JP6253553B2 - Paint composition - Google Patents
Paint composition Download PDFInfo
- Publication number
- JP6253553B2 JP6253553B2 JP2014181095A JP2014181095A JP6253553B2 JP 6253553 B2 JP6253553 B2 JP 6253553B2 JP 2014181095 A JP2014181095 A JP 2014181095A JP 2014181095 A JP2014181095 A JP 2014181095A JP 6253553 B2 JP6253553 B2 JP 6253553B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- parts
- resin
- acid
- mass
- 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.)
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- 239000000203 mixture Substances 0.000 title description 22
- 239000003973 paint Substances 0.000 title description 18
- 229920001225 polyester resin Polymers 0.000 claims description 88
- 239000004645 polyester resin Substances 0.000 claims description 88
- 238000000576 coating method Methods 0.000 claims description 80
- 239000011248 coating agent Substances 0.000 claims description 78
- 239000008199 coating composition Substances 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 9
- 229920003180 amino resin Polymers 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000010408 film Substances 0.000 description 56
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 39
- 230000007797 corrosion Effects 0.000 description 29
- 238000005260 corrosion Methods 0.000 description 29
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 25
- 238000012360 testing method Methods 0.000 description 22
- 239000005011 phenolic resin Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- 239000000796 flavoring agent Substances 0.000 description 14
- 235000019634 flavors Nutrition 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- -1 vinyl-amino Chemical group 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 229920003987 resole Polymers 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 229920000180 alkyd Polymers 0.000 description 8
- 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 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000007519 polyprotic acids Polymers 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 5
- 206010040844 Skin exfoliation Diseases 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 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
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 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
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000005029 tin-free steel Substances 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-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
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 238000005809 transesterification reaction Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- PFUKECZPRROVOD-UHFFFAOYSA-N 1,3,5-triisocyanato-2-methylbenzene Chemical compound CC1=C(N=C=O)C=C(N=C=O)C=C1N=C=O PFUKECZPRROVOD-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-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
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
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Description
本発明は、加工性と硬度とのバランスに優れ、かつ硬化性、耐レトルト性、耐食性、密着性、耐傷付性、フレーバー性、衛生性に優れ、さらに薄膜における腐食液に対する耐食性にも優れた塗膜を形成できる塗料組成物、特に缶被覆用に適した塗料組成物、この塗料組成物を塗装した塗装金属板、及びこの塗料組成物の塗膜を表面に形成した塗装金属缶に関する。 The present invention has an excellent balance between workability and hardness, and has excellent curability, retort resistance, corrosion resistance, adhesion, scratch resistance, flavor and hygiene, and also excellent corrosion resistance to a corrosive liquid in a thin film. The present invention relates to a coating composition capable of forming a coating film, particularly a coating composition suitable for can coating, a coated metal plate coated with the coating composition, and a coated metal can having a coating film of the coating composition formed on the surface.
従来、金属缶素材としては、アルミニウム、ブリキ、ティンフリースチール等の金属が用いられている。これらの金属は、その腐食を防止するために、通常、缶の内外面に密着性および耐食性に優れたエポキシ／フェノール樹脂系、エポキシ／アミノ樹脂系の塗料が多く用いられている。 Conventionally, metals such as aluminum, tin, and tin-free steel are used as the metal can material. In order to prevent the corrosion of these metals, usually epoxy / phenol resin-based and epoxy / amino resin-based paints having excellent adhesion and corrosion resistance are used on the inner and outer surfaces of the can.
しかしながら、近年、環境ホルモンとして疑いのもたれているビスフェノールＡの溶出量の問題から、ビスフェノールＡを含有しない塗料系が求められている。このような缶用塗料として、加工性を必要とする缶内外面、蓋内外面、キャップ内外面用塗料としては、ポリエステル−アクリル樹脂系の熱硬化性塗料（例えば、特許文献１参照）ポリエステル樹脂とフェノール樹脂を含有する塗料（例えば、特許文献２参照）、ビニル−アミノ樹脂、ビニルオルガノゾル等の樹脂系の塗料が使用されている。これらの塗料から得られる塗膜は、加工性と硬度とのバランスに優れ、密着性も良好であるが、缶内面に使用するには、耐レトルト性、フレーバー性（内容物の風味保持性）、衛生性などが不十分であるという問題を有している。 However, in recent years, a coating system that does not contain bisphenol A has been demanded due to the problem of elution amount of bisphenol A, which is suspected as an environmental hormone. As such a paint for cans, a polyester-acrylic resin-based thermosetting paint (for example, refer to Patent Document 1) polyester resin as a paint for can inner / outer surfaces, lid inner / outer surfaces, and cap inner / outer surfaces requiring workability. A resin-based paint such as a paint containing phenol and a phenol resin (see, for example, Patent Document 2), a vinyl-amino resin, and a vinyl organosol is used. The coatings obtained from these paints have a good balance between workability and hardness and good adhesion, but for use on the inner surface of cans, they are resistant to retort and flavor (content flavor retention). , Have the problem of insufficient hygiene.
また、特定のガラス転移温度を有する２種類のポリエステル樹脂の混合物に、架橋剤、硬化触媒を含有する塗料が、耐経時脆化性、加工性、耐食性、耐レトルト性に優れる塗膜を形成できることが特許文献３に記載されている。しかしながら、この塗料を、缶胴や缶蓋の内面塗料として使用して形成した塗膜は、低膜厚時での腐食液に対する耐食性が充分ではなく、架橋剤を増量することによって耐食性は良化するが、一方、フレーバー性が低下するといった問題があった。 In addition, a coating containing a crosslinking agent and a curing catalyst can form a coating film having excellent resistance to embrittlement with time, workability, corrosion resistance, and retort resistance in a mixture of two types of polyester resins having specific glass transition temperatures. Is described in Patent Document 3. However, the paint film formed using this paint as the inner paint of can bodies and can lids does not have sufficient corrosion resistance against corrosive liquids at low film thickness, and the corrosion resistance is improved by increasing the amount of the crosslinking agent. However, on the other hand, there was a problem that the flavor property was lowered.
そこで本発明者らは、加工性と硬度とのバランスに優れ、かつ硬化性、耐レトルト性、耐食性、密着性、耐傷付性、フレーバー性、衛生性に優れ、さらに薄膜における腐食液に対する耐食性に優れた塗膜を形成できる塗料組成物を得るべく鋭意研究の結果、特定のガラス転移温度を有する２種のポリエステル樹脂の特定割合の混合物と、特定のレゾール型フェノール樹脂架橋剤の所定量とを含有する塗料組成物によって上記目的を達成できることを見出し本発明を完成するに至った。 Therefore, the present inventors have an excellent balance between workability and hardness, and are excellent in curability, retort resistance, corrosion resistance, adhesion, scratch resistance, flavor, hygiene, and corrosion resistance to a corrosive liquid in a thin film. As a result of earnest research to obtain a coating composition capable of forming an excellent coating film, a mixture of a specific ratio of two polyester resins having a specific glass transition temperature and a predetermined amount of a specific resol type phenol resin cross-linking agent The inventors have found that the above object can be achieved by the coating composition contained, and have completed the present invention.
本発明の目的は、加工性と硬度とのバランスに優れ、かつ硬化性、耐レトルト性、耐食性、密着性、耐傷付性、フレーバー性、衛生性に優れ、さらに薄膜における腐食液に対する耐食性にも優れた塗膜を形成できる塗料組成物、特に缶被覆用に適した塗料組成物を提供することである。 The object of the present invention is excellent in balance between workability and hardness, and excellent in curability, retort resistance, corrosion resistance, adhesion, scratch resistance, flavor and hygiene, and also in corrosion resistance to a corrosive liquid in a thin film. It is an object of the present invention to provide a coating composition capable of forming an excellent coating film, particularly a coating composition suitable for can coating.
また、本発明の目的は、上記塗料組成物を塗装した塗装金属板を提供すること、及び上記塗料組成物の塗膜を表面に形成した塗装金属缶を提供することである。 Another object of the present invention is to provide a coated metal plate coated with the coating composition, and to provide a coated metal can having a coating film of the coating composition formed on the surface.
そこで本発明者らは、上記課題を解決できる塗料組成物を得るべく鋭意研究の結果、特定のガラス転移温度を有する２種のポリエステル樹脂の特定割合の混合物と、特定のレゾール型フェノール樹脂架橋剤とを所定量含有する塗料組成物によって上記目的を達成できることを見出し本発明を完成するに至った。 Therefore, as a result of intensive studies to obtain a coating composition that can solve the above problems, the present inventors have found that a mixture of two polyester resins having a specific glass transition temperature and a specific resol type phenolic resin crosslinking agent. As a result, the present invention has been completed.
すなわち、本発明は、（Ａ）ガラス転移温度が７０℃を超え、且つ１００℃以下の範囲であるポリエステル樹脂、（Ｂ）ガラス転移温度が４０℃〜７０℃の範囲であるポリエステル樹脂及び（Ｃ）フェノール成分として３官能以上のフェノール化合物を５０質量％以上含有するフェノール成分を出発原料とするレゾール型フェノール樹脂架橋剤及び（Ｄ）酸硬化触媒を含有する塗料組成物であって、該ポリエステル樹脂（Ａ）と該ポリエステル樹脂（Ｂ）との配合割合が、〔（Ａ）／（Ｂ）〕の固形分質量比で４０／６０〜５／９５であり、該ポリエステル樹脂（Ａ）と該ポリエステル樹脂（Ｂ）との固形分合計１００質量部に対し、該レゾール型フェノール樹脂（Ｃ）量が１〜２０質量部であり、かつ該酸硬化触媒の量が酸量として０．１〜５質量部であることを特徴とする塗料組成物を提供するものである。 That is, the present invention includes (A) a polyester resin having a glass transition temperature of more than 70 ° C. and not more than 100 ° C., (B) a polyester resin having a glass transition temperature of 40 ° C. to 70 ° C., and (C A coating composition containing a resole-type phenol resin cross-linking agent starting from a phenol component containing 50% by mass or more of a phenol compound having a functionality of 3 or more as a phenol component, and (D) an acid curing catalyst, the polyester resin The blending ratio of (A) to the polyester resin (B) is 40/60 to 5/95 in terms of the solid content mass ratio of [(A) / (B)], and the polyester resin (A) and the polyester The amount of the resol type phenolic resin (C) is 1 to 20 parts by mass and the amount of the acid curing catalyst is 0.1 as the amount of acid with respect to 100 parts by mass of the total solid content with the resin (B). There is provided a coating composition characterized in that 5 a mass parts.
また、本発明は、上記塗料組成物が塗装、硬化されてなることを特徴とする塗装金属板を提供するものである。 The present invention also provides a coated metal plate, wherein the coating composition is coated and cured.
さらに、本発明は、上記塗料組成物による硬化塗膜が缶表面の少なくとも一部に形成されてなることを特徴とする塗装金属缶を提供するものである。 Furthermore, the present invention provides a coated metal can characterized in that a cured coating film by the coating composition is formed on at least a part of the can surface.
本発明の塗料組成物は、加工性と硬度とのバランスに優れ、かつ硬化性、耐レトルト性、耐食性、密着性、耐傷付性、フレーバー性、衛生性に優れ、さらに薄膜における腐食液に対する耐食性にも優れた塗膜を形成でき、特に缶被覆用に適した塗料組成物である。 The coating composition of the present invention has an excellent balance between processability and hardness, and is excellent in curability, retort resistance, corrosion resistance, adhesion, scratch resistance, flavor and hygiene, and corrosion resistance to a corrosive liquid in a thin film. In particular, it is a coating composition that can form an excellent coating film and is particularly suitable for can coating.
本発明の塗装金属板は、上記本発明塗料組成物による硬化塗膜を有するものであり、上記した優れた塗膜性能を有する。 The coated metal plate of the present invention has a cured coating film formed from the above-described coating composition of the present invention, and has the above-described excellent coating film performance.
本発明の塗装金属缶は、缶表面の少なくとも一部に上記本発明塗料組成物による硬化塗膜を有するものであり、この塗膜が形成された缶表面は、上記した優れた塗膜性能を有する。 The coated metal can of the present invention has a cured coating film by the above-mentioned coating composition of the present invention on at least a part of the can surface, and the can surface on which the coating film is formed has the above-described excellent coating film performance. Have.
以下、本発明の塗料組成物について、さらに詳細に説明する。 Hereinafter, the coating composition of the present invention will be described in more detail.
本発明の塗料組成物は、ポリエステル樹脂（Ａ）、ポリエステル樹脂（Ｂ）及びレゾール型フェノール樹脂（Ｃ）を含有する。 The coating composition of the present invention contains a polyester resin (A), a polyester resin (B), and a resol type phenol resin (C).
ポリエステル樹脂（Ａ）
本発明組成物において、（Ａ）成分であるポリエステル樹脂は、水酸基を含有するポリエステル樹脂であり、オイルフリーポリエステル樹脂、油変性アルキド樹脂、また、これらの樹脂の変性物、例えばウレタン変性ポリエステル樹脂、ウレタン変性アルキド樹脂などのいずれであってもよい。なかでもオイルフリーポリエステル樹脂であることが好適である。
Polyester resin (A)
In the composition of the present invention, the polyester resin as the component (A) is a polyester resin containing a hydroxyl group, an oil-free polyester resin, an oil-modified alkyd resin, or a modified product of these resins, such as a urethane-modified polyester resin, Any of urethane-modified alkyd resins and the like may be used. Of these, an oil-free polyester resin is preferred.
上記オイルフリーポリエステル樹脂は、主に多塩基酸と多価アルコールとのエステル化物である。多塩基酸成分としては、例えば無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、ヘキサヒドロテレフタル酸、コハク酸、フマル酸、アジピン酸、セバシン酸、無水マレイン酸、フマル酸などから選ばれる１種以上の二塩基酸が主として用いられ、必要に応じて安息香酸、クロトン酸、ｐ−ｔ−ブチル安息香酸などの一塩基酸、無水トリメリット酸、メチルシクロヘキセントリカルボン酸、無水ピロメリット酸などの３価以上の多塩基酸などが併用される。これらの多塩基酸成分は単独で、あるいは２種以上を混合して使用することができる。多価アルコール成分としては、例えばエチレングリコール、ジエチレングリコール、１，２−プロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、ネオペンチルグリコール、３−メチルペンタンジオール、１，４−ヘキサンジオール、１，６−ヘキサンジオール、２−メチル−１，３−プロパンジオール、２−エチル２−ブチル−１，３−プロパンジオール、１，４−ジメチロ−ルシクロヘキサンなどの二価アルコールが主に用いられ、さらに必要に応じてグリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトールなどの３価以上の多価アルコールを併用することができる。これらの多価アルコールは単独で、あるいは２種以上を混合して使用することができる。両成分のエステル化反応は、公知の方法によって行うことができる。 The oil-free polyester resin is mainly an esterified product of a polybasic acid and a polyhydric alcohol. Examples of the polybasic acid component include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydroterephthalic acid, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride, fumaric acid. One or more dibasic acids selected from acids and the like are mainly used. If necessary, monobasic acids such as benzoic acid, crotonic acid, and pt-butylbenzoic acid, trimellitic anhydride, methylcyclohextricarboxylic acid, A tribasic or higher polybasic acid such as pyromellitic anhydride is used in combination. These polybasic acid components can be used alone or in admixture of two or more. Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, and 1,4-hexanediol. 1,6-hexanediol, 2-methyl-1,3-propanediol, 2-ethyl 2-butyl-1,3-propanediol, 1,4-dimethylolcyclohexane and other dihydric alcohols are mainly used. Further, if necessary, a trihydric or higher polyhydric alcohol such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol can be used in combination. These polyhydric alcohols can be used alone or in admixture of two or more. The esterification reaction of both components can be performed by a known method.
上記オイルフリーポリエステル樹脂は、上記エステル化反応において、多塩基酸のかわりに多塩基酸の低級アルキルエステル（例えばメチルエステル、エチルエステルなど）を用い、エステル交換反応を行うことによっても得ることができる。両成分のエステル交換反応は、公知の方法によって行うことができる。 The oil-free polyester resin can also be obtained by performing a transesterification reaction using a lower alkyl ester of a polybasic acid (eg, methyl ester, ethyl ester, etc.) in place of the polybasic acid in the esterification reaction. . The transesterification reaction of both components can be performed by a known method.
上記オイルフリーポリエステル樹脂において、二塩基酸成分のうち、芳香族ジカルボン酸の占める割合が８０〜１００モル％、且つそのうち、テレフタル酸の占める割合が４０〜１００モル％であることが好ましい。 In the oil-free polyester resin, it is preferable that the proportion of the aromatic dicarboxylic acid in the dibasic acid component is 80 to 100 mol%, and the proportion of terephthalic acid is 40 to 100 mol%.
アルキド樹脂は、上記オイルフリーポリエステル樹脂の酸成分及びアルコール成分に加えて、油脂肪酸を公知の方法で反応せしめたものであって、油脂肪酸としては、例えばヤシ油脂肪酸、大豆油脂肪酸、アマニ油脂肪酸、サフラワー油脂肪酸、トール油脂肪酸、脱水ヒマシ油脂肪酸、キリ油脂肪酸などを挙げることができる。 The alkyd resin is obtained by reacting an oil fatty acid with a known method in addition to the acid component and the alcohol component of the oil-free polyester resin. Examples of the oil fatty acid include coconut oil fatty acid, soybean oil fatty acid, and linseed oil. Examples include fatty acids, safflower oil fatty acids, tall oil fatty acids, dehydrated castor oil fatty acids, and kiri oil fatty acids.
ウレタン変性ポリエステル樹脂は、上記オイルフリーポリエステル樹脂、又は上記オイルフリーポリエステル樹脂の製造の際の、酸成分及びアルコール成分を反応させて得られる低分子量のオイルフリーポリエステル樹脂を、ポリイソシアネート化合物と公知の方法で反応せしめたものである。ウレタン変性アルキド樹脂は、上記アルキド樹脂、又は上記アルキド樹脂製造の際の各成分を反応させて得られる低分子量のアルキド樹脂を、ポリイソシアネート化合物と公知の方法で反応せしめたものである。ウレタン変性ポリエステル樹脂、ウレタン変性アルキド樹脂を製造する際に使用するポリイソシアネート化合物としては、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、トリレンジイソシアネート、４，４´−ジフェニルメタンジイソシアネート、４，４´−メチレンビス（シクロヘキシルイソシアネート）、２，４，６トリイソシアナトトルエンなどが挙げられる。 The urethane-modified polyester resin is a known low-molecular-weight oil-free polyester resin obtained by reacting an acid component and an alcohol component in the production of the oil-free polyester resin or the oil-free polyester resin. It was made to react by the method. The urethane-modified alkyd resin is obtained by reacting the alkyd resin or a low molecular weight alkyd resin obtained by reacting each component in the production of the alkyd resin with a polyisocyanate compound by a known method. Examples of the polyisocyanate compound used for producing the urethane-modified polyester resin and the urethane-modified alkyd resin include hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'- Examples include methylene bis (cyclohexyl isocyanate) and 2,4,6 triisocyanatotoluene.
本発明において、ポリエステル樹脂（Ａ）は、ガラス転移温度（以下、「Ｔｇ点」と略称することがある）が７０℃を超え、且つ１００℃以下であり、特に７５〜９０℃の範囲内であることが好ましい。 In the present invention, the polyester resin (A) has a glass transition temperature (hereinafter sometimes abbreviated as “Tg point”) of more than 70 ° C. and 100 ° C. or less, particularly in the range of 75 to 90 ° C. Preferably there is.
また、数平均分子量は３，０００〜１００，０００、特に８，０００〜５，００００、さらに特に１０，０００〜３０，０００であることが好ましく、水酸基価は０．５〜４０ｍｇＫＯＨ／ｇ、特に３〜２０ｍｇＫＯＨ／ｇであることが好ましく、酸価が２０ｍｇＫＯＨ／ｇ以下、好ましくは０．１〜１０ｍｇＫＯＨ／ｇであることが、ポリエステル樹脂の取扱い易さ、得られる塗膜の加工性、硬度、耐水性、耐沸騰水性などの点から好適である。 The number average molecular weight is preferably 3,000 to 100,000, particularly 8,000 to 50,000, more preferably 10,000 to 30,000, and the hydroxyl value is preferably 0.5 to 40 mgKOH / g, particularly It is preferably 3 to 20 mgKOH / g, and an acid value of 20 mgKOH / g or less, preferably 0.1 to 10 mgKOH / g, is easy to handle the polyester resin, workability of the resulting coating film, hardness, It is suitable from the viewpoints of water resistance, boiling water resistance and the like.
本発明明細書において、Ｔｇ点の測定は、示差走査熱量計を用いた示差熱分析（ＤＳＣ）によるものであり、また数平均分子量は、下記分子量測定方法によりゲル浸透クロマトグラフィ（ＧＰＣ）により、標準ポリスチレンの検量線を用いて測定したものである。 In the present specification, the Tg point is measured by differential thermal analysis (DSC) using a differential scanning calorimeter, and the number average molecular weight is measured by gel permeation chromatography (GPC) by the following molecular weight measurement method. It is measured using a calibration curve of polystyrene.
（分子量測定方法）
数平均分子量は、溶媒としてテトラヒドロフランを使用し、ゲルパーミエーションクロマトグラフ（東ソー（株）社製、「ＨＬＣ８１２０ＧＰＣ」）で測定した保持時間（保持容量）を、ポリスチレンの数平均分子量を基準にして換算した値である。カラムは、「ＴＳＫｇｅｌ Ｇ−４０００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ−３０００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ−２５００ＨＸＬ」、「ＴＳＫｇｅｌ Ｇ−２０００ＸＬ」（いずれも東ソー（株）社製、商品名）の４本を用い、移動相；テトラヒドロフラン、測定温度；４０℃、流速；１ｍｌ／分、検出器；ＲＩの条件で行ったものである。
(Molecular weight measurement method)
The number average molecular weight is converted from the retention time (retention capacity) measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent, based on the number average molecular weight of polystyrene. It is the value. The column used was “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL”, “TSKgel G-2000XL” (both manufactured by Tosoh Corporation, trade name), and moved. Phase: Tetrahydrofuran, Measurement temperature: 40 ° C., Flow rate: 1 ml / min, Detector: Under the conditions of RI.
ポリエステル樹脂（Ｂ）
本発明の塗料組成物に用いるポリエステル樹脂（Ｂ）は、ガラス転移温度（Ｔｇ）が４０℃〜７０℃の範囲であり、特に４５〜６５℃の範囲であることが好ましい。また、数平均分子量は３，０００〜１００，０００、特に８，０００〜５，００００、さらに特に１０，０００〜３０，０００の範囲内であることが好ましく、水酸基価は０．５〜４０ｍｇＫＯＨ／ｇ、特に３〜２０ｍｇＫＯＨ／ｇであることが好ましく、酸価は２０ｍｇＫＯＨ／ｇ以下、好ましくは０．１〜１０ｍｇＫＯＨ／ｇの範囲にあることが好ましい。
Polyester resin (B)
The polyester resin (B) used in the coating composition of the present invention has a glass transition temperature (Tg) in the range of 40 ° C to 70 ° C, and particularly preferably in the range of 45 to 65 ° C. The number average molecular weight is preferably in the range of 3,000 to 100,000, particularly 8,000 to 50,000, more preferably 10,000 to 30,000, and the hydroxyl value is 0.5 to 40 mgKOH / g, particularly 3 to 20 mgKOH / g, and the acid value is preferably 20 mgKOH / g or less, preferably 0.1 to 10 mgKOH / g.
ポリエステル樹脂（Ｂ）は、Ｔｇ点が上記範囲にあることが重要であり、上記範囲より大きい場合、十分な加工性が得られなくなる虞がある。また、上記範囲より小さい場合、本発明塗料組成物を缶内面塗料として使用した場合に、例えば、７０〜８０℃の高温貯蔵での缶内容物による腐食に対する耐性が充分ではなく、また、耐食性、耐ブロッキング性、耐レトルト性が不十分となることがある。数平均分子量が上記範囲にあることが加工性、塗装性の面から好適であり、水酸基価及び酸価が上記範囲にあることが硬化性、塗膜の耐水性などの観点から好適である。 It is important that the polyester resin (B) has a Tg point in the above range. If the polyester resin (B) is larger than the above range, sufficient processability may not be obtained. Further, when the coating composition of the present invention is used as a can inner surface paint when it is smaller than the above range, for example, the resistance to corrosion by the can contents at high temperature storage at 70 to 80 ° C. is not sufficient, and the corrosion resistance, Blocking resistance and retort resistance may be insufficient. The number average molecular weight is preferably in the above range from the viewpoints of processability and paintability, and the hydroxyl value and acid value are preferably in the above ranges from the viewpoints of curability and water resistance of the coating film.
ポリエステル樹脂（Ｂ）としては、種々の多塩基酸などの酸成分及び多価アルコールなどのアルコール成分からなるポリエステル樹脂を用いることができ、酸成分及びアルコール成分としては、ポリエステル樹脂（Ａ）について例示した多塩基酸などの酸成分及び多価アルコールなどのアルコール成分を用いることができる。 As the polyester resin (B), it is possible to use a polyester resin comprising an acid component such as various polybasic acids and an alcohol component such as a polyhydric alcohol. Examples of the acid component and alcohol component include the polyester resin (A). An acid component such as a polybasic acid and an alcohol component such as a polyhydric alcohol can be used.
レゾール型フェノール樹脂架橋剤（Ｃ）
本発明組成物における（Ｃ）成分であるレゾール型フェノール樹脂架橋剤は、上記ポリエステル樹脂（Ａ）及びポリエステル樹脂（Ｂ）と架橋反応して硬化させるために配合されるものである。
Resol type phenolic resin crosslinking agent (C)
The resol type phenolic resin crosslinking agent which is the component (C) in the composition of the present invention is blended for crosslinking and curing with the polyester resin (A) and the polyester resin (B).
本発明におけるフェノール樹脂架橋剤（Ｃ）は、フェノール成分とホルムアルデヒド類とを反応触媒の存在下で加熱して縮合反応させてメチロール基を導入して得られるメチロール化フェノール樹脂のメチロール基の一部をアルコールでアルキルエーテル化してなるレゾール型フェノール樹脂である。 The phenol resin cross-linking agent (C) in the present invention is a part of the methylol group of the methylolated phenol resin obtained by introducing a methylol group by heating and condensing a phenol component and formaldehyde in the presence of a reaction catalyst. It is a resol type phenol resin obtained by alkylating ether with alcohol.
レゾール型フェノール樹脂架橋剤（Ｃ）の製造においては、出発原料である上記フェノール成分として、３官能以上のフェノール化合物を５０重量％以上、好ましくは７０重量％以上、さらに好ましくは１００重量％含有するフェノール成分が用いられる。このフェノール樹脂架橋剤（Ｃ）は反応性に優れる。このフェノール樹脂架橋剤（Ｃ）と、ポリエステル樹脂（Ａ）と、上記ポリエステル樹脂（Ｂ）とを所定量組合せた塗料組成物とすることにより特に薄膜における腐食液に対する耐食性にも優れた塗膜を得ることができる。 In the production of the resol type phenol resin crosslinking agent (C), the phenol component as the starting material contains a trifunctional or higher functional phenol compound in an amount of 50% by weight or more, preferably 70% by weight or more, more preferably 100% by weight. A phenol component is used. This phenol resin cross-linking agent (C) is excellent in reactivity. By forming a coating composition in which a predetermined amount of the phenol resin cross-linking agent (C), the polyester resin (A), and the polyester resin (B) is combined, a coating film having excellent corrosion resistance against a corrosive liquid particularly in a thin film. Can be obtained.
レゾール型フェノール樹脂架橋剤（Ｃ）の製造に用いられる３官能以上のフェノール化合物としては、フェノール、ｍ−クレゾール、ｍ−エチルフェノール、３，５−キシレノール、ｍ−メトキシフェノール等の３官能性フェノール；ビスフェノールＡ、ビスフェノールＦ等の４官能性フェノール等が挙げられ、これらは１種で、又は２種以上混合して使用することができる。上記ビスフェノールＡは、環境ホルモンの疑いがある観点から好ましくない場合がある。 Trifunctional phenols used in the production of the resol type phenol resin crosslinking agent (C) include trifunctional phenols such as phenol, m-cresol, m-ethylphenol, 3,5-xylenol, and m-methoxyphenol. Tetrafunctional phenols such as bisphenol A and bisphenol F, and the like, and these may be used alone or in combination of two or more. The bisphenol A may not be preferable from the viewpoint of suspected environmental hormones.
上記出発原料であるフェノール成分として、上記３官能以上のフェノール化合物に加えて、フェノール成分中に５０重量％以下の量含有してもよいフェノール化合物としては、ｏ−クレゾール、ｐ−クレゾール、ｐ−tert−ブチルフェノール、ｐ−エチルフェノール、２，３−キシレノール、２，５−キシレノールなどの２官能性フェノールなどを挙げることができる。 As the phenol component as the starting material, in addition to the trifunctional or higher functional phenol compound, the phenol component which may be contained in the phenol component in an amount of 50% by weight or less includes o-cresol, p-cresol, p- Bifunctional phenols such as tert-butylphenol, p-ethylphenol, 2,3-xylenol and 2,5-xylenol can be exemplified.
レゾール型フェノール樹脂架橋剤（Ｃ）の製造に用いられるホルムアルデヒド類としては、ホルムアルデヒド、パラホルムアルデヒド又はトリオキサンなどが挙げられ、１種で、又は２種以上混合して使用することができる。 Examples of the formaldehydes used in the production of the resol type phenol resin crosslinking agent (C) include formaldehyde, paraformaldehyde, or trioxane, and these can be used alone or in combination of two or more.
メチロール化フェノール樹脂のメチロール基の一部をアルキルエーテル化するのに用いられるアルコールとしては、炭素原子数１〜８個、好ましくは１〜４個の１価アルコールを好適に使用することができる。好適な１価アルコールとしてはメタノール、エタノール、ｎ−プロパノール、ｎ−ブタノール、イソブタノールなどを挙げることができる。 As the alcohol used for alkyl etherifying a part of the methylol group of the methylolated phenol resin, a monohydric alcohol having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, can be suitably used. Suitable monohydric alcohols include methanol, ethanol, n-propanol, n-butanol, isobutanol and the like.
レゾール型フェノール樹脂架橋剤（Ｃ）は、ポリエステル樹脂（Ａ）及びポリエステル樹脂（Ｂ）との反応性などの点からベンゼン核１核当り平均してアルコキシメチル基とメチロール基との合計が０．８〜２．５個であることがより好ましい。 The resol type phenolic resin cross-linking agent (C) has an average of an alkoxymethyl group and a methylol group of 0.1 per benzene nucleus in terms of reactivity with the polyester resin (A) and the polyester resin (B). More preferably, the number is 8 to 2.5.
酸硬化触媒（Ｄ）
本発明組成物における（Ｄ）成分である酸硬化触媒は、本発明組成物の硬化反応を促進するものであり、例えば、パラ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スルホン酸、ジノニルナフタレンジスルホン酸、燐酸などの酸又はこれらの酸のアミン中和物などを具体例として挙げることができる。なかでも上記スルホン酸化合物又はスルホン酸化合物のアミン中和物が好適である。
Acid curing catalyst (D)
The acid curing catalyst as component (D) in the composition of the present invention accelerates the curing reaction of the composition of the present invention. For example, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonyl Specific examples include acids such as naphthalenedisulfonic acid and phosphoric acid or neutralized amines of these acids. Among these, the sulfonic acid compound or an amine neutralized product of the sulfonic acid compound is preferable.
酸硬化触媒を配合することによって本発明組成物から得られる塗膜の硬化性、フレーバー性を向上させることができ、また鮮映性を向上させることもできる。 By blending the acid curing catalyst, the curability and flavor of the coating film obtained from the composition of the present invention can be improved, and the sharpness can also be improved.
本発明塗料組成物
本発明塗料組成物は、前述したポリエステル樹脂（Ａ）、ポリエステル樹脂（Ｂ）、レゾール型フェノール樹脂架橋剤（Ｃ）及び酸硬化触媒（Ｄ）を下記配合割合にて含有するものである。
This invention coating composition This invention coating composition contains the polyester resin (A), polyester resin (B), resol type phenol resin crosslinking agent (C), and acid curing catalyst (D) which were mentioned above in the following compounding ratio. Is.
前記ポリエステル樹脂（Ａ）と上記ポリエステル樹脂（Ｂ）との配合割合は、〔（Ａ）／（Ｂ）〕の固形分質量比で４０／６０〜５／９５であり、好ましくは３５／６５〜１０／９０である。ポリエステル樹脂（Ａ）の上記配合割合が４０を超えると塗膜の加工性が低下し、また５未満となると缶内面塗料として使用した場合に薄膜での缶内容物による腐食に対する耐性が劣り、また耐ブロッキング性が低下する虞があり、実用上問題となる場合がある。 The blending ratio of the polyester resin (A) and the polyester resin (B) is 40/60 to 5/95, preferably 35/65 to [(A) / (B)] in the solid content mass ratio. 10/90. When the blending ratio of the polyester resin (A) exceeds 40, the processability of the coating film decreases, and when it is less than 5, when used as a can inner surface paint, the resistance to corrosion by the can contents in the thin film is inferior. There is a possibility that the blocking resistance may be lowered, which may cause a practical problem.
本発明組成物におけるレゾール型フェノール樹脂架橋剤（Ｃ）の配合割合は、ポリエステル樹脂（Ａ）及びポリエステル樹脂（Ｂ）のポリエステル樹脂混合物１００質量部に対し、１〜２０質量部、好ましくは１〜１５質量部、さらに好ましくは２〜１３質量部の範囲内である。上記範囲内にあることが、得られる塗膜の硬化性、耐水性、塗膜硬度、可撓性などの点から好適である。 The blending ratio of the resol type phenol resin crosslinking agent (C) in the composition of the present invention is 1 to 20 parts by mass, preferably 1 to 100 parts by mass with respect to 100 parts by mass of the polyester resin (A) and the polyester resin (B). It is 15 mass parts, More preferably, it exists in the range of 2-13 mass parts. It exists in the said range from points, such as sclerosis | hardenability of a coating film obtained, water resistance, coating-film hardness, and flexibility.
本発明組成物における酸硬化触媒（Ｄ）の配合割合は、ポリエステル樹脂（Ａ）及びポリエステル樹脂（Ｂ）のポリエステル樹脂混合物１００質量部に対し、酸量（例えば、スルホン酸化合物のアミン中和物の場合は、この中和物からアミンを除去した残りのスルホン酸化合物量）として０．１〜５質量部、好ましくは０．２〜２質量部の範囲内であることが好適である。上記範囲内にあることが、得られる塗膜の硬化性、フレーバー性、塗料の貯蔵安定性などの点から好適である。 The blending ratio of the acid curing catalyst (D) in the composition of the present invention is an acid amount (for example, an amine neutralized product of a sulfonic acid compound) with respect to 100 parts by mass of the polyester resin mixture of the polyester resin (A) and the polyester resin (B). In this case, the amount of the remaining sulfonic acid compound obtained by removing the amine from the neutralized product is 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass. It is suitable from the point of sclerosis | hardenability of the coating film obtained, flavor property, the storage stability of a coating material, etc. to exist in the said range.
本発明塗料組成物には、上記ポリエステル樹脂（Ａ）、ポリエステル樹脂（Ｂ）、レゾール型フェノール樹脂架橋剤（Ｃ）及び酸硬化触媒（Ｄ）に加えて、さらに潤滑性付与剤、溶剤、塗膜改質用樹脂；顔料；凝集防止剤、消泡剤、レベリング剤などの塗料用添加剤を適宜配合することができる。 In addition to the polyester resin (A), polyester resin (B), resol type phenol resin cross-linking agent (C) and acid curing catalyst (D), the coating composition of the present invention further comprises a lubricity-imparting agent, solvent, coating Film modifying resins; pigments; additives for paints such as anti-agglomeration agents, antifoaming agents, leveling agents and the like can be appropriately blended.
上記潤滑性付与剤は、得られる塗膜の潤滑性を向上させる目的で配合されるものであり、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及びカルナウバワックスなどを挙げることができる。潤滑性付与剤は、１種で又は２種以上を混合して使用することができる。 The lubricity imparting agent is blended for the purpose of improving the lubricity of the resulting coating film. For example, a fatty acid ester wax that is an esterified product of a polyol compound and a fatty acid, a silicon wax, a fluorine wax, Examples thereof include polyolefin waxes such as polyethylene, lanolin wax, montan wax, microcrystalline wax, and carnauba wax. The lubricity-imparting agent can be used alone or in combination of two or more.
本発明組成物中に潤滑性付与剤を適当量配合することによって、該組成物から得られる塗膜表面に滑り性を付与することができ、塗面の摩擦抵抗が小さくなり、成型加工性が向上し加工後における耐食性も向上する。潤滑性付与剤の配合量は、塗膜の柔軟性、滑り性などに基づく成型加工性、耐食性などの点からポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）との合計固形分量１００質量部に対して、０．１〜５質量部、好ましくは０．２〜３質量部の範囲内であることが好適である。 By blending an appropriate amount of a lubricity-imparting agent in the composition of the present invention, slipperiness can be imparted to the coating surface obtained from the composition, the frictional resistance of the coated surface is reduced, and molding processability is reduced. Improves corrosion resistance after processing. The blending amount of the lubricity-imparting agent is based on 100 parts by mass of the total solid content of the polyester resin (A) and the polyester resin (B) in terms of molding processability and corrosion resistance based on the flexibility and slipperiness of the coating film. In the range of 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass.
本発明組成物には、塗装性の観点などから、通常、溶剤が配合される。上記溶剤としては、上記成分（Ａ）、（Ｂ）、（Ｃ）などの各成分を溶解ないし分散できるものが使用でき、具体的には、例えば、トルエン、キシレン、高沸点石油系炭化水素などの炭化水素系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロンなどのケトン系溶剤、酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテートなどのエステル系溶剤、メタノール、エタノール、ブタノールなどのアルコール系溶剤、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ブチルエーテル、ジエチレングリコールモノブチルエーテルなどのエーテルアルコール系溶剤などを挙げることができ、これらは単独で、あるいは２種以上を混合して使用することができる。 The composition of the present invention is usually mixed with a solvent from the viewpoint of paintability. As said solvent, what can melt | dissolve or disperse | distribute each component, such as said component (A), (B), (C), can be used, Specifically, for example, toluene, xylene, a high boiling point petroleum hydrocarbon etc. Hydrocarbon solvents, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, methanol, ethanol, butanol And alcohol solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and the like. It can be used as a mixture of at least.
本発明組成物に配合できる上記塗膜改質用樹脂としては、例えば、アミノ樹脂硬化剤、エチレン−重合性不飽和カルボン酸共重合体及びエチレン−重合性不飽和カルボン酸共重合体アイオノマーなどを挙げることができる。 Examples of the coating film modifying resin that can be blended in the composition of the present invention include amino resin curing agents, ethylene-polymerizable unsaturated carboxylic acid copolymers, and ethylene-polymerizable unsaturated carboxylic acid copolymer ionomers. Can be mentioned.
上記アミノ樹脂硬化剤は、塗料組成物の硬化性向上、得られる塗膜の硬度向上、密着性の向上などを目的に配合されるものである。アミノ樹脂硬化剤は、ホルムアルデヒド、アセトアルデヒド、クロトンアルデヒド及びベンズアルデヒドのようなアルデヒドと、尿素、メラミン及びベンゾグアナミンのようなアミノ又はアミド基含有物質との縮合生成物であり、アルコールによってアルキルエーテル化されていてもよい。有用なアルコールは、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、ベンジルアルコール、シクロヘキサノール及びエトキシエタノールのような一価アルコールを包含する。アミノ樹脂硬化剤の例としては、ベンゾグアナミン−ホルムアルデヒド樹脂、メラミン−ホルムアルデヒド樹脂、尿素−ホルムアルデヒド樹脂などを挙げることができる。 The amino resin curing agent is blended for the purpose of improving the curability of the coating composition, improving the hardness of the resulting coating film, and improving adhesion. Amino resin curing agents are condensation products of aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde and benzaldehyde with amino or amide group containing materials such as urea, melamine and benzoguanamine, which are alkyl etherified with alcohols. Also good. Useful alcohols include monohydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, benzyl alcohol, cyclohexanol and ethoxyethanol. Examples of amino resin curing agents include benzoguanamine-formaldehyde resin, melamine-formaldehyde resin, urea-formaldehyde resin, and the like.
アミノ樹脂硬化剤を配合する場合、その配合量は、ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）との合計固形分量１００質量部に対して、０．１〜１０質量部、好ましくは０．２〜７質量部の範囲内であることが好適である。 When mix | blending an amino resin hardening | curing agent, the compounding quantity is 0.1-10 mass parts with respect to 100 mass parts of total solid content of a polyester resin (A) and a polyester resin (B), Preferably it is 0.2. It is suitable to be within a range of ˜7 parts by mass.
上記エチレン−重合性不飽和カルボン酸共重合体及びエチレン−重合性カルボン不飽和酸共重合体アイオノマーは、塗膜の可撓性を改良することなどを目的に配合することができる。 The ethylene-polymerizable unsaturated carboxylic acid copolymer and the ethylene-polymerizable carboxylic unsaturated acid copolymer ionomer can be blended for the purpose of improving the flexibility of the coating film.
本発明組成物に配合できる顔料としては、塗料分野において公知の着色顔料（例えば、チタン白）、体質顔料などを使用することができる。 As a pigment that can be blended in the composition of the present invention, a known color pigment (for example, titanium white), extender pigment, and the like in the paint field can be used.
本発明組成物は、例えば、金属板、金属缶、プラスチックス、ガラス板などの種々の被塗物に塗装することができる。 The composition of the present invention can be applied to various objects such as metal plates, metal cans, plastics and glass plates.
塗装金属板
本発明の塗装金属板は、本発明の塗料組成物を金属板に塗装することにより得られる。
Painted metal plate The coated metal plate of the present invention can be obtained by coating the metal plate with the coating composition of the present invention.
上記金属板としては、例えば、熱延鋼板、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、必要に応じて各種表面処理、プライマー塗装が施されたものが使用される。 Examples of the metal plate include hot rolled steel plate, cold rolled steel plate, hot dip galvanized steel plate, electrogalvanized steel plate, alloy plated steel plate, aluminum zinc alloy plated steel plate, aluminum plate, tin plated steel plate, 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. are used, and those with various surface treatments and primer coating are used as necessary.
塗装金属板を缶に加工して用いる場合、その金属板としては、飲料缶、缶詰用缶、蓋、キャップに用いることができる金属板であればいずれも使用することができ、例えばアルミニウム板、ティンフリースチール板、ブリキ板等を挙げることができる。 When processing a coated metal plate into a can, the metal plate can be any metal plate that can be used for beverage cans, cans for cans, lids, caps, such as aluminum plates, Examples include tin-free steel plates and tin plates.
本発明の塗装金属板は、本発明の塗料組成物を、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、連続焼付け炉等の加熱手段によって焼き付けることにより得ることができる。焼付条件は特に制限されるものではないが、例えば、素材到達最高温度が、９０℃〜３００℃、好ましくは１８０℃〜２６０℃となる条件で５秒〜３０分間、好ましくは８〜６０秒間焼付けることが適している。 The coated metal plate of the present invention can be obtained by coating the coating composition of the present invention on a metal plate by a known coating method such as roll coater coating or spray coating, and baking it by a heating means such as a continuous baking furnace. . Although the baking conditions are not particularly limited, for example, baking is performed for 5 to 30 minutes, preferably 8 to 60 seconds under the condition that the maximum material arrival temperature is 90 ° C to 300 ° C, preferably 180 ° C to 260 ° C. It is suitable to attach.
塗装金属板における塗膜厚は特に限定されるものではないが、乾燥膜厚で３〜１８μｍ、更には３〜１２μｍの範囲であることが好ましい。乾燥膜厚は塗装金属板の用途により適宜決めることができる。
塗装金属缶
本発明の塗装金属缶は、金属缶の少なくとも缶胴もしくは缶蓋の内面及び／又は外面に本発明の塗料組成物による塗膜が形成されてなるものであり、本発明の塗料組成物は、特に密着性、フレーバー性、及び缶内面塗料として使用した場合に薄膜においても缶内容物による腐食に対する耐性等に優れているので、金属缶の少なくとも内面に本発明の塗料組成物による硬化塗膜が形成されていることが望ましい。
Although the coating film thickness in a coating metal plate is not specifically limited, It is preferable that it is the range of 3-18 micrometers by dry film thickness, Furthermore, it is the range of 3-12 micrometers. The dry film thickness can be appropriately determined depending on the use of the coated metal plate.
Painted metal can The coated metal can of the present invention is formed by forming a coating film of the present invention on at least the inner surface and / or the outer surface of the can body or the lid of the metal can. Since the product is particularly excellent in adhesion, flavor, and resistance to corrosion by the can contents even in a thin film when used as a can inner surface paint, it is cured on at least the inner surface of the metal can by the coating composition of the present invention. It is desirable that a coating film is formed.
本発明の塗装金属缶は、前述した塗装金属板から金属缶を成形することもできるが、予め成形された金属容器に本発明の塗料組成物を塗装、硬化して硬化塗膜を形成することによって得ることもできる。 The coated metal can of the present invention can be formed from the aforementioned coated metal plate, but the coated composition of the present invention is applied to a previously formed metal container and cured to form a cured coating film. Can also be obtained.
硬化塗膜を形成する金属容器としては、従来公知の金属缶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、ツーピース缶の例えば、缶胴等を挙げることができる。 As the metal container for forming the cured coating film, all conventionally known metal cans can be used, but are not limited thereto, and examples thereof include a three-piece can having a side seam, a two-piece can, and the like.
上記缶蓋は、前述した本発明の塗装金属板から、従来公知の任意の製蓋法によって成形することができる。一般的には、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として成形される。 The said can lid can be shape | molded by the conventionally well-known arbitrary lid making methods from the coating metal plate of this invention mentioned above. Generally, it is formed as a stay-on-tab type easy open can lid or a full open type easy open can lid.
以下、製造例、実施例によって本発明をより具体的に説明する。本発明は下記の実施例に限定されるものではない。なお、以下、「部」および「％」はいずれも質量基準によるものである。 Hereinafter, the present invention will be described more specifically with reference to production examples and examples. The present invention is not limited to the following examples. Hereinafter, “parts” and “%” are based on mass.
ポリエステル樹脂（Ａ）の製造
製造例１
テレフタル酸２６６０部、トリメリット酸１５．５部、プロピレングリコール２４５０部、１，４−シクロヘキサンジメタノール３５０部、チタンテトラブトキシド１．８部を１０Ｌオートクレーブに仕込み、３．５Ｋｇ／ｃｍ・Ｇの窒素加圧下で３時間かけて２３５℃まで徐々に昇温し、エステル化を行った。次いで、１時間かけて１０ｍｍＨｇまで減圧重合を行うと共に温度を２５０℃まで昇温し、さらにこのまま１ｍｍＨｇ以下で９０分間後期重合を行ない、数平均分子量１５，０００、水酸基価３ｍｇＫＯＨ／ｇ、酸価１ｍｇＫＯＨ／ｇ、Ｔｇ点８９℃のポリエステル樹脂を得た。得られた樹脂をメチルエチルケトン／シクロヘキサノン＝５０／５０（重量比）の混合溶剤にて希釈して固形分３０％のポリエステル樹脂（Ａ−１）溶液を得た。
Production Example 1 of Polyester Resin (A)
2660 parts of terephthalic acid, 15.5 parts of trimellitic acid, 2450 parts of propylene glycol, 350 parts of 1,4-cyclohexanedimethanol, and 1.8 parts of titanium tetrabutoxide are charged into a 10 L autoclave and 3.5 kg / cm · G of nitrogen Esterification was carried out by gradually raising the temperature to 235 ° C. over 3 hours under pressure. Next, the polymerization was carried out under reduced pressure to 10 mmHg over 1 hour and the temperature was raised to 250 ° C., and then the latter polymerization was carried out for 90 minutes at 1 mmHg or less, and the number average molecular weight 15,000, hydroxyl value 3 mgKOH / g, acid value 1 mgKOH / G, a polyester resin having a Tg point of 89 ° C. was obtained. The obtained resin was diluted with a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 (weight ratio) to obtain a polyester resin (A-1) solution having a solid content of 30%.
製造例２
フタル酸３７．７部、イソフタル酸６６．４部、ヘキサヒドロフタル酸４６．２部、トリメリット酸６．７部、エチレングリコール１２．４部、ネオペンチルグリコール７８．８部、トリメチロールプロパン６．８部及び重縮合触媒を仕込み、加熱、撹拌し、生成する水を除去しながらエステル化反応を行い、数平均分子量１５，０００、水酸基価５ｍｇＫＯＨ／ｇ、酸価２ｍｇＫＯＨ／ｇ、Ｔｇ点８０℃ の樹脂を得た。得られた樹脂をメチルエチルケトン／シクロヘキサノン＝５０／５０の混合溶剤にて希釈し固形分３０％のポリエステル樹脂（Ａ−２）溶液を得た。
Production Example 2
37.7 parts of phthalic acid, 66.4 parts of isophthalic acid, 46.2 parts of hexahydrophthalic acid, 6.7 parts of trimellitic acid, 12.4 parts of ethylene glycol, 78.8 parts of neopentyl glycol, trimethylolpropane 6 .8 parts and a polycondensation catalyst were charged, heated and stirred, and the esterification reaction was carried out while removing the generated water. The number average molecular weight was 15,000, the hydroxyl value was 5 mgKOH / g, the acid value was 2 mgKOH / g, and the Tg point was 80. A resin at ℃ was obtained. The obtained resin was diluted with a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 to obtain a polyester resin (A-2) solution having a solid content of 30%.
製造例３
テレフタル酸１６６部、シクロヘキサンジメタノール２８．８部、１，２−プロピレングリコール４５．６部、エチレングリコール１２．４部、トリメチロールプロパン１．３４部及び重縮合触媒を仕込み、加熱、撹拌し、生成する水を除去しながらエステル化反応を行い、数平均分子量１３，０００、水酸基価１６ｍｇＫＯＨ／ｇ、酸価２ｍｇＫＯＨ／ｇ、Ｔｇ点７３℃の樹脂を得た。得られた樹脂をメチルエチルケトン／シクロヘキサノン＝５０／５０の混合溶剤にて希釈し固形分３０％のポリエステル樹脂（Ａ−３）溶液を得た。
Production Example 3
166 parts of terephthalic acid, 28.8 parts of cyclohexanedimethanol, 45.6 parts of 1,2-propylene glycol, 12.4 parts of ethylene glycol, 1.34 parts of trimethylolpropane and a polycondensation catalyst were added, heated and stirred. An esterification reaction was carried out while removing the generated water to obtain a resin having a number average molecular weight of 13,000, a hydroxyl value of 16 mgKOH / g, an acid value of 2 mgKOH / g, and a Tg point of 73 ° C. The obtained resin was diluted with a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 to obtain a polyester resin (A-3) solution having a solid content of 30%.
製造例４ （比較用）
エボニック社製のポリエステル樹脂「ＤＹＮＡＰＯＬ Ｌ９１２」（数平均分子量１５，０００、水酸基価５ｍｇＫＯＨ／ｇ、酸価３ｍｇＫＯＨ／ｇ以下、Ｔｇ点１０５℃）をメチルエチルケトン／シクロヘキサノン＝５０／５０（重量比）の混合溶剤にて希釈して固形分３０％のポリエステル樹脂（ＡＣ−４）溶液を得た。
Production Example 4 (for comparison)
Polyester resin “DYNAPOL L912” manufactured by Evonik Co., Ltd. (number average molecular weight 15,000, hydroxyl value 5 mgKOH / g, acid value 3 mgKOH / g or less, Tg point 105 ° C.) mixed with methyl ethyl ketone / cyclohexanone = 50/50 (weight ratio) Dilution with a solvent gave a polyester resin (AC-4) solution having a solid content of 30%.
ポリエステル樹脂（Ｂ）の製造
製造例５
テレフタル酸４９．８部、イソフタル酸４９．８部、ヘキサヒドロテレフタル酸３４．４部、アジピン酸２８．３部、ネオペンチルグリコール９９．８部、トリメチロールプロパン６．８部及び重縮合触媒を仕込み、加熱、撹拌して生成する水を除去しながらエステル化反応を行い、数平均分子量２４，０００、水酸基価１０ｍｇＫＯＨ／ｇ、酸価０．５ｍｇＫＯＨ／ｇ、Ｔｇ点６０℃の樹脂を得た。得られた樹脂をメチルエチルケトン／シクロヘキサノン＝５０／５０（質量比）の混合溶剤にて希釈して固形分３０％のポリエステル樹脂（Ｂ−１）溶液を得た。
Production Example 5 of Polyester Resin (B)
49.8 parts of terephthalic acid, 49.8 parts of isophthalic acid, 34.4 parts of hexahydroterephthalic acid, 28.3 parts of adipic acid, 99.8 parts of neopentyl glycol, 6.8 parts of trimethylolpropane and a polycondensation catalyst The esterification reaction was carried out while removing water generated by charging, heating and stirring to obtain a resin having a number average molecular weight of 24,000, a hydroxyl value of 10 mgKOH / g, an acid value of 0.5 mgKOH / g, and a Tg point of 60 ° C. . The obtained resin was diluted with a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 (mass ratio) to obtain a polyester resin (B-1) solution having a solid content of 30%.
製造例６
反応容器にジメチルテレフタレート３２０部、ジメチルイソフタレート８０部、プロピレングリコール２６１部１，４−ブタンジオール１０４部、及び酢酸マグネシウム０．１８部、テトラ−ｎ−ブチルチタネート０．２９部を加え徐々に昇温し、反応温度が２２０℃になるまで４時間反応を続けた。次いでトリフェニルフォスファイト０．１４部を加えて反応温度を２５０℃まで昇温し、反応系を徐々に減圧した後０．５ｍｍＨｇ以下の減圧下で４時間反応を行い、数平均分子量１９，０００、水酸基価３ｍｇＫＯＨ／ｇ、酸価２ｍｇＫＯＨ／ｇ、Ｔｇ点５２℃の樹脂を得た。得られた樹脂をメチルエチルケトン／シクロヘキサノン＝５０／５０（質量比）の混合溶剤にて希釈して固形分３０％のポリエステル樹脂（Ｂ−２）溶液を得た。
Production Example 6
To the reaction vessel was added 320 parts of dimethyl terephthalate, 80 parts of dimethyl isophthalate, 261 parts of propylene glycol, 104 parts of 1,4-butanediol, 0.18 parts of magnesium acetate, and 0.29 parts of tetra-n-butyl titanate. The reaction was continued for 4 hours until the reaction temperature reached 220 ° C. Next, 0.14 part of triphenyl phosphite was added, the reaction temperature was raised to 250 ° C., the pressure of the reaction system was gradually reduced, and the reaction was carried out for 4 hours under a reduced pressure of 0.5 mmHg or less. A resin having a hydroxyl value of 3 mgKOH / g, an acid value of 2 mgKOH / g, and a Tg point of 52 ° C. was obtained. The obtained resin was diluted with a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 (mass ratio) to obtain a polyester resin (B-2) solution having a solid content of 30%.
製造例７
東洋紡績（株）製のポリエステル樹脂「バイロン１０３」（数平均分子量２２，０００、水酸基価５ｍｇＫＯＨ／ｇ、酸価２ｍｇＫＯＨ／ｇ以下、Ｔｇ点４５℃）をメチルエチルケトン／シクロヘキサノン＝５０／５０（重量比）の混合溶剤にて希釈して固形分３０％のポリエステル樹脂（Ｂ−３）溶液を得た。
Production Example 7
Polyester resin “Byron 103” manufactured by Toyobo Co., Ltd. (number average molecular weight 22,000, hydroxyl value 5 mg KOH / g, acid value 2 mg KOH / g or less, Tg point 45 ° C.) methyl ethyl ketone / cyclohexanone = 50/50 (weight ratio) ) To obtain a polyester resin (B-3) solution having a solid content of 30%.
製造例８
テレフタル酸１３２．８部、イソフタル酸１６．６部、セバシン酸２０．２部、１，２−プロピレングリコール２２．８部、ネオペンチルグリコール４１．６部、１，４−ブタンジオール２７．０部、トリメチロールプロパン１．３４部及び重縮合触媒を仕込み、加熱、撹拌し、生成する水を除去しながらエステル化反応を行い、数平均分子量１５，０００、水酸基価１２ｍｇＫＯＨ／ｇ、酸価１ｍｇＫＯＨ／ｇ、Ｔｇ点６５℃ の樹脂を得た。得られた樹脂をメチルエチルケトン／シクロヘキサノン＝５０／５０の混合溶剤にて希釈し固形分３０％のポリエステル樹脂（Ｂ−４）溶液を得た。
Production Example 8
132.8 parts of terephthalic acid, 16.6 parts of isophthalic acid, 20.2 parts of sebacic acid, 22.8 parts of 1,2-propylene glycol, 41.6 parts of neopentyl glycol, 27.0 parts of 1,4-butanediol , 1.34 parts of trimethylolpropane and a polycondensation catalyst were charged, heated and stirred, and the esterification reaction was carried out while removing the generated water. The number average molecular weight was 15,000, the hydroxyl value was 12 mgKOH / g, and the acid value was 1 mgKOH / g, a resin having a Tg point of 65 ° C. was obtained. The obtained resin was diluted with a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 to obtain a polyester resin (B-4) solution having a solid content of 30%.
製造例９ （比較用）
テレフタル酸４９８部、イソフタル酸４９８部、アジピン酸２９２部、１，４−シクロヘキサンジカルボン酸３４４部、ネオペンチルグリコール９９８部、トリメチロールプロパン６６部、チタンテトラブトキシド０．１８部を１０Ｌオートクレーブに仕込み、３．５Ｋｇ／ｃｍ・Ｇの窒素加圧下で３時間かけて２３５℃まで徐々に昇温し、エステル化を行った。次いで、１時間かけて１０ｍｍＨｇまで減圧重合を行うと共に温度を２５０℃まで昇温し、さらにこのまま１ｍｍＨｇ以下で９０分間後期重合を行ない、数平均分子量２４，０００、水酸基価３ｍｇＫＯＨ／ｇ、酸価１ｍｇＫＯＨ／ｇ、Ｔｇ点３８℃のポリエステル樹脂を得た。得られた樹脂をメチルエチルケトン／シクロヘキサノン＝５０／５０（重量比）の混合溶剤にて希釈して固形分３０％のポリエステル樹脂（ＢＣ−５）溶液を得た。
Production Example 9 (for comparison)
A 10 L autoclave was charged with 498 parts of terephthalic acid, 498 parts of isophthalic acid, 292 parts of adipic acid, 344 parts of 1,4-cyclohexanedicarboxylic acid, 998 parts of neopentyl glycol, 66 parts of trimethylolpropane, and 0.18 part of titanium tetrabutoxide. Esterification was performed by gradually raising the temperature to 235 ° C. over 3 hours under a nitrogen pressure of 3.5 kg / cm · G. Subsequently, the polymerization was performed under reduced pressure to 10 mmHg over 1 hour and the temperature was raised to 250 ° C., and then the latter polymerization was performed for 90 minutes at 1 mmHg or less, and the number average molecular weight was 24,000, the hydroxyl value was 3 mgKOH / g, and the acid value was 1 mgKOH. / G, a polyester resin having a Tg point of 38 ° C. was obtained. The obtained resin was diluted with a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 (weight ratio) to obtain a polyester resin (BC-5) solution having a solid content of 30%.
製造例１０ （比較用）
撹拌機、温度計、充填カラム、水凝縮器、トラップ及び窒素導入口が適当に備えられた四口フラスコ中に、１２７部の２−メチル−１，３−プロパンジオール、２２．３部のエチレングリコール、２６２．５部のテレフタル酸及び０．４５グラムのスズ酸ブチル触媒を装填した。充填カラムの上の頭部温度を１００℃未満に連続的に維持しながら、２２０℃に加熱した。水凝縮物を除去しながら反応を進め、液状内容物が清澄になった後、１８０℃に冷却した後、６９．３部のダイマー脂肪酸及び６９．３部のイソフタル酸を添加した。次いで、この内容物を２２０℃に加熱し、水凝縮物を捕集し、２５部のシクロヘキサノン及び５０部の芳香族石油系溶剤「スワゾール１５００」（丸善石油化学（株）社製）を添加し、そして温度を２３４℃に加熱した。次いで、この反応物を冷却し、メチルエチルケトン／シクロヘキサノン＝５０／５０（質量比）の混合溶剤にて希釈して固形分３０％のポリエステル樹脂（ＢＣ−６）溶液を得た。得られた樹脂固形分は、数平均分子量９，４５０、水酸基価７ｍｇＫＯＨ／ｇ、酸価２ｍｇＫＯＨ／ｇ、Ｔｇ点２７℃を有していた。
Production Example 10 (for comparison)
127 parts 2-methyl-1,3-propanediol, 22.3 parts ethylene in a four-neck flask suitably equipped with stirrer, thermometer, packed column, water condenser, trap and nitrogen inlet Glycol, 262.5 parts terephthalic acid and 0.45 grams butyl stannate catalyst were charged. The head temperature above the packed column was heated to 220 ° C. while continuously maintaining below 100 ° C. The reaction was carried out while removing water condensate, and after the liquid content became clear, after cooling to 180 ° C., 69.3 parts of dimer fatty acid and 69.3 parts of isophthalic acid were added. The contents are then heated to 220 ° C. to collect water condensate, and 25 parts cyclohexanone and 50 parts aromatic petroleum solvent “Swazole 1500” (manufactured by Maruzen Petrochemical Co., Ltd.) are added. And the temperature was heated to 234 ° C. Next, this reaction product was cooled and diluted with a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 (mass ratio) to obtain a polyester resin (BC-6) solution having a solid content of 30%. The obtained resin solid content had a number average molecular weight of 9,450, a hydroxyl value of 7 mgKOH / g, an acid value of 2 mgKOH / g, and a Tg point of 27 ° C.
レゾール型フェノール樹脂架橋剤（Ｃ）の製造
製造例１１
ｍ−クレゾール１００部、３７％ホルムアルデヒド水溶液１７８部及び水酸化ナトリウム１部を加え、６０℃で３時間反応させた後、減圧下、５０℃で１時間脱水した。ついでｎ−ブタノール１００部とリン酸３部を加え、１１０〜１２０℃で２時間反応を行った。反応終了後、得られた溶液を濾過して生成したリン酸ナトリウムを濾別し、固形分約５０％のレゾール型フェノール樹脂架橋剤（Ｃ−１）溶液を得た。得られた樹脂は、数平均分子量９００で、ベンゼン核１核当り、平均メチロール基数が０．３個で平均ブトキシメチル基数が１．２個であった。
Production of resol type phenolic resin crosslinking agent (C) Production Example 11
100 parts of m-cresol, 178 parts of 37% formaldehyde aqueous solution and 1 part of sodium hydroxide were added and reacted at 60 ° C. for 3 hours, and then dehydrated at 50 ° C. for 1 hour under reduced pressure. Then, 100 parts of n-butanol and 3 parts of phosphoric acid were added and reacted at 110 to 120 ° C. for 2 hours. After completion of the reaction, the resulting solution was filtered to remove the sodium phosphate produced to obtain a resol type phenol resin crosslinking agent (C-1) solution having a solid content of about 50%. The obtained resin had a number average molecular weight of 900, an average number of methylol groups of 0.3 and an average number of butoxymethyl groups of 1.2 per benzene nucleus.
製造例１２〜１６
製造例１１において、ｍ−クレゾール１００部のかわりに後記表１に示すフェノール成分を１００部使用する以外は製造例９と同様に行い、固形分約５０％の各レゾール型フェノール樹脂架橋剤溶液を得た。製造例１５及び１６は、各々比較用の製造例である。
Production Examples 12-16
In Production Example 11, the same procedure as in Production Example 9 was conducted except that 100 parts of the phenol component shown in Table 1 below was used instead of 100 parts of m-cresol, and each resol-type phenol resin crosslinking agent solution having a solid content of about 50% was prepared. Obtained. Production Examples 15 and 16 are comparative production examples.
実施例１
製造例１で得たポリエステル樹脂（Ａ−１）溶液２３３部（固形分量で７０部）、製造例５で得たポリエステル樹脂（Ｂ−１）溶液１００部（固形分量で３０部）に、製造例１１で得たフェノール樹脂（Ｃ−１）溶液６０部（固形分量で３０部）及びカルナウバワックス０．５部及び「ネイキュア５２２５」（＊１）２．０部（ドデシルベンゼンスルホン酸量として０．５質量部）を混合、溶解させ、ついでメチルエチルケトン／シクロヘキサノン＝５０／５０（質量比）の混合溶剤を加えて固形分３０％の塗料を得た。
（＊１）ネイキュア５２２５：米国、キング インダストリイズ社製、商品名、ドデシルベンゼンスルホン酸のアミン中和溶液、ドデシルベンゼンスルホン酸含有量は２５％。
Example 1
Manufactured into 233 parts of polyester resin (A-1) solution obtained in Production Example 1 (70 parts by solid content) and 100 parts of polyester resin (B-1) solution obtained in Production Example 5 (30 parts by solid content). 60 parts of phenol resin (C-1) solution obtained in Example 11 (30 parts by solid content), 0.5 part of carnauba wax, and 2.0 parts of “Nicure 5225” (* 1) (as dodecylbenzenesulfonic acid amount) 0.5 parts by mass) was mixed and dissolved, and then a mixed solvent of methyl ethyl ketone / cyclohexanone = 50/50 (mass ratio) was added to obtain a paint having a solid content of 30%.
(* 1) Nature 5225: manufactured by King Industries, USA, trade name, amine neutralized solution of dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid content 25%.
実施例２〜１７及び比較例１〜１５
後記表２に示す配合とする以外は実施例１と同様に行い、固形分３０％の各塗料を得た。表２における各成分の配合量は、固形分表示によるものとする。但し、ネイキュア５２２５の配合量はドデシルベンゼンスルホン酸の量にて表示する。
表２における（註）は、下記のとおりの意味を有する。
（＊２）サイメル３０３：三井サイテック（株）製、メチルエーテル化メラミン樹脂。
（＊３）スーパーベッカミンＴＤ−１２６：ＤＩＣ（株）製、ブチル化ベンゾグアナミン樹脂。
Examples 2-17 and Comparative Examples 1-15
Except for the formulation shown in Table 2 below, the same procedure as in Example 1 was carried out to obtain each paint having a solid content of 30%. The amount of each component in Table 2 is based on solid content display. However, the amount of NACURE 5225 is indicated by the amount of dodecylbenzenesulfonic acid.
(註) in Table 2 has the following meaning.
(* 2) Cymel 303: a methyl etherified melamine resin manufactured by Mitsui Cytec Co., Ltd.
(* 3) Superbecamine TD-126: manufactured by DIC Corporation, butylated benzoguanamine resin.
試験塗板の作成
上記実施例及び比較例で得た水性塗料組成物を、厚さ０．２７ｍｍの＃５１８２アルミニウム板に乾燥塗膜重量が約８．５ｇ／ｍ２、約５．０ｇ／ｍ２の２水準となるようにロールコート塗装し、コンベア搬送式の熱風乾燥炉内を通過させて焼付け、試験塗板を得た。焼付け条件は、素材到達最高温度（ＰＭＴ）が２５５℃、乾燥炉内通過時間が２０秒間の条件とした。得られた試験塗板について下記の試験方法に基いて各種試験を行った。耐食性試験については、乾燥塗膜重量が約８．５ｇ／ｍ２、約５．０ｇ／ｍ２の２水準の試験塗板について試験を行った。その他の試験項目については、乾燥塗膜重量が約８．５ｇ／ｍ２の試験塗板について試験を行った。試験結果を後記表２に示す。
Preparation of test coating plate The aqueous coating compositions obtained in the above examples and comparative examples were dried on a # 5182 aluminum plate having a thickness of 0.27 mm and the dry coating weight was about 8.5 g / m 2 and about 5.0 g / m 2. The coating was roll-coated so as to satisfy the following two levels, and was baked by passing through a conveyor-carrying hot-air drying furnace to obtain a test coated plate. The baking conditions were such that the maximum material temperature (PMT) was 255 ° C. and the passage time in the drying furnace was 20 seconds. The obtained test coated plate was subjected to various tests based on the following test methods. For the corrosion resistance test, the test was conducted on two levels of test coated plates having a dry coating weight of about 8.5 g / m 2 and about 5.0 g / m 2 . For other test items, a test coated plate having a dry coating film weight of about 8.5 g / m 2 was tested. The test results are shown in Table 2 below.
試験方法
塗膜外観：試験塗板の塗膜外観を肉眼で観察した。塗面にハジキ、凹み、曇り、濁りなどの塗面異常の認められないものを良好（○）とした。
Test Method Coating Film Appearance: The coating film appearance of the test coating plate was observed with the naked eye. A coating having no coating surface abnormalities such as repellency, dents, cloudiness, and turbidity on the coating surface was evaluated as good (◯).
硬化性：塗装面積１００ｃｍ２の試験塗板を１００ｃｃのメチルエチルケトン中にて６０分間還流下で抽出処理を行い、抽出されなかった塗膜残分から下記基準にて評価した。
◎：塗膜残分が９０％以上
○：塗膜残分が８０％以上で９０％未満
□：塗膜残分が７０％以上で８０％未満
△：塗膜残分が４０％以上で７０％未満
×：塗膜残分が４０％未満。
Curability: A test coated plate having a coating area of 100 cm 2 was subjected to an extraction treatment in 100 cc of methyl ethyl ketone under reflux for 60 minutes, and evaluated based on the following criteria from the coating film residue that was not extracted.
A: 90% or more of the coating film residue O: 80% or more and less than 90% of the coating film □: 70% or more and less than 80% of the coating film Δ: 70 when the coating film residue is 40% or more Less than% x: The coating film residue is less than 40%.
耐レトルト性：試験塗板を水に浸漬し、オートクレーブ中で１２５℃で３０分間処理した塗膜の白化や膨れの状態を下記基準により評価した。
◎：全く白化、膨れが認められない、
○：膨れが認められず、ごくわずかに白化が認められる、
□：若干の白化又は膨れが認められるが、実用上問題がない、
△：少し白化又は膨れがかなり認められる、
×：著しく白化又は膨れが認められる。
Retort resistance: The test coating plate was immersed in water, and the state of whitening or swelling of the coating film treated at 125 ° C. for 30 minutes in an autoclave was evaluated according to the following criteria.
A: No whitening or swelling is observed,
○: Swelling is not recognized and whitening is observed slightly.
□: Some whitening or swelling is observed, but there is no practical problem.
Δ: Slightly whitening or swelling is observed,
X: Remarkably whitening or swelling is observed.
加工性：特殊ハゼ折り型デュポン衝撃試験器を用い、塗膜面が外側になるように下部を２つ折りにした試験塗板の折り曲げ部の間に厚さ０．２７ｍｍのアルミニウム板を２枚挟んで試験器に設置し、接触面が平らな厚さ１ｋｇの鉄の錘を高さ５０ｃｍから落下させて折り曲げ部に衝撃を与えた後、折り曲げ先端部に６．５Ｖの電圧を６秒間通過させた際の、折り曲げ先端部２ｍｍ幅の電流値（ｍＡ）を測定し、下記基準にて評価した。
◎：電流値が０．５ｍＡ未満、
○：電流値が０．５ｍＡ以上で２．０ｍＡ未満、
□：電流値が２．０ｍＡ以上で５．０ｍＡ未満、
△：電流値が５．０ｍＡ以上で１０ｍＡ未満、
×：電流値が１０ｍＡ以上。
Workability: Using a special goby fold type DuPont impact tester, sandwich two aluminum plates with a thickness of 0.27 mm between the bent portions of the test coating plate folded in two so that the coating surface is on the outside The test piece was placed on a tester, a 1 kg thick iron weight with a flat contact surface was dropped from a height of 50 cm to give an impact to the bent portion, and then a voltage of 6.5 V was passed through the bent tip for 6 seconds. At that time, the current value (mA) of the bent tip portion 2 mm width was measured and evaluated according to the following criteria.
A: Current value is less than 0.5 mA,
○: Current value is 0.5 mA or more and less than 2.0 mA,
□: Current value is 2.0 mA or more and less than 5.0 mA,
Δ: Current value is 5.0 mA or more and less than 10 mA,
X: Current value is 10 mA or more.
耐食性：乾燥塗膜重量が約８．５ｇ／ｍ２及び約５．０ｇ／ｍ２の２水準の試験塗板について試験を行った。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３００ｇ、落錘高さ２５ｃｍの条件で試験塗板の塗面に凸加工した試験塗板を、缶内容物擬似液である腐食液（クエン酸／食塩／水＝３／３／９４〔質量比〕）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、４０℃で７日間とした。
◎：腐食なし
○：極僅かに腐食
□：僅かに腐食
△：少し腐食
×：著しい腐食。
Corrosion resistance: Tests were conducted on two levels of test coated plates having dry film weights of about 8.5 g / m 2 and about 5.0 g / m 2 . Corrosion, which is a simulated liquid of can contents, using a DuPont impact tester and a test coating that has been convexly processed on the coating surface of the test coating under the conditions of a tip diameter of 1/4 inch, a weight load of 300 g, and a falling weight height of 25 cm. The sample was immersed in a solution (citric acid / salt / water = 3/3/94 [mass ratio]), and the degree of corrosion was visually evaluated according to the following criteria. The immersion conditions were 7 days at 40 ° C.
◎: No corrosion ○: Very slight corrosion □: Slight corrosion △: Slight corrosion ×: Significant corrosion
密着性：試験塗板の塗膜に、カッターで１ｍｍ×１ｍｍの碁盤目を１００個作成し、この試料片を水道水中で１２０℃−９０分間のレトルト処理を施した。その後碁盤目部分に、セロハン粘着テープを貼ったのち、セロハン粘着テープを急速に剥離し、塗膜の剥離状態を観察し、下記基準によって評価した。
◎：塗膜剥離が全くなく、碁盤目塗膜のフチ欠けも認められない、
○：塗膜剥離が全くないが、碁盤目塗膜のフチ欠けが認められる、
□：塗膜の剥離が１００個中、１〜２個認められる、
△：塗膜の剥離が１００個中、３〜１０個認められる、
×：塗膜の剥離が１００個中、１１個以上認められる。
Adhesiveness: 100 grids of 1 mm × 1 mm were prepared on the coating film of the test coating plate, and this sample piece was retorted at 120 ° C. for 90 minutes in tap water. The cellophane pressure-sensitive adhesive tape was then applied to the grid area, the cellophane pressure-sensitive adhesive tape was rapidly peeled off, and the peeled state of the coating film was observed and evaluated according to the following criteria.
A: There is no peeling of the coating film and no chipping of the cross-cut coating film is observed.
○: There is no peeling of the coating film, but the chipping of the cross-cut coating film is observed.
□: 1 to 2 of 100 peelings are recognized,
(Triangle | delta): 3-10 pieces of peeling of a coating film are recognized among 100 pieces,
X: The peeling of a coating film is recognized 11 or more out of 100 pieces.
フレーバー性：試験塗板を、塗装面積：活性炭で処理した水道水が１００ｃｍ２：１００ｃｃとなるように耐熱ガラス製ボトルに入れ、蓋をし、１２５℃−３０分間の殺菌処理後、常温に冷却し、その抽出液について以下の基準にて評価した。
◎：風味に変化が全く認められない、
○：風味に極わずかに変化が認められる、
△：風味に少し変化が認められる、
×：風味に著しく変化が認められる。
Flavorability: The test coated plate is placed in a heat-resistant glass bottle so that the coated area: tap water treated with activated carbon is 100 cm 2 : 100 cc, covered, sterilized at 125 ° C. for 30 minutes, and then cooled to room temperature. The extract was evaluated according to the following criteria.
A: No change in flavor is observed,
○: A slight change in flavor is observed,
Δ: A slight change in flavor is observed,
X: Significant change is recognized in flavor.
耐傷付性：バウデン摩擦試験機（神鋼造機社製、曽田式付着滑り試験機）を用い、摩擦部３／１６鋼球、荷重１ｋｇ、摩擦速度７往復／分の条件で摩擦試験を行い、塗膜にキズが発生するまでの摩擦回数を測定した。下記の基準によって評価した。
◎：摩擦回数２００回でもキズが発生しない、
○：摩擦回数１５０回〜２００回でキズが発生、
□：摩擦回数５０回〜１５０回でキズが発生、
△：摩擦回数１０回〜５０回でキズが発生、
×：摩擦回数１０回以下でキズが発生。
Scratch resistance: A friction test was performed using a Bowden friction tester (Shinko Engineering Co., Ltd., Iwata-type adhesion slip tester) under the conditions of a friction part 3/16 steel ball, a load of 1 kg, and a friction speed of 7 reciprocations per minute. The number of frictions until the film was scratched was measured. Evaluation was made according to the following criteria.
◎: Scratch does not occur even after 200 times of friction,
○: Scratches occur at 150 to 200 times of friction,
□: Scratches occur when the friction frequency is 50 to 150 times.
Δ: Scratches occur when the number of frictions is 10 to 50 times.
X: Scratches occur when the number of frictions is 10 or less.
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