JP2019157102A - Aqueous coating composition - Google Patents
Aqueous coating composition Download PDFInfo
- Publication number
- JP2019157102A JP2019157102A JP2018092501A JP2018092501A JP2019157102A JP 2019157102 A JP2019157102 A JP 2019157102A JP 2018092501 A JP2018092501 A JP 2018092501A JP 2018092501 A JP2018092501 A JP 2018092501A JP 2019157102 A JP2019157102 A JP 2019157102A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- coating composition
- curing agent
- group
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 68
- 229920001225 polyester resin Polymers 0.000 claims abstract description 133
- 239000004645 polyester resin Substances 0.000 claims abstract description 133
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 70
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 239000011248 coating agent Substances 0.000 claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 239000002253 acid Substances 0.000 claims abstract description 37
- 125000000524 functional group Chemical group 0.000 claims abstract description 32
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 12
- UUCAVBDCVCFNIN-UHFFFAOYSA-N n,n,n',n'-tetrakis(2-hydroxypropyl)hexanediamide Chemical compound CC(O)CN(CC(C)O)C(=O)CCCCC(=O)N(CC(C)O)CC(C)O UUCAVBDCVCFNIN-UHFFFAOYSA-N 0.000 claims description 11
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 8
- OKRNLSUTBJUVKA-UHFFFAOYSA-N n,n,n',n'-Tetrakis(2-hydroxyethyl)adipamide Chemical compound OCCN(CCO)C(=O)CCCCC(=O)N(CCO)CCO OKRNLSUTBJUVKA-UHFFFAOYSA-N 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 abstract description 19
- 238000005260 corrosion Methods 0.000 abstract description 19
- 229920000728 polyester Polymers 0.000 abstract description 7
- 235000013361 beverage Nutrition 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 35
- 239000000178 monomer Substances 0.000 description 22
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 239000012736 aqueous medium Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 150000002918 oxazolines Chemical class 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JTINZFQXZLCHNS-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)butan-1-ol Chemical compound C1OC1COCC(CO)(CC)COCC1CO1 JTINZFQXZLCHNS-UHFFFAOYSA-N 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- WHYQMPJLTUMFFV-UHFFFAOYSA-N 2-(4-sulfophenoxy)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1OC1=CC=C(S(O)(=O)=O)C=C1 WHYQMPJLTUMFFV-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical compound CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- HMEVYZZCEGUONQ-UHFFFAOYSA-N 2-ethenyl-5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=C(C=C)O1 HMEVYZZCEGUONQ-UHFFFAOYSA-N 0.000 description 1
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-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
- CTJFNNZDSZIGOM-UHFFFAOYSA-N 3-methylcyclohex-2-ene-1,1,2-tricarboxylic acid Chemical compound CC1=C(C(O)=O)C(C(O)=O)(C(O)=O)CCC1 CTJFNNZDSZIGOM-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- SQAJRDHPLTWZQT-UHFFFAOYSA-N 3-methylhexane-1,6-diol Chemical compound OCCC(C)CCCO SQAJRDHPLTWZQT-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、水性塗料組成物に関するものであり、より詳細には、加工性に優れると共に、硬化性や耐食性等に優れた塗膜を形成可能な水性塗料組成物に関する。 The present invention relates to an aqueous coating composition, and more particularly to an aqueous coating composition capable of forming a coating film having excellent processability and excellent curability and corrosion resistance.
飲料缶等の金属容器或いは金属蓋に用いられる塗料組成物には、金属容器或いは金属蓋を成形する際の過酷な加工（例えばネックイン加工、ビード加工、スコア加工、リベット加工）にも耐え得る加工性が要求される。その他、用途によっては、良好な硬化性を有していることや内容物等による金属基体の腐食を防止し得る耐食性を有していること、内容物のフレーバーを損なうことがないこと、塗料成分の溶出がなく衛生性に優れること、耐レトルト性に優れること等の様々な特性が要求される。さらに、塗装時や焼付時の有機溶剤の揮散による環境汚染や作業環境などへの影響を考慮する必要もある。 The coating composition used for metal containers such as beverage cans or metal lids can withstand severe processing (for example, neck-in processing, bead processing, score processing, rivet processing) when forming metal containers or metal lids. Workability is required. In addition, depending on the application, it has good curability, has corrosion resistance that can prevent corrosion of the metal substrate due to the contents, etc., does not impair the flavor of the contents, paint components Various characteristics such as excellent hygiene and anti-retort resistance are required. In addition, it is necessary to consider the environmental pollution and the working environment caused by the volatilization of organic solvents during painting and baking.
従来より、金属容器或いは金属蓋等に用いられる塗料組成物として、エポキシーフェノール系塗料、エポキシーアミノ系塗料、エポキシーアクリル系塗料等のエポキシ系塗料が広く使用されているが、エポキシ系塗料はビスフェノールＡを原料として製造されるものが多いため、ビスフェノールＡを含有しない塗料が望まれている。 Conventionally, epoxy-based paints such as epoxy-phenolic paints, epoxy-amino-based paints, epoxy-acrylic paints and the like have been widely used as coating compositions used for metal containers or metal lids. Therefore, a paint containing no bisphenol A is desired.
このような観点から、金属容器或いは金属蓋用の塗料組成物として、ビスフェノールＡを使用せず、さらには環境汚染や作業環境への影響をも考慮したポリエステル系水性塗料組成物が提案されている。
このようなポリエステル系水性塗料組成物としては、例えば、カルボキシル基を有する芳香族ポリエステル樹脂を主体とするものであって、１０〜３０ｍｇＫＯＨ／ｇの酸価（ＡＶ）と、３０００〜１００００の数平均分子量（Ｍｎ）とを有するものを用い、これを硬化剤、前記ポリエステル樹脂に対する中和剤、及び共溶剤と組み合わせたことを特徴とする硬化性、耐レトルト性に優れた金属包装体用塗料が提案されている（特許文献１）。
From such a point of view, a polyester-based aqueous coating composition that does not use bisphenol A as a coating composition for a metal container or a metal lid, and further considers environmental pollution and influence on the working environment has been proposed. .
As such a polyester-based water-based coating composition, for example, an aromatic polyester resin having a carboxyl group is mainly used, and an acid value (AV) of 10 to 30 mgKOH / g and a number average of 3000 to 10,000 are used. A coating for a metal packaging body excellent in curability and retort resistance, characterized by using a material having a molecular weight (Mn) and combining it with a curing agent, a neutralizing agent for the polyester resin, and a cosolvent. It has been proposed (Patent Document 1).
また水性塗料組成物として、例えば、エチレン性二重結合を樹脂端部に持つ数平均分子量２，０００〜５０，０００のポリエステル樹脂（Ａ）に、カルボキシル基含有重合性不飽和モノマーを含む重合性不飽和モノマー成分（Ｂ）をグラフト重合してなるアクリル変性ポリエステル樹脂（Ｃ）と、β−ヒドロキシアルキルアミド架橋剤（Ｄ）とが水性媒体中に安定に分散されてなる水性塗料組成物が提案されている（特許文献２）。 In addition, as an aqueous coating composition, for example, a polymer containing a carboxyl group-containing polymerizable unsaturated monomer in a polyester resin (A) having an ethylenic double bond at the resin end and a number average molecular weight of 2,000 to 50,000. Proposed is an aqueous coating composition in which an acrylic modified polyester resin (C) obtained by graft polymerization of an unsaturated monomer component (B) and a β-hydroxyalkylamide crosslinking agent (D) are stably dispersed in an aqueous medium. (Patent Document 2).
しかしながら、特許文献１のように、硬化剤として自己縮合体を形成するフェノール樹脂を用いた場合には、塗膜内においてフェノール樹脂の自己縮合体に由来する硬く脆いドメインが形成されることから、塗膜の加工性の点で未だ充分満足するものではなかった。
また特許文献２のように、酸価が高いポリエステル樹脂を用いた場合には、硬化剤との反応点（架橋点）が多くなることで硬化性には優れるものの、架橋密度が高くなり過ぎることで成形時に塗膜が割れやすくなり、過酷な加工に耐えることができず、充分な加工性を得ることができなかった。
従って本発明の目的は、加工性に優れると共に、硬化性や耐食性等の塗膜性能に優れた塗膜を形成可能なポリエステル樹脂系の水性塗料組成物を提供することである。
However, as in Patent Document 1, when a phenol resin that forms a self-condensate is used as a curing agent, a hard and brittle domain derived from the phenol resin self-condensate is formed in the coating film. The processability of the coating film was not yet satisfactory.
Further, as in Patent Document 2, when a polyester resin having a high acid value is used, the number of reaction points (crosslinking points) with the curing agent increases, but the curability is excellent, but the crosslinking density becomes too high. Thus, the coating film was easily broken at the time of molding, could not withstand severe processing, and sufficient workability could not be obtained.
Accordingly, an object of the present invention is to provide a polyester resin-based aqueous coating composition capable of forming a coating film having excellent processability and excellent coating performance such as curability and corrosion resistance.
本発明によれば、酸価５ｍｇＫＯＨ／ｇ以上３０ｍｇＫＯＨ／ｇ未満のポリエステル樹脂と、該ポリエステル樹脂が有するカルボキシル基と反応可能な官能基を有する硬化剤が含有されて成ることを特徴とする水性塗料組成物が提供される。
本発明の水性塗料組成物においては、
１．前記ポリエステル樹脂の固形分１００質量部に対する前記硬化剤の固形分配合量が１〜１０質量部であること、
２．前記硬化剤の官能基当量が、３０〜５００ｇ／ｅｑであること、
３．前記硬化剤の平均分子量が、１０００以下であること、
４．前記官能基が、β―ヒドロキシアルキルアミド基、エポキシ基、オキサゾリン基から選択される少なくとも１種であること、
５．前記官能基が、β―ヒドロキシアルキルアミド基であること、
６．前記硬化剤が、β―ヒドロキシアルキルアミド化合物であること、
７．前記β―ヒドロキシアルキルアミド化合物が、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシエチル）アジポアミド及び／又はＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシプロピル）アジポアミドであること、
８．前記ポリエステル樹脂が、Ｔｇが３５℃〜１００℃のポリエステル樹脂（Ａ）と、Ｔｇが−３０℃〜２５℃のポリエステル樹脂（Ｂ）を混合して成り、ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）の質量比が（Ａ）：（Ｂ）＝９８：２〜１０：９０であること、
が好適である。
According to the present invention, a water-based paint comprising: a polyester resin having an acid value of 5 mgKOH / g or more and less than 30 mgKOH / g; and a curing agent having a functional group capable of reacting with a carboxyl group of the polyester resin. A composition is provided.
In the aqueous coating composition of the present invention,
1. The solid content of the curing agent with respect to 100 parts by mass of the solid content of the polyester resin is 1 to 10 parts by mass,
2. The functional group equivalent of the curing agent is 30 to 500 g / eq,
3. The average molecular weight of the curing agent is 1000 or less,
4). The functional group is at least one selected from a β-hydroxyalkylamide group, an epoxy group, and an oxazoline group;
5). The functional group is a β-hydroxyalkylamide group;
6). The curing agent is a β-hydroxyalkylamide compound;
7). The β-hydroxyalkylamide compound is N, N, N ′, N′-tetrakis (2-hydroxyethyl) adipamide and / or N, N, N ′, N′-tetrakis (2-hydroxypropyl) adipamide. thing,
8). The polyester resin comprises a polyester resin (A) having a Tg of 35 ° C. to 100 ° C. and a polyester resin (B) having a Tg of −30 ° C. to 25 ° C., and the polyester resin (A) and the polyester resin (B ) Mass ratio of (A) :( B) = 98: 2 to 10:90,
Is preferred.
本発明によればまた、金属板の少なくとも片面に、上記水性塗料組成物から成る塗膜が形成されてなることを特徴とする塗装金属板が提供される。
本発明によれば更に、上記水性塗料組成物から成る塗膜が形成されて成ることを特徴とする塗装金属容器又は塗装金属蓋が提供される。
According to the present invention, there is also provided a coated metal plate characterized in that a coating film made of the aqueous coating composition is formed on at least one surface of the metal plate.
According to the present invention, there is further provided a painted metal container or a painted metal lid, characterized in that a coating film made of the above-mentioned aqueous coating composition is formed.
本発明者等は、ポリエステル系水性塗料組成物から形成される塗膜の加工性向上について鋭意検討した結果、特定のポリエステル樹脂及び硬化剤を用いることにより、過酷な加工にも耐え得る優れた加工性を有した塗膜を形成できることを見出した。また、本発明の水性塗料組成物から形成される塗膜は優れた硬化性や耐食性をも有しているため飲料缶等の金属容器或いは金属蓋に用いられる塗料組成物として好適に用いることができる。 As a result of intensive investigations on improving the workability of a coating film formed from a polyester-based aqueous coating composition, the present inventors have achieved excellent processing that can withstand severe processing by using a specific polyester resin and a curing agent. It has been found that a coating film having properties can be formed. Moreover, since the coating film formed from the aqueous coating composition of the present invention also has excellent curability and corrosion resistance, it can be suitably used as a coating composition used for metal containers such as beverage cans or metal lids. it can.
（ポリエステル樹脂）
本発明の塗料組成物において、主剤となるポリエステル樹脂は、酸価が５ｍｇＫＯＨ／ｇ以上３０ｍｇＫＯＨ／ｇ未満、特に１０〜２９ｍｇＫＯＨ／ｇの範囲にあることが重要である。
すなわち本発明においては、主剤となるポリエステル樹脂が適度なカルボキシル基量（酸価）を有することが、硬化性及び加工性、更に塗膜の密着性を兼ね備える上で重要になる。上記範囲よりも酸価が小さい場合には、硬化剤との架橋点となるカルボキシル基が少なく充分な硬化性を得ることができないと共に、塗膜と金属基体間の密着性に寄与するカルボキシル基が少ないため、塗膜の密着性が劣るようになる。一方上記範囲よりも酸価が大きい場合には、硬化剤との架橋点が多くなることで硬化性には優れるものの、架橋密度が過度に高くなりやすく、加工性が劣るようになる。
なお、上記範囲よりも酸価が大きい場合においても、硬化剤の配合量を少なくするなど調整すれば架橋密度を低く抑えることは可能であるが、その場合においては、架橋に用いられない遊離のカルボキシル基が塗膜に残存することになるため、塗膜の耐水性に劣るようになり、結果として充分な耐食性が得られない。
(Polyester resin)
In the coating composition of the present invention, it is important that the polyester resin as the main component has an acid value in the range of 5 mgKOH / g or more and less than 30 mgKOH / g, particularly 10 to 29 mgKOH / g.
That is, in the present invention, it is important that the polyester resin as the main component has an appropriate amount of carboxyl group (acid value) in order to combine curability and processability, and further adhesion of the coating film. When the acid value is smaller than the above range, there are few carboxyl groups that become crosslinking points with the curing agent, and sufficient curability cannot be obtained, and carboxyl groups that contribute to adhesion between the coating film and the metal substrate are not present. Since there are few, the adhesiveness of a coating film becomes inferior. On the other hand, when the acid value is larger than the above range, the number of cross-linking points with the curing agent is increased, but the curability is excellent, but the cross-linking density tends to be excessively high and the workability is inferior.
Even when the acid value is larger than the above range, it is possible to keep the crosslinking density low by adjusting the blending amount of the curing agent to be small. Since carboxyl groups remain in the coating film, the water resistance of the coating film becomes poor, and as a result, sufficient corrosion resistance cannot be obtained.
また、本発明においては酸価の異なる２種以上のポリエステル樹脂をブレンドして用いても良く、その場合においては各々のポリエステル樹脂の酸価と配合比（質量比）を乗じて得られた値の総和をブレンド体の平均酸価とし、その平均酸価が５ｍｇＫＯＨ／ｇ以上３０ｍｇＫＯＨ／ｇ未満の範囲内であれば良い。（単独の酸価が上記範囲外のポリエステル樹脂を用いても、酸価の異なる別のポリエステル樹脂とのブレンド体の平均酸価が上記範囲内に入れば良い。） In the present invention, two or more kinds of polyester resins having different acid values may be blended and used, and in that case, the value obtained by multiplying the acid value of each polyester resin and the blending ratio (mass ratio). Is the average acid value of the blend, and the average acid value may be in the range of 5 mgKOH / g or more and less than 30 mgKOH / g. (Even if a polyester resin having a single acid value outside the above range is used, the average acid value of a blend with another polyester resin having a different acid value may be within the above range.)
本発明で用いるポリエステル樹脂は、上述した酸価を有する以外は、塗料組成物に用いられる公知の水分散性ポリエステル樹脂及び／又は水溶性ポリエステル樹脂を使用することができる。
水分散性ポリエステル樹脂及び水溶性ポリエステル樹脂は、親水基を成分として含むポリエステル樹脂であり、これらの成分は、ポリエステル分散体表面に物理吸着されていてもよいが、ポリエステル樹脂骨格中に共重合されていていることが特に好ましい。
親水基としては、水酸基、アミノ基、カルボキシル基、スルホン酸基、又はこれらの誘導体や金属塩、エーテル等であり、これらを分子内に含むことにより水に分散可能な状態で存在することができる。
親水性基を含む成分としては、具体的には無水フタル酸、無水コハク酸、無水マレイン酸、無水トリメリット酸、無水イタコン酸、無水シトラコン酸等のカルボン酸無水物、ポリエチレングリコール、ポリプロピレングリコール、グリセリン、ポリグリセリン等の水酸基含有ポリエーテルモノマー、５−スルホイソフタル酸、４−スルホナフタレン−２，７−ジカルボン酸、５（４−スルホフェノキシ）イソフタル酸等のスルホン酸含有モノマーの金属塩、又はアンモニウム塩等を挙げることができる。
As the polyester resin used in the present invention, a known water-dispersible polyester resin and / or water-soluble polyester resin used in the coating composition can be used except that it has the acid value described above.
The water-dispersible polyester resin and the water-soluble polyester resin are polyester resins containing a hydrophilic group as a component, and these components may be physically adsorbed on the surface of the polyester dispersion, but are copolymerized in the polyester resin skeleton. It is particularly preferred that
The hydrophilic group is a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, or a derivative or metal salt thereof, an ether, or the like, and can exist in a state dispersible in water by including these in the molecule. .
Specific examples of the component containing a hydrophilic group include phthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, itaconic anhydride, citraconic anhydride and other carboxylic acid anhydrides, polyethylene glycol, polypropylene glycol, Hydroxyl group-containing polyether monomers such as glycerin and polyglycerin, metal salts of sulfonic acid-containing monomers such as 5-sulfoisophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5 (4-sulfophenoxy) isophthalic acid, or An ammonium salt etc. can be mentioned.
また親水性基を有するビニル系モノマーをポリエステル樹脂にグラフト重合させたアクリル樹脂変性ポリエステル樹脂でもよい。親水性基を有するビニル系モノマーとしては、カルボキシル基、水酸基、スルホン酸基、アミド基等を含むもの、親水性基に変化させることができる基としては酸無水物基、グリシジル基、クロル基等を含むものを挙げることができる。しかしながら、アクリル樹脂で変性されたポリエステル樹脂は、その変性のために製造工程数が増え、製造コストも高くなる場合があるため、本発明に用いるポリエステル樹脂としては、アクリル樹脂で変性していないポリエステル樹脂であることが好ましい。
本発明においては、ポリエステル樹脂としては、親水基としてカルボキシル基を有するカルボキシル基含有水分散性ポリエステル樹脂及び／又はカルボキシル基含有水溶性ポリエステル樹脂を好適に用いることができる。
Further, an acrylic resin-modified polyester resin obtained by graft polymerization of a vinyl monomer having a hydrophilic group onto a polyester resin may be used. Examples of vinyl monomers having a hydrophilic group include those containing a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, etc., and groups that can be changed to a hydrophilic group include an acid anhydride group, a glycidyl group, a chloro group, and the like. Can be included. However, since the polyester resin modified with an acrylic resin may increase the number of manufacturing steps and increase the manufacturing cost due to the modification, the polyester resin used in the present invention is a polyester not modified with an acrylic resin. A resin is preferred.
In the present invention, a carboxyl group-containing water-dispersible polyester resin and / or a carboxyl group-containing water-soluble polyester resin having a carboxyl group as a hydrophilic group can be suitably used as the polyester resin.
また、前記親水性基を含むモノマーと組み合わせて、ポリエステル樹脂を形成するモノマー成分としては、ポリエステル樹脂の重合に通常用いられるモノマーであれば特に限定されるものではない。ポリエステル樹脂を構成する多価カルボン酸成分としては、例えばテレフタル酸、イソフタル酸、オルソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジオン酸、ダイマー酸等の脂肪族ジカルボン酸、（無水）マレイン酸、フマル酸、テルペン−マレイン酸付加体などの不飽和ジカルボン酸、１，４−シクロヘキサンジカルボン酸、テトラヒドロフタル酸、ヘキサヒドロイソフタル酸、１，２−シクロヘキセンジカルボン酸などの脂環族ジカルボン酸、（無水）トリメリット酸、（無水）ピロメリット酸、メチルシクロへキセントリカルボン酸等の３価以上の多価カルボン酸等が挙げられ、これらの中から１種または２種以上を選択し使用できる。
本発明においては、耐食性や耐レトルト性、フレーバー性等の観点からポリエステル樹脂を構成する多価カルボン酸成分に占めるテレフタル酸やイソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸の割合が６０モル％以上であることが好ましく、特に８０％以上であることが好ましい。
The monomer component that forms the polyester resin in combination with the monomer containing the hydrophilic group is not particularly limited as long as it is a monomer that is usually used for polymerization of the polyester resin. Examples of the polyvalent carboxylic acid component constituting the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedione. Aliphatic dicarboxylic acids such as acids and dimer acids, unsaturated dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid and terpene-maleic acid adducts, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydroisophthalic acid, Examples include alicyclic dicarboxylic acids such as 1,2-cyclohexene dicarboxylic acid, trivalent or higher polyvalent carboxylic acids such as (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, and methylcyclohexentricarboxylic acid. One or two or more types can be selected and used.
In the present invention, the proportion of aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid in the polyvalent carboxylic acid component constituting the polyester resin is 60 mol% from the viewpoint of corrosion resistance, retort resistance, flavor and the like. It is preferable that it is above, and 80% or more is particularly preferable.
ポリエステル樹脂を構成する多価アルコール成分としては、特に限定はなく、エチレングリコール、プロピレングリコール（１，２−プロパンジオール）、１，３−プロパンジオール、１，４−ブタンジオール、１，２−ブタンジオール、１，３−ブタンジオール、２−メチル−１，３−プロパンジオール、ネオペンチルグリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、２−エチル−２−ブチル−１，３−プロパンジオール、２，４−ジエチル−１，５−ペンタンジオール、１−メチル−１，８−オクタンジオール、３−メチル−１，６−ヘキサンジオール、４−メチル−１，７−ヘプタンジオール、４−メチル−１，８−オクタンジオール、４−プロピル−１，８−オクタンジオール、１，９−ノナンジオール、などの脂肪族グリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のエーテルグリコール類、１，４−シクロヘキサンジメタノール、１，３−シクロヘキサンジメタノール、１，２−シクロヘキサンジメタノール、トリシクロデカングリコール類、水添加ビスフェノール類、などの脂環族ポリアルコール、トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトール、などの３価以上のポリアルコール等から１種、または２種以上の組合せで使用することができる。本発明においては、衛生性等の観点から上記の多価アルコール成分の中でも、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノールを、ポリエステル樹脂を構成する成分として好適に用いることできる。 The polyhydric alcohol component constituting the polyester resin is not particularly limited, and ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,4-butanediol, 1,2-butane. Diol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2 -Ethyl-2-butyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1-methyl-1,8-octanediol, 3-methyl-1,6-hexanediol, 4 -Methyl-1,7-heptanediol, 4-methyl-1,8-octanediol, 4-propyl-1,8-octane Aliphatic glycols such as all, 1,9-nonanediol, ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol, 1,3-cyclohexane Trivalent or higher polyalcohols such as alicyclic polyalcohols such as dimethanol, 1,2-cyclohexanedimethanol, tricyclodecane glycols, water-added bisphenols, trimethylolpropane, trimethylolethane, pentaerythritol, etc. Can be used alone or in combination of two or more. In the present invention, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferable as components constituting the polyester resin among the above polyhydric alcohol components from the viewpoint of hygiene and the like. Can be used.
ポリエステル樹脂は、上記の多価カルボン酸成分の１種類以上と多価アルコール成分の１種類以上とを重縮合させることや、重縮合後に多価カルボン酸成分、例えばテレフタル酸、イソフタル酸、無水トリメリット酸、トリメリット酸、ピロメリット酸等で解重合する方法、また、重縮合後に酸無水物、例えば 無水フタル酸、無水マレイン酸、無水トリメリト酸、エチレングリコールビストリメリテート二無水物等を開環付加させること等、公知の方法によって製造することができる。 Polyester resins can be obtained by polycondensation of one or more of the polyhydric carboxylic acid components and one or more of the polyhydric alcohol components, or after polycondensation, such as polycarboxylic acid components such as terephthalic acid, isophthalic acid, Depolymerization with merit acid, trimellitic acid, pyromellitic acid, etc., and after polycondensation, acid anhydrides such as phthalic anhydride, maleic anhydride, trimellitic anhydride, ethylene glycol bistrimellitic dianhydride, etc. It can be produced by a known method such as cycloaddition.
また、これらポリエステル樹脂のガラス転移温度（Ｔｇ）は、これに限定されるものではないが、−３０℃〜１２０℃、特に１５℃〜１００℃の範囲にあることが好ましい。上記範囲よりもＴｇが高い場合には、形成される塗膜が硬くなるため、加工性が劣るおそれがある。一方上記範囲よりもＴｇが低い場合には、塗膜のバリアー性が低下し耐食性や耐レトルト性が劣るようになる。 Moreover, although the glass transition temperature (Tg) of these polyester resins is not limited to this, it is preferable that it exists in the range of -30 degreeC-120 degreeC, especially 15 degreeC-100 degreeC. When Tg is higher than the above range, the formed coating film becomes hard, so that the workability may be inferior. On the other hand, when Tg is lower than the above range, the barrier properties of the coating film are lowered, and the corrosion resistance and retort resistance are inferior.
また、本発明においては、Ｔｇの異なる２種以上のポリエステル樹脂をブレンドして用いることが好ましい。Ｔｇの異なるポリエステル樹脂をブレンドすることで、ポリエステル樹脂１種のみを使用した場合に比べ、耐衝撃性に優れ、外部から衝撃を受けても塗膜欠陥のできにくい塗膜を形成できる場合がある。
その場合においても、下記式（１）により算出されるポリエステル樹脂ブレンドのＴｇｍｉｘが上記のＴｇ範囲にあれば良い。
１／Ｔｇｍｉｘ＝（Ｗ１／Ｔｇ１）＋（Ｗ２／Ｔｇ２）＋…＋（Ｗｍ／Ｔｇｍ）
・・・（１）
Ｗ１＋Ｗ２＋…＋Ｗｍ＝１
式中、Ｔｇｍｉｘはポリエステル樹脂ブレンドのガラス転移温度（Ｋ）を表わし、Ｔｇ１，Ｔｇ２，…，Ｔｇｍは使用する各ポリエステル樹脂（ポリエステル樹脂１，ポリエステル樹脂２，…ポリエステル樹脂ｍ）単体のガラス転移温度（Ｋ）を表わす。また、Ｗ１，Ｗ２，…，Ｗｍは各ポリエステル樹脂（ポリエステル樹脂１，ポリエステル樹脂２，…ポリエステル樹脂ｍ）の重量分率を表わす。
In the present invention, it is preferable to use a blend of two or more polyester resins having different Tg. By blending polyester resins with different Tg, compared to the case of using only one type of polyester resin, there is a case where it is possible to form a coating film that is superior in impact resistance and hardly causes coating film defects even when subjected to external impact. .
Even in that case, the Tg mix of the polyester resin blend calculated by the following formula (1) may be in the above Tg range.
1 / Tg mix = (W1 / Tg1) + (W2 / Tg2) + ... + (Wm / Tgm)
... (1)
W1 + W2 + ... + Wm = 1
In the formula, Tg mix represents the glass transition temperature (K) of the polyester resin blend, and Tg1, Tg2,..., Tgm are the glass transition of each polyester resin used (polyester resin 1, polyester resin 2,... Polyester resin m) alone. Represents temperature (K). W1, W2,..., Wm represent the weight fraction of each polyester resin (polyester resin 1, polyester resin 2,... Polyester resin m).
本発明の水性塗料組成物においては、ポリエステル樹脂として、Ｔｇが３５℃〜１００℃のポリエステル樹脂（Ａ）と、Ｔｇが−３０℃〜２５℃のポリエステル樹脂（Ｂ）を混合して用いることが、塗膜の耐衝撃性の観点から特に好ましい。その場合の配合比率は質量比で（Ａ）：（Ｂ）＝９８：２〜１０：９０、特に９５：５〜３０：７０であることが好ましい。また、上記式（１）で算出されるガラス転移温度（Ｔｇｍｉｘ）が３０℃以上であることが、耐食性や耐レトルト性の観点から好ましい。 In the aqueous coating composition of the present invention, a polyester resin (A) having a Tg of 35 ° C. to 100 ° C. and a polyester resin (B) having a Tg of −30 ° C. to 25 ° C. are used as a polyester resin. From the viewpoint of impact resistance of the coating film, it is particularly preferable. The blending ratio in that case is preferably (A) :( B) = 98: 2 to 10:90, particularly 95: 5 to 30:70 in terms of mass ratio. Moreover, it is preferable from a viewpoint of corrosion resistance or retort resistance that the glass transition temperature (Tg mix ) calculated by the said Formula (1) is 30 degreeC or more.
ポリエステル樹脂の数平均分子量（Ｍｎ）はこれに限定されるものではないが、１，０００〜１００，０００、特に３，０００〜５０，０００の範囲にあることが好ましい。上記範囲よりも小さいと塗膜が脆くなり、加工性に劣る場合があり、上記範囲よりも大きいと塗料安定性が低下するおそれがある。 The number average molecular weight (Mn) of the polyester resin is not limited to this, but is preferably in the range of 1,000 to 100,000, particularly 3,000 to 50,000. If it is smaller than the above range, the coating film becomes brittle and the processability may be poor. If it is larger than the above range, the coating stability may be lowered.
水分散性ポリエステル樹脂におけるポリエステル樹脂の平均分散粒子径は１０〜１，０００ｎｍ、特に２０〜５００ｎｍの範囲にあることが好ましい。 The average dispersed particle size of the polyester resin in the water-dispersible polyester resin is preferably in the range of 10 to 1,000 nm, particularly 20 to 500 nm.
ポリエステル樹脂の水酸基価については、これに限定されるものではないが、２０ｍｇＫＯＨ／ｇ以下、より好ましくは１０ｍｇＫＯＨ／ｇ以下であることが好ましい。硬化剤として、ポリエステル樹脂のカルボキシル基とは反応するが、水酸基とは反応しにくい、或いは反応しないと考えられるもの、例えばβ−ヒドロキシアルキルアミド化合物等を用いた場合は、ポリエステル樹脂の水酸基の大部分は未反応のまま塗膜に残存することとなる。そのため、上記範囲よりも水酸基価が大きい場合は、残存する水酸基が多くなり、耐食性が低下するおそれがある。 The hydroxyl value of the polyester resin is not limited to this, but is preferably 20 mgKOH / g or less, more preferably 10 mgKOH / g or less. When a curing agent is used which reacts with the carboxyl group of the polyester resin but does not react with the hydroxyl group, or does not react, such as a β-hydroxyalkylamide compound, the hydroxyl group of the polyester resin is large. The portion remains unreacted in the coating film. Therefore, when the hydroxyl value is larger than the above range, the remaining hydroxyl group is increased and the corrosion resistance may be lowered.
（硬化剤）
本発明においては、主剤であるポリエステル樹脂が有するカルボキシル基と架橋反応可能な官能基を有する特定の硬化剤を用いることが重要な特徴である。
本発明に用いる硬化剤における前記官能基の官能基当量としては、３０〜５００ｇ／ｅｑであることが好ましく、特に４０〜２００ｇ／ｅｑの範囲にあることが好ましい。なお、本発明における官能基当量とは、分子量を硬化剤１分子当たりの官能基数（ここで言う官能基は主剤ポリエステル樹脂のカルボキシル基と架橋反応可能な官能基を指す）で除した値であり、硬化剤の前記官能基１個当たりの分子量を意味し、例えばエポキシ当量などで表される。官能基当量が上記範囲よりも小さいと架橋点間距離を長くとることができないため、塗膜の柔軟性が低下し、加工性が劣る。一方で上記範囲よりも大きすぎると硬化性が不足し、加工性、耐レトルト性が劣る。
また、硬化剤の平均分子量は１０００以下であることが好ましい。上記範囲よりも大きいと、主剤のポリエステル樹脂との相溶性が低下するおそれがあり、反応性が低下する場合がある。さらに、硬化剤１分子当たりの平均官能基数が３以上であることが、良好な硬化性を得る上で好ましい。
(Curing agent)
In the present invention, it is an important feature to use a specific curing agent having a functional group capable of undergoing a crosslinking reaction with a carboxyl group of the polyester resin as the main agent.
The functional group equivalent of the functional group in the curing agent used in the present invention is preferably 30 to 500 g / eq, and particularly preferably 40 to 200 g / eq. The functional group equivalent in the present invention is a value obtained by dividing the molecular weight by the number of functional groups per molecule of the curing agent (the functional group here refers to a functional group capable of crosslinking reaction with the carboxyl group of the main polyester resin). , Means the molecular weight per functional group of the curing agent, and is expressed by, for example, epoxy equivalent. If the functional group equivalent is smaller than the above range, the distance between cross-linking points cannot be increased, so that the flexibility of the coating film is lowered and the processability is inferior. On the other hand, when it is larger than the above range, curability is insufficient, and workability and retort resistance are inferior.
Moreover, it is preferable that the average molecular weight of a hardening | curing agent is 1000 or less. When larger than the said range, there exists a possibility that compatibility with the polyester resin of a main ingredient may fall, and reactivity may fall. Furthermore, the average number of functional groups per molecule of the curing agent is preferably 3 or more in order to obtain good curability.
また、前記硬化剤としては、硬化剤同士で自己縮合反応しにくいもの、特に自己縮合反応しないものが好ましい。一般にポリエステル系塗料組成物の硬化剤として使用されているレゾール型フェノール樹脂やアミノ樹脂等は硬化剤同士の自己縮合反応を起こしやすく、塗膜形成時に硬く脆いドメインである自己縮合体が形成され、それにより塗膜が硬くなり加工性を低下させる場合がある。また自己縮合反応に硬化剤の反応点（官能基）が消費されてしまうため、充分な硬化性を得るために必要となる硬化剤の量は当然多くなり非効率であると共に、塗膜に含まれる多量の硬化剤の存在が、加工性及び耐食性などの塗膜特性に悪影響を与えるおそれがある。これに対して、自己縮合反応しにくい、或いは自己縮合反応しない硬化剤を使用した場合は、硬く脆い自己縮合体の形成を抑制できると共に、ポリエステル樹脂のカルボキシル基量に対応した最低限の量を配合すれば良いため効率的であると共に、塗膜中の硬化剤量も少なくでき、結果として加工性及び耐食性に優れた塗膜を形成することができる。
従って硬化剤としては、ポリエステル樹脂のカルボキシル基との反応性を有する官能基として、上述した理由により、硬化剤同士の自己縮合反応を誘発しにくい官能基を有する硬化剤が好ましく、そのような官能基としては、例えばエポキシ基、カルボジイミド基、オキサゾリン基、アミノ基、水酸基（ただし、レゾール型フェノール樹脂やアミノ樹脂等に含まれる自己縮合性メチロール基由来の水酸基やシランカップリング剤等に含まれる自己縮合性シラノール基由来の水酸基は除く）、β−ヒドロキシアルキルアミド基等が挙げられる。それらの中でもエポキシ基、オキサゾリン基、β−ヒドロキシアルキルアミド基を有する硬化剤が好ましく、特にβ−ヒドロキシアルキルアミド基を有する硬化剤を好適に使用することができる。
Moreover, as said hardening | curing agent, what is hard to carry out self-condensation reaction between hardening | curing agents, especially the thing which does not carry out self-condensation reaction is preferable. In general, resol type phenol resins and amino resins that are used as curing agents for polyester-based coating compositions are susceptible to self-condensation reactions between curing agents, and self-condensates that are hard and brittle domains are formed during coating formation, Thereby, a coating film may become hard and workability may be reduced. In addition, since the reaction point (functional group) of the curing agent is consumed in the self-condensation reaction, the amount of the curing agent necessary to obtain sufficient curability is naturally increased and inefficient, and included in the coating film. The presence of a large amount of the curing agent may adversely affect the coating properties such as processability and corrosion resistance. On the other hand, when a curing agent that is difficult to self-condensate or does not self-condensate is used, formation of a hard and brittle self-condensate can be suppressed, and a minimum amount corresponding to the amount of carboxyl groups of the polyester resin can be reduced. It is efficient because it only needs to be blended, and the amount of the curing agent in the coating film can be reduced, and as a result, a coating film excellent in workability and corrosion resistance can be formed.
Therefore, as the curing agent, a functional group having reactivity with the carboxyl group of the polyester resin is preferable, and for the reasons described above, a curing agent having a functional group that hardly induces a self-condensation reaction between the curing agents is preferable. Examples of the group include an epoxy group, a carbodiimide group, an oxazoline group, an amino group, a hydroxyl group (however, a self-condensed methylol group-derived hydroxyl group or a silane coupling agent contained in a resole type phenol resin or amino resin). Except for a hydroxyl group derived from a condensable silanol group) and a β-hydroxyalkylamide group. Among these, a curing agent having an epoxy group, an oxazoline group, and a β-hydroxyalkylamide group is preferable, and a curing agent having a β-hydroxyalkylamide group can be preferably used.
（β−ヒドロキシアルキルアミド基含有硬化剤）
β−ヒドロキシアルキルアミド基を有する硬化剤としては、β―ヒドロキシアルキルアミド化合物が挙げられ、例えば下記一般式〔Ｉ〕で示されるものが挙げられる。
一般式〔Ｉ〕；
［ＨＯ―ＣＨ（Ｒ１）―ＣＨ２―Ｎ（Ｒ２）―ＣＯ―］ｍ―Ａ―［―ＣＯ―Ｎ（Ｒ２’）―ＣＨ２―ＣＨ（Ｒ１’）―ＯＨ］ｎ
［式中、Ｒ１およびＲ１’は水素原子又は炭素数１から５までのアルキル基、Ｒ２およびＲ２’は水素原子又は炭素数１から５までのアルキル基又は一般式〔ＩＩ〕で示されるもの、Ａは多価の有機基、ｍは１又は２、ｎは０から２（ｍとｎの合計は少なくとも２である。）を表わす。］
(Β-Hydroxyalkylamide group-containing curing agent)
Examples of the curing agent having a β-hydroxyalkylamide group include β-hydroxyalkylamide compounds, such as those represented by the following general formula [I].
General formula [I];
[HO—CH (R 1 ) —CH 2 —N (R 2 ) —CO—] m —A — [— CO—N (R 2 ′) —CH 2 —CH (R 1 ′) —OH] n
[Wherein R 1 and R 1 ′ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 and R 2 ′ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or a general formula [II] As shown, A represents a polyvalent organic group, m represents 1 or 2, and n represents 0 to 2 (the sum of m and n is at least 2). ]
一般式〔ＩＩ〕；ＨＯ―ＣＨ（Ｒ３）―ＣＨ２―
［式中、Ｒ３は水素原子又は炭素数１から５までのアルキル基を表わす。］
General formula [II]; HO—CH (R 3 ) —CH 2 —
[Wherein R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]
前記一般式〔Ｉ〕中のＡは、脂肪族、脂環族又は芳香族炭化水素であることが好ましく、炭素数２から２０の脂肪族、脂環族又は芳香族炭化水素がより好ましく、炭素数４から１０の脂肪族炭化水素が更に好ましい。
また、前記一般式〔Ｉ〕におけるｍとｎの合計は、２又は３又は４であることが好ましい。
上記一般式〔Ｉ〕で示されるもの中でも、硬化剤として用いるβ−ヒドロキシアルキルアミド基含有硬化剤（β−ヒドロキシアルキルアミド化合物）としては、特にＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシエチル）アジポアミド［ＣＡＳ：６３３４−２５−４、分子量：約３２０、官能基当量：約８０ｇ／ｅｑ、１分子当たりの官能基数：４、製品例：ＥＭＳ社製Ｐｒｉｍｉｄ ＸＬ５５２］やＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシプロピル）アジポアミド［ＣＡＳ：５７８４３−５３−５、分子量：約３７６、官能基当量：約９５ｇ／ｅｑ、１分子当たりの官能基数：４、製品例：ＥＭＳ社製Ｐｒｉｍｉｄ ＱＭ１２６０］が好ましい。これらの中でも、硬化性や耐レトルト性の観点からＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシプロピル）アジポアミドを用いることがより好ましい。Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシエチル）アジポアミドに比べて、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシプロピル）アジポアミドの方が、ポリエステル樹脂との反応性が高く、硬化性に優れると共に、より緻密な架橋構造を形成することで、レトルト時にも塗膜が白化しにくく、耐レトルト性に優れた塗膜を形成することができる。
A in the general formula [I] is preferably an aliphatic, alicyclic or aromatic hydrocarbon, more preferably an aliphatic, alicyclic or aromatic hydrocarbon having 2 to 20 carbon atoms, An aliphatic hydrocarbon having a number of 4 to 10 is more preferable.
The total of m and n in the general formula [I] is preferably 2 or 3 or 4.
Among those represented by the above general formula [I], a β-hydroxyalkylamide group-containing curing agent (β-hydroxyalkylamide compound) used as a curing agent is particularly N, N, N ′, N′-tetrakis (2 -Hydroxyethyl) adipamide [CAS: 6334-25-4, molecular weight: about 320, functional group equivalent: about 80 g / eq, number of functional groups per molecule: 4, product example: Primid XL552 manufactured by EMS, N, N , N ′, N′-tetrakis (2-hydroxypropyl) adipamide [CAS: 57843-53-5, molecular weight: about 376, functional group equivalent: about 95 g / eq, number of functional groups per molecule: 4, product example: Primid QM1260] manufactured by EMS is preferable. Among these, it is more preferable to use N, N, N ′, N′-tetrakis (2-hydroxypropyl) adipamide from the viewpoint of curability and retort resistance. N, N, N ′, N′-tetrakis (2-hydroxyethyl) adipamide is more reactive with polyester resin than N, N, N ′, N′-tetrakis (2-hydroxypropyl) adipamide In addition to being high and excellent in curability, by forming a denser cross-linked structure, it is difficult to whiten the coating film even during retorting, and a coating film having excellent retort resistance can be formed.
（エポキシ基含有硬化剤）
エポキシ基を有する硬化剤としては、例えばポリエチレングリコールジグリシジルエーテル、ソルビトールテトラグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル等の水に溶解するポリエポキシ化合物が好ましく、具体的には、ナガセケムテックス株式会社製デナコールＥＸ−３１４［分子量：約３２０、官能基（エポキシ）当量：約１４４ｇ／ｅｑ］、ＥＸ−４２１［分子量：約４４０、官能基（エポキシ）当量：約１５９ｇ／ｅｑ］、ＥＸ−６１１［分子量：約６３０、官能基（エポキシ）当量：約１６７ｇ／ｅｑ］が挙げられる。
(Epoxy group-containing curing agent)
Examples of the curing agent having an epoxy group include polyepoxy compounds that dissolve in water, such as polyethylene glycol diglycidyl ether, sorbitol tetraglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, and polyglycerol polyglycidyl ether. Preferably, specifically, Denacol EX-314 [molecular weight: about 320, functional group (epoxy) equivalent: about 144 g / eq], EX-421 [molecular weight: about 440, functional group (epoxy), manufactured by Nagase ChemteX Corporation Equivalent: about 159 g / eq], EX-611 [molecular weight: about 630, functional group (epoxy) equivalent: about 167 g / eq].
（オキサゾリン基含有硬化剤）
オキサゾリン基を有する硬化剤としては、例えばオキサゾリン誘導体を含むモノマー組成物を重合させた水溶性重合体が挙げられ、そのようなオキサゾリン誘導体としては、例えば、２−ビニル−２−オキサゾリン、２−ビニル−４−メチル−２−オキサゾリン、２−ビニル−５−メチル−２−オキサゾリン、２−イソプロペニル−２−オキサゾリン、２−イソプロペニル−４−メチル−２−オキサゾリン、２−イソプロペニル−５−メチル−２−オキサゾリン、２−イソプロペニル−５−エチル−２−オキサゾリン等が挙げられる。また、オキサゾリン誘導体を含むモノマー組成物に含まれるオキサゾリン誘導体以外のモノマーとしては、オキサゾリン誘導体と共重合し、かつ、オキサゾリン基に対して不活性な化合物であればよく、特に限定されるものではない。オキサゾリン基含有重合体中において、オキサゾリン誘導体に由来する構造単位が占める割合としては、５質量％以上であることが好ましい。具体的には、株式会社日本触媒製エポクロスＷＳ−３００［数平均分子量：約４万、官能基（オキサゾリン）当量：約１３０ｇ／ｅｑ］、エポクロスＷＳ−７００［数平均分子量：約２万、官能基（オキサゾリン）当量：約２２０ｇ／ｅｑ］が挙げられる。
(Oxazoline group-containing curing agent)
Examples of the curing agent having an oxazoline group include a water-soluble polymer obtained by polymerizing a monomer composition containing an oxazoline derivative. Examples of such an oxazoline derivative include 2-vinyl-2-oxazoline and 2-vinyl. -4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5 Examples include methyl-2-oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline. The monomer other than the oxazoline derivative contained in the monomer composition containing the oxazoline derivative is not particularly limited as long as it is a compound that is copolymerized with the oxazoline derivative and is inert to the oxazoline group. . In the oxazoline group-containing polymer, the proportion of structural units derived from the oxazoline derivative is preferably 5% by mass or more. Specifically, Nippon Shokubai Epocross WS-300 [number average molecular weight: about 40,000, functional group (oxazoline) equivalent: about 130 g / eq], Epocross WS-700 [number average molecular weight: about 20,000, functional Group (oxazoline) equivalent: about 220 g / eq].
硬化剤は、ポリエステル樹脂（固形分）１００質量部に対して、１〜１０質量部で配合することが好ましく、２〜８質量部がより好ましく、３〜７質量部が更に好ましい。上記範囲よりも硬化剤の配合量が少ない場合には、充分な硬化性を得ることができず、一方上記範囲よりも硬化剤の配合量が多い場合には、経済性に劣るだけでなく、ポリエステル樹脂のカルボキシル基量に対して、硬化剤の官能基が大過剰になると、硬化剤１分子が２分子以上のポリエステル樹脂と反応することが困難になり、結果として架橋形成に不備が生じ、かえって硬化性が低下する場合がある。また長期保存の安定性に劣るおそれがある。
また、ポリエステル樹脂のカルボキシル基量に対する硬化剤の官能基量（β−ヒドロキシアルキルアミド基等）としては、０．２〜３．０当量の範囲が好ましく、０．５〜２．５当量の範囲が更に好ましい。
It is preferable to mix | blend a hardening | curing agent with 1-10 mass parts with respect to 100 mass parts of polyester resins (solid content), 2-8 mass parts is more preferable, and 3-7 mass parts is still more preferable. When the amount of the curing agent is less than the above range, sufficient curability cannot be obtained, while when the amount of the curing agent is larger than the above range, not only is the economy low, When the functional group of the curing agent is excessively large with respect to the amount of carboxyl groups of the polyester resin, it becomes difficult for one molecule of the curing agent to react with two or more polyester resins, resulting in deficiencies in cross-linking formation, On the contrary, the curability may be lowered. Moreover, there is a risk of poor long-term storage stability.
Moreover, as a functional group amount ((beta) -hydroxyalkylamide group etc.) of the hardening | curing agent with respect to the carboxyl group amount of a polyester resin, the range of 0.2-3.0 equivalent is preferable, The range of 0.5-2.5 equivalent Is more preferable.
（水性媒体）
本発明の水性塗料組成物は上述したポリエステル樹脂及び硬化剤、並びに水性媒体を含有する。水性媒体としては、公知の水性塗料組成物と同様に、水、或いは水とアルコールや多価アルコール、その誘導体等の有機溶剤を混合したものを水性媒体として用いることができる。有機溶剤を用いる場合には、水性塗料組成物中の水性媒体全体に対して、１〜４５質量％の量で含有することが好ましく、特に５〜３０質量％の量で含有することが好ましい。上記範囲で溶剤を含有することにより、製膜性能が向上する。
このような有機溶媒としては、両親媒性を有するものが好ましく、例えば、メチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ―ブタノール、エチレングリコール、メチルエチルケトン、ブチルセロソルブ、カルビトール、ブチルカルビトール、プロピレングリコールモノプロピルエーテル、プロピレングリコールエチレングリコールモノブルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、３−メチル３−メトキシブタノールなどが挙げられる。
(Aqueous medium)
The aqueous coating composition of the present invention contains the above-described polyester resin and curing agent, and an aqueous medium. As the aqueous medium, water or a mixture of water and an organic solvent such as alcohol, a polyhydric alcohol, or a derivative thereof can be used as the aqueous medium, as in a known aqueous coating composition. When using an organic solvent, it is preferable to contain in the quantity of 1-45 mass% with respect to the whole aqueous medium in a water-based coating composition, and it is preferable to contain in the quantity of 5-30 mass% especially. By containing the solvent in the above range, the film forming performance is improved.
As such an organic solvent, those having amphiphilic properties are preferable. For example, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, ethylene glycol, methyl ethyl ketone, butyl cellosolve, carbitol, butyl carbitol, propylene glycol monopropyl Examples include ether, propylene glycol ethylene glycol monoble ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and 3-methyl 3-methoxybutanol.
（塩基性化合物）
本発明の水性塗料組成物において、ポリエステル樹脂に水分散性又は水溶性を付与するために、ポリエステル樹脂のカルボキシル基を中和可能な塩基性化合物が含有されていることが好ましい。塩基性化合物としては塗膜形成時の焼付で揮散する化合物、すなわち、アンモニア及び／又は沸点が２５０℃以下の有機アミン化合物などが好ましい。
具体的には、トリメチルアミン、トリエチルアミン、ｎ−ブチルアミン等のアルキルアミン類、２−ジメチルアミノエタノール、ジエタノールアミン、トリエタノールアミン、アミノメチルプロパノール、ジメチルアミノメチルプロパノール等アルコールアミン類等が使用される。またエチレンジアミン、ジエチレントリアミン等多価アミンも使用できる。更に、分岐鎖アルキル基を有するアミンや複素環アミンも好適に使用される。分岐鎖アルキル基を有するアミンとしては、イソプロピルアミン、ｓｅｃ−ブチルアミン、ｔｅｒｔ−ブチルアミン、イソアミルアミン等の炭素数３〜６、特に炭素数３〜４の分岐鎖アルキルアミンが使用される。複素環アミンとしては、ピロリジン、ピペリジン、モルホリン等の１個の窒素原子を含む飽和複素環アミンが使用される。
本発明においては、上記の中でもトリエチルアミン、又は２−ジメチルアミノエタノールを好適に使用することができ、その使用量は、カルボキシル基に対して０．５〜１．５当量で用いるのがよい。
(Basic compound)
The aqueous coating composition of the present invention preferably contains a basic compound capable of neutralizing the carboxyl group of the polyester resin in order to impart water dispersibility or water solubility to the polyester resin. As the basic compound, a compound that volatilizes by baking at the time of forming the coating film, that is, an ammonia and / or an organic amine compound having a boiling point of 250 ° C. or less is preferable.
Specifically, alkylamines such as trimethylamine, triethylamine and n-butylamine, alcohol amines such as 2-dimethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol and dimethylaminomethylpropanol are used. Polyvalent amines such as ethylenediamine and diethylenetriamine can also be used. Furthermore, amines having a branched alkyl group and heterocyclic amines are also preferably used. As the amine having a branched chain alkyl group, a branched chain alkylamine having 3 to 6 carbon atoms, particularly 3 to 4 carbon atoms such as isopropylamine, sec-butylamine, tert-butylamine, isoamylamine and the like is used. As the heterocyclic amine, a saturated heterocyclic amine containing one nitrogen atom such as pyrrolidine, piperidine, morpholine and the like is used.
In the present invention, among the above, triethylamine or 2-dimethylaminoethanol can be preferably used, and the amount used is preferably 0.5 to 1.5 equivalents relative to the carboxyl group.
（硬化触媒）
本発明の水性塗料組成物には、必要に応じてポリエステル樹脂と硬化剤の架橋反応を促進する目的で従来公知の硬化触媒を配合しても良い。
硬化触媒としては、従来公知の硬化触媒を用いることができ、ｐ−トルエンスルホン酸、ドデシルベンゼンスルホン酸、ジノニルナフタレンジスルホン酸、またはこれらのアミンブロック化物等の酸触媒、有機スズ化合物、有機チタン化合物、有機亜鉛化合物、有機コバルト化合物、有機アルミニウム化合物等の有機金属化合物、酸化亜鉛、酸化チタン、酸化アルミニウム等の金属酸化物、アルカリ金属次亜リン酸塩、アルカリ金属亜リン酸塩、次亜リン酸、アルキルホスフィン酸等のリン系化合物などを使用することができる。
硬化触媒は、ポリエステル樹脂の固形分１００質量部に対して、０．１〜５質量部の範囲で配合することが好ましい。上記範囲よりも硬化触媒の配合量が少ない場合には、硬化触媒を配合することにより得られる硬化反応促進効果を充分に得ることができない。一方上記範囲よりも硬化触媒の配合量が多い場合には、それ以上の効果が望めず、経済性に劣る。
(Curing catalyst)
The water-based coating composition of the present invention may be blended with a conventionally known curing catalyst for the purpose of accelerating the crosslinking reaction between the polyester resin and the curing agent, if necessary.
As the curing catalyst, a conventionally known curing catalyst can be used. Acid catalysts such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenedisulfonic acid, or amine-blocked products thereof, organic tin compounds, organic titanium Compounds, organometallic compounds such as organozinc compounds, organocobalt compounds, organoaluminum compounds, metal oxides such as zinc oxide, titanium oxide, aluminum oxide, alkali metal hypophosphites, alkali metal phosphites, hypoxia Phosphorus compounds such as phosphoric acid and alkylphosphinic acid can be used.
It is preferable to mix | blend a curing catalyst in 0.1-5 mass parts with respect to 100 mass parts of solid content of a polyester resin. When the amount of the curing catalyst is less than the above range, the curing reaction promoting effect obtained by blending the curing catalyst cannot be sufficiently obtained. On the other hand, when the blending amount of the curing catalyst is larger than the above range, no further effect can be expected and the economy is inferior.
（潤滑剤）
本発明の水性塗料組成物には、必要に応じ潤滑剤を含有することができる。ポリエステル樹脂１００質量部に対し、潤滑剤０．１質量部〜１０質量部を加えることが好ましい。
潤滑剤を加えることにより、缶蓋等の成形加工時の塗膜の傷付きを抑制でき、また成形加工時の塗膜の滑り性を向上させることができる。
(lubricant)
The water-based coating composition of the present invention can contain a lubricant as necessary. It is preferable to add 0.1 to 10 parts by mass of a lubricant with respect to 100 parts by mass of the polyester resin.
By adding a lubricant, it is possible to suppress damage to the coating film during molding processing such as a can lid, and to improve the slipping property of the coating film during molding processing.
本発明の水性塗料組成物に加えることのできる潤滑剤としては、例えば、ポリオール化合物と脂肪酸とのエステル化物である脂肪酸エステルワックス、シリコン系ワックス、フッ素系ワックス、ポリエチレンなどのポリオレフィンワックス、ラノリン系ワックス、モンタンワックス、マイクロクリスタリンワックス、カルナバろう、およびシリコン系化合物、などを挙げることができる。これらの潤滑剤は一種、または二種以上を混合し使用できる。 Examples of the lubricant that can be added to the aqueous coating composition of the present invention include, for example, fatty acid ester waxes that are esterified products of polyol compounds and fatty acids, silicone waxes, fluorine waxes, polyolefin waxes such as polyethylene, and lanolin waxes. , Montan wax, microcrystalline wax, carnauba wax, and silicon-based compounds. These lubricants can be used alone or in combination of two or more.
（その他）
本発明の水性塗料組成物には、上記成分の他、従来より塗料組成物に配合されている、レベリング剤、顔料、消泡剤等を従来公知の処方に従って添加することもできる。
また、本発明の目的を損なわない範囲で、ポリエステル樹脂と併せてその他の樹脂成分が含まれていても良く、例えばポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、ポリオレフィン系樹脂、エポキシ樹脂、ポリウレタン樹脂、アクリル樹脂、フェノール樹脂、メラミン樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニル−酢酸ビニル共重合樹脂、ポリビニルアルコール、エチレン・ビニルアルコール共重合体、ポリビニルピロリドン、ポリビニルエチルエーテル、ポリアクリルアミド、アクリルアミド系化合物、ポリエチレンイミン、澱粉、アラビアガム、メチルセルロース等の水分散或いは水溶性樹脂が含まれていても良い。
(Other)
In addition to the components described above, leveling agents, pigments, antifoaming agents, and the like that have been conventionally blended in coating compositions can be added to the aqueous coating composition of the present invention according to conventionally known formulations.
In addition, other resin components may be included in addition to the polyester resin as long as the object of the present invention is not impaired. For example, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyolefin resin, epoxy resin, polyurethane Resin, acrylic resin, phenol resin, melamine resin, polyvinyl chloride resin, polyvinyl chloride-vinyl acetate copolymer resin, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, acrylamide A water dispersion or water-soluble resin such as a compound, polyethyleneimine, starch, gum arabic, or methylcellulose may be contained.
本発明の水性塗料組成物においては、ポリエステル樹脂が固形分として５〜５５質量％の量で含有されていることが好適である。上記範囲よりも樹脂固形分が少ない場合には、適正な塗膜量を確保することができず、被覆性が劣るようになる。一方、上記範囲よりも樹脂固形分が多い場合には、作業性及び塗工性に劣る場合がある。 In the aqueous coating composition of the present invention, it is preferable that the polyester resin is contained in an amount of 5 to 55% by mass as a solid content. When the resin solid content is less than the above range, an appropriate amount of coating film cannot be ensured, and the coverage is inferior. On the other hand, when there is more resin solid content than the said range, workability | operativity and coating property may be inferior.
本発明の水性塗料組成物は、ロールコーター塗装、スプレー塗装、ディップ塗装などの公知の塗装方法によって金属板又は予め成形された金属容器に塗装し、コイルオーブン等の加熱手段によって焼き付けることにより使用することができる。
本発明の水性塗料組成物の焼き付け条件は、ポリエステル樹脂、硬化剤、金属基材の種類、塗工量等によって適宜調節されるが、本発明の水性塗料組成物は、充分な硬化性を得るために、焼付け温度が１５０℃〜３５０℃、好ましくは２００℃より高く３２０℃以下の温度で、５秒以上、好ましくは５秒〜３０分間、より好ましくは８秒〜１８０秒間、特に好ましくは１０秒〜１２０秒間の条件で加熱硬化させることが好ましい。
また形成する塗膜の膜厚はこれに限定されるものではないが、乾燥膜厚で０．５〜３０μｍ、特に１〜１５μｍの膜厚となるように塗装することが望ましい。
The aqueous coating composition of the present invention is used by coating a metal plate or a pre-formed metal container by a known coating method such as roll coater coating, spray coating, or dip coating, and baking it by a heating means such as a coil oven. be able to.
The baking condition of the aqueous coating composition of the present invention is appropriately adjusted according to the type of polyester resin, curing agent, metal substrate, coating amount, etc., but the aqueous coating composition of the present invention has sufficient curability. Therefore, the baking temperature is 150 ° C. to 350 ° C., preferably higher than 200 ° C. and not higher than 320 ° C., for 5 seconds or more, preferably 5 seconds to 30 minutes, more preferably 8 seconds to 180 seconds, particularly preferably 10 It is preferable to heat-harden on the conditions for 1 second-120 second.
Moreover, the film thickness of the coating film to be formed is not limited to this, but it is desirable to coat the film so as to have a dry film thickness of 0.5 to 30 μm, particularly 1 to 15 μm.
（塗装金属板）
本発明の水性塗料組成物を、ロールコーター塗装、スプレー塗装などの公知の塗装方法によって金属板に塗装し、オーブン等の加熱手段によって焼き付けることにより塗装金属板を得ることができる。
金属板としては、これに限定されないが、例えば、熱延伸鋼板、冷延鋼板、溶融亜鉛メッキ鋼板、電気亜鉛メッキ鋼板、合金メッキ鋼板、アルミニウム亜鉛合金メッキ鋼板、アルミニウム板、スズメッキ鋼板、ステンレス鋼板、銅板、銅メッキ鋼板、ティンフリースチール、ニッケルメッキ鋼板、極薄スズメッキ鋼板、クロム処理鋼板などが挙げられ、必要に応じてこれらに各種表面処理、例えばリン酸クロメート処理やジルコニウム系の化成処理等を行ったものが使用できる。
また、上記塗装金属板の塗膜上に更に、有機樹脂被覆層としてポリエステル樹脂フィルム等の熱可塑性樹脂フィルムをラミネートし、有機樹脂被覆塗装金属板を形成することもできる。
(Painted metal plate)
A coated metal plate can be obtained by applying the aqueous coating composition of the present invention to a metal plate by a known coating method such as roll coater coating or spray coating, and baking it by heating means such as an oven.
Examples of the metal plate include, but are not limited to, a hot-drawn steel plate, a cold-rolled steel plate, a hot-dip galvanized steel plate, an electrogalvanized steel plate, an alloy-plated steel plate, an aluminum zinc alloy-plated steel plate, an aluminum plate, a tin-plated steel plate, a stainless steel plate, Copper plate, copper-plated steel plate, tin-free steel, nickel-plated steel plate, ultra-thin tin-plated steel plate, chrome-treated steel plate, etc., and various surface treatments such as phosphate chromate treatment and zirconium-based chemical conversion treatment etc. You can use what you did.
Moreover, a thermoplastic resin film such as a polyester resin film can be further laminated as an organic resin coating layer on the coating film of the coated metal plate to form an organic resin coated metal plate.
（塗装金属容器）
金属容器の内面及び／又は外面に本発明の水性塗料組成物から成る塗膜を形成することで塗装金属容器を得ることができる。本発明の水性塗料組成物は特に加工性、耐食性に優れているので、金属容器の少なくとも内面に本発明の塗料組成物から成る塗膜が形成されていることが望ましい。
塗膜を形成する金属容器としては、従来公知の金属容器を全て用いることができ、これに限定されないが、側面継ぎ目を有するスリーピース缶、シームレス缶（ツーピース缶）を挙げることができる。
塗装金属容器は、前述した塗装金属板から成形することで得ることもできるが、シームレス缶のような過酷な加工により成形される金属容器の場合には、予め成形された金属容器に本発明の水性塗料組成物をスプレー塗装等の方法により施すことによって得ることもできる。また前述の塗装金属板上に有機樹脂被覆層を形成した有機樹脂被覆塗装金属板からシームレス缶等の金属容器に成形することもできる。
(Painted metal container)
A coated metal container can be obtained by forming a coating film made of the aqueous coating composition of the present invention on the inner surface and / or outer surface of the metal container. Since the aqueous coating composition of the present invention is particularly excellent in workability and corrosion resistance, it is desirable that a coating film comprising the coating composition of the present invention is formed on at least the inner surface of the metal container.
As a metal container which forms a coating film, all conventionally well-known metal containers can be used, Although not limited to this, The three-piece can and a seamless can (two-piece can) which have a side seam can be mentioned.
The painted metal container can also be obtained by molding from the above-mentioned painted metal plate. However, in the case of a metal container that is formed by harsh processing such as a seamless can, the pre-formed metal container can It can also be obtained by applying the aqueous coating composition by a method such as spray coating. Moreover, it can also shape | mold into metal containers, such as a seamless can, from the organic resin coating coating metal plate which formed the organic resin coating layer on the above-mentioned coating metal plate.
（塗装金属蓋）
本発明の水性塗料組成物を塗装した前述の塗装金属板から、従来公知の任意の製蓋法によって成形することで塗装金属蓋を得ることができ、例えばステイ・オン・タブタイプのイージーオープン缶蓋やフルオープンタイプのイージーオープン缶蓋用として利用できる。
(Painted metal lid)
A coated metal lid can be obtained from the above-mentioned coated metal plate coated with the aqueous coating composition of the present invention by any conventionally known lid-making method. For example, a stay-on-tab type easy open can It can be used as a lid or a full open type easy open can lid.
以下実施例を挙げて、本発明を具体的に説明する。実施例において単に部とあるものは質量部を示す。 Hereinafter, the present invention will be specifically described with reference to examples. In the examples, the term “parts” means parts by mass.
ポリエステル樹脂の各種測定項目は以下の方法に従った。なお、測定にはカルボキシル基含有ポリエステル樹脂の水分散液から、エバポレーターを用いて水性媒体を除去した後、真空乾燥により得られた固形物を用いた。
（数平均分子量の測定）
ゲル浸透クロマトグラフィー（ＧＰＣ）によって標準ポリスチレンの検量線を用いて測定した。
（ガラス転移温度の測定）
示差走査熱量計（ＤＳＣ）を用いて２０℃／分の昇温速度で測定した。
（酸価の測定）
ポリエステル樹脂０．２ｇを２０ｍｌのクロロホルムに溶解し、０．１ＮのＫＯＨエタノール溶液で滴定し、樹脂酸価（ｍｇＫＯＨ／ｇ）を求めた。指示薬はフェノールフタレインを用いた。ポリエステル樹脂が溶解しない場合には、溶媒にテトラヒドロフラン等の溶媒を用いた。
（モノマー組成の測定）
ポリエステル樹脂のモノマー組成は、真空乾燥した樹脂３０ｍｇを重クロロホルム０．６ｍｌに溶解させ、１Ｈ−ＮＭＲ測定し、ピーク強度から組成比を求めた。なおごく微量な成分（全モノマー成分に対して１モル％未満）は除き、組成比を決定した。
Various measurement items of the polyester resin were according to the following methods. In addition, the solid substance obtained by vacuum-drying was used for the measurement, after removing the aqueous medium using the evaporator from the aqueous dispersion of the carboxyl group-containing polyester resin.
(Measurement of number average molecular weight)
Measurement was performed by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
(Measurement of glass transition temperature)
It measured with the temperature increase rate of 20 degree-C / min using the differential scanning calorimeter (DSC).
(Measurement of acid value)
0.2 g of the polyester resin was dissolved in 20 ml of chloroform, and titrated with a 0.1N KOH ethanol solution to obtain the resin acid value (mgKOH / g). Phenolphthalein was used as the indicator. When the polyester resin did not dissolve, a solvent such as tetrahydrofuran was used as the solvent.
(Measurement of monomer composition)
As for the monomer composition of the polyester resin, 30 mg of the vacuum-dried resin was dissolved in 0.6 ml of deuterated chloroform, 1 H-NMR measurement was performed, and the composition ratio was obtained from the peak intensity. The composition ratio was determined except for a very small amount of components (less than 1 mol% based on the total monomer components).
（塗装金属板の作成）
実施例、比較例、参考例の各水性塗料組成物を、表面処理としてリン酸クロメート系処理を施したアルミニウム板（３１０４合金、板厚：０．２８ｍｍ、表面処理皮膜中のクロム重量：２０ｍｇ／ｍ２）にバーコーターで乾燥後の塗膜厚が１．５μｍとなるように塗装し、オーブンで焼付し、塗装金属板を作製した。焼付条件は、焼付け温度２６０℃、焼き付け時間５０〜６０秒とした。得られた塗装金属板は下記の評価方法に基づいて各種評価を行った。
(Creation of painted metal plate)
Each of the aqueous coating compositions of Examples, Comparative Examples, and Reference Examples was subjected to a phosphoric acid chromate treatment as a surface treatment (3104 alloy, plate thickness: 0.28 mm, chromium weight in the surface treatment film: 20 mg / m 2 ) was coated with a bar coater so that the coating thickness after drying was 1.5 μm, and baked in an oven to prepare a coated metal plate. The baking conditions were a baking temperature of 260 ° C. and a baking time of 50 to 60 seconds. The obtained coated metal plate was subjected to various evaluations based on the following evaluation methods.
（硬化性）
塗装金属板の硬化性はＭＥＫ抽出率で評価した。塗装金属板から５ｃｍ×５ｃｍサイズの試験片を切り出し、サンプルの質量測定後（Ｗ１）、２００ｍｌのＭＥＫ（メチルエチルケトン）を用い、室温で１時間の抽出を行った。抽出後の塗装板を１３０℃×１時間の条件で乾燥し、抽出後のサンプルの質量（Ｗ２）を測定した。さらに塗膜を濃硫酸による分解法で剥離し、サンプルの質量（Ｗ３）を測定した。塗装板のＭＥＫ抽出率は下記式（３）で求められる。結果を表１に示す。
ＭＥＫ抽出率％＝１００×（Ｗ１−Ｗ２）／（Ｗ１−Ｗ３）・・・（３）
評価基準は次の通りである。
◎：１０％未満
○：１０％以上３０％未満
△：３０％以上５０％未満
×：５０％以上
(Curable)
The curability of the painted metal plate was evaluated by the MEK extraction rate. A test piece having a size of 5 cm × 5 cm was cut out from the coated metal plate, and after mass measurement of the sample (W1), extraction was performed at room temperature for 1 hour using 200 ml of MEK (methyl ethyl ketone). The extracted coated plate was dried under conditions of 130 ° C. × 1 hour, and the mass (W2) of the sample after extraction was measured. Furthermore, the coating film was peeled off by a decomposition method using concentrated sulfuric acid, and the mass (W3) of the sample was measured. The MEK extraction rate of the coated plate is obtained by the following formula (3). The results are shown in Table 1.
MEK extraction rate% = 100 × (W1-W2) / (W1-W3) (3)
The evaluation criteria are as follows.
◎: Less than 10% ○: 10% or more and less than 30% △: 30% or more and less than 50% ×: 50% or more
（加工性）
塗装金属板をアルミニウム板の圧延方向が長辺となるように３．５×４ｃｍの大きさに切り出し、この試験片の塗装面が外になるように短辺に平行に折り曲げた。２５℃の雰囲気下で折り曲げ部の内側に０．２８ｍｍのアルミニウム板を２枚挟み、ハゼ折タイプデュポン衝撃試験器を用い衝撃屈曲させた。衝撃屈曲させる接触面が平らな鉄の錘の重さは３ｋｇで、これを高さは４０ｃｍから落下させ、この折り曲げられた先端部分の２ｃｍ幅の電流値（ｍＡ）を１％塩化ナトリウム水溶液に浸漬したスポンジに接触させ、電圧６．３Ｖをかけ４秒後に測定した。結果を表１に示す。
◎：５ｍＡ未満
○：５ｍＡ以上２０ｍＡ未満
△：２０ｍＡ以上３０ｍＡ未満
×：３０ｍＡ以上
(Processability)
The coated metal plate was cut into a size of 3.5 × 4 cm so that the rolling direction of the aluminum plate was the long side, and was bent parallel to the short side so that the coated surface of the test piece was outside. Two 0.28 mm aluminum plates were sandwiched inside the bent portion in an atmosphere at 25 ° C., and impact bent using a goby folding type DuPont impact tester. The weight of the iron weight with a flat contact surface for impact bending is 3 kg, the height is dropped from 40 cm, and the current value (mA) of the 2 cm width of the bent tip is changed to 1% sodium chloride aqueous solution. The measurement was performed after 4 seconds by applying a voltage of 6.3 V to the immersed sponge. The results are shown in Table 1.
◎: Less than 5 mA ○: 5 mA or more and less than 20 mA Δ: 20 mA or more and less than 30 mA ×: 30 mA or more
（耐食性）
塗装金属板から５ｃｍ×５ｃｍサイズの試験片を切り出した後、デュポン衝撃試験器を用い、撃芯の尖端直径１／４インチ、錘荷重１２０ｇ、落錘高さ３０ｃｍの条件で試験塗板の塗面に凸加工した試験片を、缶内容物擬似液であるモデル液に浸漬し、腐食の程度を下記基準により目視で評価した。浸漬条件は、３７℃で１４日間とした。試験に用いたモデル液は、食塩を０．２％とし、これにクエン酸を加えてｐＨが２．５となるよう調製したものを用いた。結果を表１示す。
◎：腐食なし
○：僅かに腐食
△：部分的に腐食
×：大部分で腐食
(Corrosion resistance)
After cutting a test piece of 5cm x 5cm size from a painted metal plate, using a DuPont impact tester, the coating surface of the test coating plate under the conditions of a tip diameter of 1/4 inch, a weight load of 120g, and a falling weight height of 30cm The test piece convexly processed was immersed in a model liquid which is a can contents simulated liquid, and the degree of corrosion was visually evaluated according to the following criteria. The immersion conditions were 14 days at 37 ° C. The model solution used for the test was prepared so that sodium chloride was 0.2% and citric acid was added thereto to adjust the pH to 2.5. The results are shown in Table 1.
◎: No corrosion ○: Slightly corrosion △: Partially corrosive ×: Mostly corrosive
（耐レトルト性）
塗装金属板をオートクレーブに入れ、１２５℃３０分のレトルト処理を施し、塗膜の白化状態（白化性）を目視で評価した。結果を表２に示す。
◎：白化なし
○：僅かに白化
△：少し白化
×：著しく白化
(Retort resistance)
The coated metal plate was placed in an autoclave, subjected to a retort treatment at 125 ° C. for 30 minutes, and the whitening state (whitening property) of the coating film was visually evaluated. The results are shown in Table 2.
◎: No whitening ○: Slightly whitening △: Slightly whitening ×: Remarkably whitening
［水性塗料組成物の調製］
（実施例１）
ポリエステル樹脂としてポリエステル樹脂Ａ（酸価：２３ｍｇＫＯＨ／ｇ、Ｔｇ：８０℃、Ｍｎ＝７，５００、モノマー組成：テレフタル酸成分／エチレングリコール成分／プロピレングリコール成分＝５０／１０／４０ｍｏｌ％）、β−ヒドロキシアルキルアミド基含有硬化剤（β−ヒドロキシアルキルアミド化合物）としてＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシエチル）アジポアミド［東京化成工業社製；表中「β−ヒドロキシアルキルアミドＡ」と表記］を用いた。ポリエステル樹脂Ａの水分散液（固形分濃度：３０ｗｔ％）を３３３部（固形分１００部）、予めイオン交換水を用いて調整しておいたβ−ヒドロキシアルキルアミド基含有硬化剤の水溶液（固形分濃度：１０ｗｔ％）を５０部（固形分５部）、２−プロパノール１５０部、イオン交換水５１７部をガラス容器内に入れて１０分間攪拌し、固形分濃度１０質量％、固形分配合比がポリエステル樹脂／硬化剤＝１００／５（質量比）の水性塗料組成物を得た。
[Preparation of aqueous coating composition]
Example 1
Polyester resin A (acid value: 23 mgKOH / g, Tg: 80 ° C., Mn = 7,500, monomer composition: terephthalic acid component / ethylene glycol component / propylene glycol component = 50/10/40 mol%), β- As a hydroxyalkylamide group-containing curing agent (β-hydroxyalkylamide compound), N, N, N ′, N′-tetrakis (2-hydroxyethyl) adipamide [manufactured by Tokyo Chemical Industry Co., Ltd .; ] Is used. 333 parts (solid content 100 parts) of an aqueous dispersion of polyester resin A (solid content concentration: 30 wt%), an aqueous solution (solid) of a β-hydroxyalkylamide group-containing curing agent prepared in advance using ion-exchanged water (Concentration: 10 wt%) 50 parts (solid content 5 parts), 2-propanol 150 parts, ion exchange water 517 parts in a glass container and stirred for 10 minutes, solid content concentration 10% by mass, solid content ratio Of polyester resin / curing agent = 100/5 (mass ratio) was obtained.
（実施例２〜６）
表１に示すように、ポリエステル樹脂を、ポリエステル樹脂Ｂ（Ｔｇ：６７℃、Ｍｎ＝９，０００、酸価：１８ｍｇＫＯＨ／ｇ、モノマー組成：テレフタル酸成分／イソフタル酸成分／エチレングリコール成分／ネオペンチルグリコール成分＝３６／１４／２４／２６ｍｏｌ％）、ポリエステル樹脂Ｃ（Ｔｇ：４０℃、Ｍｎ＝８，５００、酸価：１７ｍｇＫＯＨ／ｇ、モノマー組成：テレフタル酸成分／イソフタル酸成分／アジピン酸／エチレングリコール成分／ネオペンチルグリコール成分＝２８／１５／７／２５／２５ ｍｏｌ％）、ポリエステル樹脂Ｄ（Ｔｇ：２０℃、Ｍｎ＝１７，０００、酸価：１１ｍｇＫＯＨ／ｇ、モノマー組成：テレフタル酸成分／イソフタル酸成分／セバシン酸成分／エチレングリコール成分／ネオペンチルグリコール成分＝３１／７／１２／３０／２０ｍｏｌ％）、ポリエステル樹脂Ｇ（Ｔｇ：４０℃、Ｍｎ＝５，０００、酸価：２９ｍｇＫＯＨ／ｇ）、ポリエステル樹脂Ｈ（Ｔｇ：５２℃、Ｍｎ＝１７，０００、酸価：５ｍｇＫＯＨ／ｇ、モノマー組成：テレフタル酸成分／イソフタル酸成分／アジピン酸成分／エチレングリコール成分／ネオペンチルグリコール成分＝２３／２３／４／２４／２６ｍｏｌ％）に変えた以外は、実施例１と同様に行い、塗料組成物を得た。
(Examples 2 to 6)
As shown in Table 1, the polyester resin is represented by polyester resin B (Tg: 67 ° C., Mn = 9,000, acid value: 18 mgKOH / g, monomer composition: terephthalic acid component / isophthalic acid component / ethylene glycol component / neopentyl). Glycol component = 36/14/24/26 mol%), polyester resin C (Tg: 40 ° C., Mn = 8,500, acid value: 17 mg KOH / g, monomer composition: terephthalic acid component / isophthalic acid component / adipic acid / ethylene Glycol component / neopentyl glycol component = 28/15/7/25/25 mol%), polyester resin D (Tg: 20 ° C., Mn = 17,000, acid value: 11 mgKOH / g, monomer composition: terephthalic acid component / Isophthalic acid component / Sebacic acid component / Ethylene glycol component / Neopentyling Recall component = 31/7/12/30/20 mol%), polyester resin G (Tg: 40 ° C., Mn = 5,000, acid value: 29 mgKOH / g), polyester resin H (Tg: 52 ° C., Mn = 17) , 000, acid value: 5 mg KOH / g, monomer composition: terephthalic acid component / isophthalic acid component / adipic acid component / ethylene glycol component / neopentyl glycol component = 23/23/4/24/26 mol%) The coating composition was obtained in the same manner as in Example 1.
（実施例７）
ポリエステル樹脂として、ポリエステル樹脂Ａとポリエステル樹脂Ｄを、質量比で６０：４０となるように混合したもの（Ｔｇｍｉｘ：５３℃、平均酸価：１８ｍｇＫＯＨ／ｇ）を用いた以外は、実施例１と同様に行い、塗料組成物を調製した。
(Example 7)
Example 1 except that polyester resin A and polyester resin D mixed at a mass ratio of 60:40 (Tgmix: 53 ° C., average acid value: 18 mgKOH / g) were used as the polyester resin. In the same manner, a coating composition was prepared.
（実施例８）
ポリエステル樹脂として、ポリエステル樹脂Ａとポリエステル樹脂Ｆ（Ｔｇ：−２５℃、Ｍｎ＝１７，０００、酸価：１２ｍｇＫＯＨ／ｇ、モノマー組成：テレフタル酸成分／イソフタル酸成分／セバシン酸成分／１，４−ブタンジオール成分＝１４／１７／１９／５０ｍｏｌ％）を、質量比で７０：３０となるように混合したもの（Ｔｇｍｉｘ：４０℃、平均酸価＝２０ｍｇＫＯＨ／ｇ）を用いた以外は、実施例１と同様に行い、塗料組成物を調製した。
(Example 8)
As polyester resins, polyester resin A and polyester resin F (Tg: −25 ° C., Mn = 17,000, acid value: 12 mg KOH / g, monomer composition: terephthalic acid component / isophthalic acid component / sebacic acid component / 1,4- Example except that a butanediol component = 14/17/19/50 mol%) mixed at a mass ratio of 70:30 (Tgmix: 40 ° C., average acid value = 20 mgKOH / g) was used In the same manner as in No. 1, a coating composition was prepared.
（実施例９）
ポリエステル樹脂として、ポリエステル樹脂Ｂとポリエステル樹脂Ｅ（Ｔｇ：８℃、Ｍｎ＝１９，０００、酸価：１２ｍｇＫＯＨ／ｇ、モノマー組成：テレフタル酸成分／イソフタル酸成分／セバシン酸成分／エチレングリコール成分／ネオペンチルグリコール成分＝３０／５／１５／２２／２８ｍｏｌ％）を、質量比で５０：５０となるように混合したもの（Ｔｇｍｉｘ：３３℃、平均酸価＝１５ｍｇＫＯＨ／ｇ）を用いた以外は、実施例１と同様に行い、塗料組成物を調製した。
Example 9
As polyester resins, polyester resin B and polyester resin E (Tg: 8 ° C., Mn = 19000, acid value: 12 mg KOH / g, monomer composition: terephthalic acid component / isophthalic acid component / sebacic acid component / ethylene glycol component / neo Except that a pentyl glycol component = 30/5/15/22/28 mol%) mixed at a mass ratio of 50:50 (Tgmix: 33 ° C., average acid value = 15 mgKOH / g) was used. In the same manner as in Example 1, a coating composition was prepared.
（実施例１０〜１４）
表１に示す固形分配合比となるようにした以外は、実施例１と同様に水性塗料組成物を調製した。
(Examples 10 to 14)
An aqueous coating composition was prepared in the same manner as in Example 1 except that the solid content blending ratio shown in Table 1 was used.
（実施例１５）
β−ヒドロキシアルキルアミド基含有硬化物（β−ヒドロキシアルキルアミド化合物）としてＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシプロピル）アジポアミド［ＥＭＳ社製Ｐｒｉｍｉｄ ＱＭ１２６０；表中「β−ヒドロキシアルキルアミドＢ」と表記］を用いた以外は、実施例１と同様に水性塗料組成物を調製した。
(Example 15)
N-, N-, N ', N'-tetrakis (2-hydroxypropyl) adipamide [Primid QM1260 manufactured by EMS; "β-hydroxyalkylamide" as a β-hydroxyalkylamide group-containing cured product (β-hydroxyalkylamide compound) A water-based coating composition was prepared in the same manner as in Example 1 except that the expression “amide B” was used.
（比較例１〜３）
表１に示す各種ポリエステル樹脂、或いは、固形分配合比となるようにした以外は、実施例１と同様に水性塗料組成物を調製した。
(Comparative Examples 1-3)
An aqueous coating composition was prepared in the same manner as in Example 1 except that various polyester resins shown in Table 1 or a solid content blending ratio were used.
（参考例１）
ポリエステル樹脂として、ポリエステル樹脂Ａ、硬化剤としてレゾール型フェノール樹脂を用いた。レゾール型フェノール樹脂としては、メチロール基をブチルエーテル化したメタクレゾール系フェノール樹脂（エーテル化されたメチロール基の割合：９０モル％、Ｍｎ＝１，６００）を用いた。ポリエステル樹脂Ａの水分散液３３３部（固形分１００部）、上記レゾール型フェノール樹脂のｎ−ブタノール溶液４０部（固形分２０部）、ドデシルベンゼンスルホン酸１部（硬化触媒）、トリエチルアミン０．３部、２−プロパノール２００部、イオン交換水６３５部を用いて水性塗料組成物（固形分濃度：１０質量％、固形分配合比：ポリエステル樹脂／硬化剤＝１００／１５）を調製した。なお、ドデシルベンゼンスルホン酸としては、東京化成工業社製「ドデシルベンゼンスルホン酸（ソフト型）（混合物）」を用いた。
(Reference Example 1)
Polyester resin A was used as the polyester resin, and resol type phenol resin was used as the curing agent. As the resol-type phenol resin, a metacresol phenol resin in which methylol groups were butyl etherified (ratio of etherified methylol groups: 90 mol%, Mn = 1,600) was used. Aqueous dispersion of polyester resin A 333 parts (solid content 100 parts), n-butanol solution 40 parts (solid content 20 parts) of the above-mentioned resol type phenol resin, 1 part dodecylbenzenesulfonic acid (curing catalyst), triethylamine 0.3 Part, 200 parts of 2-propanol, and 635 parts of ion-exchanged water were used to prepare an aqueous coating composition (solid content concentration: 10% by mass, solid content ratio: polyester resin / curing agent = 100/15). As dodecylbenzenesulfonic acid, “Dodecylbenzenesulfonic acid (soft type) (mixture)” manufactured by Tokyo Chemical Industry Co., Ltd. was used.
（参考例２）
水性塗料組成物中の固形分配合比がポリエステル樹脂／硬化剤＝１００／５（質量比）となるように硬化剤のｎ―ブタノール溶液及びイオン交換水の配合量を調整した以外は、参考例１と同様に水性塗料組成物を調製した。
(Reference Example 2)
Reference Example, except that the blending amount of the n-butanol solution and ion-exchanged water of the curing agent was adjusted so that the solid content blending ratio in the aqueous coating composition was polyester resin / curing agent = 100/5 (mass ratio) An aqueous coating composition was prepared in the same manner as in 1.
（実施例１６）
ポリエステル樹脂として、ポリエステル樹脂Ａとポリエステル樹脂Ｆを、質量比で８０：２０となるように混合したもの（Ｔｇｍｉｘ：５２℃、平均酸価：２１ｍｇＫＯＨ／ｇ）を用いた以外は、実施例１と同様に行い、塗料組成物を調製した。
(Example 16)
Example 1 except that polyester resin A and polyester resin F mixed at a mass ratio of 80:20 (Tgmix: 52 ° C., average acid value: 21 mgKOH / g) were used as the polyester resin. In the same manner, a coating composition was prepared.
（実施例１７）
ポリエステル樹脂として、ポリエステル樹脂Ａとポリエステル樹脂Ｆを、質量比で８０：２０となるように混合したもの（Ｔｇｍｉｘ：５２℃、平均酸価：２１ｍｇＫＯＨ／ｇ）、β−ヒドロキシアルキルアミド基含有硬化剤として、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ヒドロキシプロピル）アジポアミド［ＥＭＳ社製Ｐｒｉｍｉｄ ＱＭ１２６０；表中「β−ヒドロキシアルキルアミドＢ」と表記］を用いた以外は、実施例１と同様に水性塗料組成物を調製した。
(Example 17)
As polyester resin, polyester resin A and polyester resin F mixed at a mass ratio of 80:20 (Tgmix: 52 ° C., average acid value: 21 mgKOH / g), β-hydroxyalkylamide group-containing curing agent As Example 1, except that N, N, N ′, N′-tetrakis (2-hydroxypropyl) adipamide [Primid QM1260 manufactured by EMS; expressed as “β-hydroxyalkylamide B” in the table] was used. Similarly, an aqueous coating composition was prepared.
表１、表２に、各水性塗料組成物の組成（ポリエステル樹脂の種類、硬化剤の種類、固形分配合比）と評価結果を示す。 Tables 1 and 2 show the composition of each aqueous coating composition (type of polyester resin, type of curing agent, blending ratio of solid content) and evaluation results.
本発明の水性塗料組成物は、優れた加工性及び硬化性、耐食性を有する塗膜を形成可能であることから、金属缶や缶蓋等の内面塗料又は外面塗料として好適に使用できる。 Since the aqueous coating composition of the present invention can form a coating film having excellent processability, curability, and corrosion resistance, it can be suitably used as an inner surface coating or outer surface coating such as a metal can or a can lid.
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| JP2017094779 | 2017-05-11 | ||
| JP2017094779 | 2017-05-11 | ||
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| JP2017150489 | 2017-08-03 | ||
| JP2018040710 | 2018-03-07 | ||
| JP2018040710 | 2018-03-07 |
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| JP2019157102A true JP2019157102A (en) | 2019-09-19 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020100775A1 (en) * | 2018-11-13 | 2020-05-22 | 東洋製罐グループホールディングス株式会社 | Aqueous coating material composition and coated metal base body |
| US20220001417A1 (en) * | 2018-11-13 | 2022-01-06 | Toyo Seikan Group Holdings, Ltd. | Coated metal sheet and drawn-ironed can |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5117970A (en) * | 1974-03-25 | 1976-02-13 | Roehm & Haas Gmbh | |
| JP2003026992A (en) * | 2001-07-19 | 2003-01-29 | Kansai Paint Co Ltd | Aqueous coating composition |
| JP2003321646A (en) * | 2002-05-01 | 2003-11-14 | Toyo Seikan Kaisha Ltd | Water-based coating material for metallic packaging material and metallic packaging material coated therewith |
| JP2004107568A (en) * | 2002-09-20 | 2004-04-08 | Unitika Ltd | Aqueous dispersion of resin |
| JP2004339493A (en) * | 2003-04-22 | 2004-12-02 | Kansai Paint Co Ltd | Thermosetting aqueous coating composition |
| JP2005194494A (en) * | 2003-12-09 | 2005-07-21 | Kansai Paint Co Ltd | Method for producing aqueous polyester resin composition, thermosetting water-borne coating composition obtained by using aqueous polyester resin composition and coating material obtained by using thermosetting water-borne coating composition |
| JP2008007627A (en) * | 2006-06-29 | 2008-01-17 | Dainippon Ink & Chem Inc | Polyester resin-based aqueous coating composition for outer surface of can |
| JP2013249376A (en) * | 2012-05-31 | 2013-12-12 | Toyo Seikan Co Ltd | Coating material composition, and coated metal plate, metal container and metal lid formed by coating the coating material composition |
| JP2014514370A (en) * | 2011-03-02 | 2014-06-19 | ダウ グローバル テクノロジーズ エルエルシー | Coating composition and articles made therefrom |
-
2018
- 2018-05-11 JP JP2018092501A patent/JP7067253B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5117970A (en) * | 1974-03-25 | 1976-02-13 | Roehm & Haas Gmbh | |
| JP2003026992A (en) * | 2001-07-19 | 2003-01-29 | Kansai Paint Co Ltd | Aqueous coating composition |
| JP2003321646A (en) * | 2002-05-01 | 2003-11-14 | Toyo Seikan Kaisha Ltd | Water-based coating material for metallic packaging material and metallic packaging material coated therewith |
| JP2004107568A (en) * | 2002-09-20 | 2004-04-08 | Unitika Ltd | Aqueous dispersion of resin |
| JP2004339493A (en) * | 2003-04-22 | 2004-12-02 | Kansai Paint Co Ltd | Thermosetting aqueous coating composition |
| JP2005194494A (en) * | 2003-12-09 | 2005-07-21 | Kansai Paint Co Ltd | Method for producing aqueous polyester resin composition, thermosetting water-borne coating composition obtained by using aqueous polyester resin composition and coating material obtained by using thermosetting water-borne coating composition |
| JP2008007627A (en) * | 2006-06-29 | 2008-01-17 | Dainippon Ink & Chem Inc | Polyester resin-based aqueous coating composition for outer surface of can |
| JP2014514370A (en) * | 2011-03-02 | 2014-06-19 | ダウ グローバル テクノロジーズ エルエルシー | Coating composition and articles made therefrom |
| JP2013249376A (en) * | 2012-05-31 | 2013-12-12 | Toyo Seikan Co Ltd | Coating material composition, and coated metal plate, metal container and metal lid formed by coating the coating material composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020100775A1 (en) * | 2018-11-13 | 2020-05-22 | 東洋製罐グループホールディングス株式会社 | Aqueous coating material composition and coated metal base body |
| US20220001417A1 (en) * | 2018-11-13 | 2022-01-06 | Toyo Seikan Group Holdings, Ltd. | Coated metal sheet and drawn-ironed can |
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| JP7067253B2 (en) | 2022-05-16 |
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