer made of the aqueous coating composition for a seamless metal outer surface of the present invention changes greatly in the color tone of the reflected light depending on the position of the light source and the viewing angle. Beverage cans with a pearly luster-like enhanced design that exhibits strong color flip-flop properties, and (a) N-alkoxymethyl groups in acrylic resin and (b) imino groups in amino resin It has heat resistance and water resistance that can withstand the pressurized steam treatment process of food can sterilization treatment, and adhesion and workability that can be processed into various can forms.
Claims (6)
(A)顔料成分が、
二酸化ケイ素フレーク表面に金属酸化物を被覆し、さらにシランカップリング剤及びジルコニウム酸化物で表面処理を施したカラーフリップフロップ顔料を含有し、
(B)バインダー樹脂成分が、
(a)α、β−モノエチレン性不飽和カルボン酸(I)、炭素数1〜4のアルコキシ基を含有するN−アルコキシメチル(メタ)アクリルアミド(II)、及び芳香族ビニルモノマー又はアルキル(メタ)アクリレート(III)、を共重合させてなる水性樹脂、及び
(b)活性水素を有するアミノ化合物、ホルムアルデヒド、及び炭素数1〜4のアルコールの反応生成物であり、アミノ化合物の1構造単位当たり1以上のイミノ基を有するアミノ樹脂、
を含有する水性樹脂である、ことを特徴とするシームレス金属缶外面用水性塗料組成物。 In the water-based coating composition for the outer surface of a seamless metal can containing (A) a pigment component and (B) a binder resin component,
(A) The pigment component is
It contains a color flip-flop pigment that is coated with a metal oxide on the surface of silicon dioxide flakes and further surface-treated with a silane coupling agent and zirconium oxide,
(B) the binder resin component is
(A) α, β-monoethylenically unsaturated carboxylic acid (I), N-alkoxymethyl (meth) acrylamide (II) containing an alkoxy group having 1 to 4 carbon atoms, and an aromatic vinyl monomer or alkyl (meta An aqueous resin obtained by copolymerization of acrylate (III), and (b) a reaction product of an amino compound having active hydrogen, formaldehyde, and an alcohol having 1 to 4 carbon atoms, per structural unit of the amino compound An amino resin having one or more imino groups,
An aqueous coating composition for an outer surface of a seamless metal can, characterized in that the aqueous coating composition contains an aqueous resin.
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JPH07316489A (en) * | 1994-05-20 | 1995-12-05 | Toyo Ink Mfg Co Ltd | Water-based coating composition and metallic sheet or plate coated therewith |
JPH0834954A (en) * | 1994-07-25 | 1996-02-06 | Dainippon Ink & Chem Inc | Water-based coating composition |
JPH1191031A (en) * | 1997-09-18 | 1999-04-06 | Ueno Hiroshi | Can wall constituting laminate with excellent sense of luster and seamless can |
JP2000502401A (en) * | 1996-09-27 | 2000-02-29 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Modified pearlescent pigments for aqueous coating systems |
JP2000086943A (en) * | 1998-09-10 | 2000-03-28 | Nippon Paint Co Ltd | Dichroic coating composition |
JP2002080776A (en) * | 2000-06-29 | 2002-03-19 | Nippon Yushi Basf Coatings Kk | One coat metallic coating material composition |
JP2002256174A (en) * | 2001-02-28 | 2002-09-11 | Asahi Glass Co Ltd | Color luster pigment and its manufacturing method |
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JPH07316489A (en) * | 1994-05-20 | 1995-12-05 | Toyo Ink Mfg Co Ltd | Water-based coating composition and metallic sheet or plate coated therewith |
JPH0834954A (en) * | 1994-07-25 | 1996-02-06 | Dainippon Ink & Chem Inc | Water-based coating composition |
JP2000502401A (en) * | 1996-09-27 | 2000-02-29 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Modified pearlescent pigments for aqueous coating systems |
JPH1191031A (en) * | 1997-09-18 | 1999-04-06 | Ueno Hiroshi | Can wall constituting laminate with excellent sense of luster and seamless can |
JP2000086943A (en) * | 1998-09-10 | 2000-03-28 | Nippon Paint Co Ltd | Dichroic coating composition |
JP2002080776A (en) * | 2000-06-29 | 2002-03-19 | Nippon Yushi Basf Coatings Kk | One coat metallic coating material composition |
JP2002256174A (en) * | 2001-02-28 | 2002-09-11 | Asahi Glass Co Ltd | Color luster pigment and its manufacturing method |
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