JP2004002671A - Method for producing polyester resin dispersion - Google Patents
Method for producing polyester resin dispersion Download PDFInfo
- Publication number
- JP2004002671A JP2004002671A JP2003015482A JP2003015482A JP2004002671A JP 2004002671 A JP2004002671 A JP 2004002671A JP 2003015482 A JP2003015482 A JP 2003015482A JP 2003015482 A JP2003015482 A JP 2003015482A JP 2004002671 A JP2004002671 A JP 2004002671A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- crystalline polyester
- temperature
- resin
- coating
- 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
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 176
- 239000004645 polyester resin Substances 0.000 title claims abstract description 176
- 239000006185 dispersion Substances 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 238000010791 quenching Methods 0.000 claims abstract description 4
- 230000000171 quenching effect Effects 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 59
- 239000011248 coating agent Substances 0.000 claims description 56
- 239000011342 resin composition Substances 0.000 claims description 23
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000003973 paint Substances 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 6
- 230000003028 elevating effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 40
- 239000001993 wax Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 22
- -1 polyethylene terephthalate Polymers 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 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 12
- 238000001556 precipitation Methods 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 230000008719 thickening Effects 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920003987 resole Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000010409 ironing Methods 0.000 description 5
- 150000007519 polyprotic acids Polymers 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 240000007930 Oxalis acetosella Species 0.000 description 4
- 235000008098 Oxalis acetosella Nutrition 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance 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
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 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
- 235000019743 Choline chloride Nutrition 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-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
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 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
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-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
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- QWJSAWXRUVVRLH-LREBCSMRSA-M 2-hydroxyethyl(trimethyl)azanium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound C[N+](C)(C)CCO.OC(=O)[C@H](O)[C@@H](O)C([O-])=O QWJSAWXRUVVRLH-LREBCSMRSA-M 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- PSVQKOKKLWHNRP-UHFFFAOYSA-N 3-ethylheptane Chemical compound CCCCC(CC)CC PSVQKOKKLWHNRP-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
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 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
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000005643 Pelargonic acid Substances 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
- 229920001800 Shellac Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 239000003006 anti-agglomeration agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- FCBQCNJKXDUDPV-UHFFFAOYSA-N oxaldehyde;phenol Chemical compound O=CC=O.OC1=CC=CC=C1 FCBQCNJKXDUDPV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、有機溶剤中に結晶性ポリエステル樹脂を分散してなるポリエステル樹脂分散液の製造方法に関するものであり、該製造方法により得られるポリエステル樹脂分散液を用いた被覆用樹脂組成物に関するものであり、該被覆用樹脂組成物を用いて得られる缶体及び缶体の製造方法に関する。
【０００２】
【従来の技術およびその課題】
従来、缶内面被覆用樹脂として、ビスフェノールＡ型エポキシ樹脂を含有するものが多く用いられてきた。しかしながら、近年、外因性内分泌攪乱化学物質（環境ホルモン）の一つとしてビスフェノールＡが挙げられたことにより、塗膜からビスフェノールＡが溶出しない塗料の開発が強く望まれるようになってきた。
【０００３】
エポキシ樹脂に代わるものとしてポリエステル樹脂が検討されてきたが、缶内面用被膜に要求される、硬度、密着性、防食性、風味保持性などの厳しい塗膜性能を満足させることは容易ではなく、ＰＥＴ樹脂に代表されるような高結晶性ポリエステル樹脂を使いこなすことが重要になってきた。
【０００４】
また、近年樹脂被覆缶体の製造コスト削減及び成形加工後のプレスオイルの処理の問題から、金属板を缶状に成形加工してから塗装を行うポストコート方式から、予め塗装が施された金属平板を缶状に成形加工するプレコート方式に替わってきており、硬度と加工性を兼ね備えた高結晶性ポリエステル樹脂の塗料への利用が要望されている。
【０００５】
結晶性ポリエステル樹脂を利用する方法としては、ポリエステルフィルムを使用することが検討されており、例えば、２軸延伸した熱可塑性フィルムを直接、あるいは接着剤を介して、金属板に熱ラミネートする方法（例えば、特開特許文献１、特許文献２等参照。）、樹脂を熱溶融させ、金属板上に直接押出しラミネートする方法（例えば、特許文献３等参照。）などが開示されており一部実用化されている。
【０００６】
しかしながら、フィルムラミネートを利用するためには新たな設備投資を必要とするだけでなく、フィルムラミネート法は塗装に比較して作業性が劣るため、このような結晶性ポリエステル樹脂を利用した塗料の開発が望まれているが、結晶性ポリエステル樹脂は一般に溶剤への溶解性が低く、また、貯蔵中に結晶が析出してくるなどの問題があり、結晶性ポリエステル樹脂をそのまま塗料に応用するには、多くの問題があった。このような問題を解決するための一方法として、有機溶剤に可溶な非結晶ポリエステル樹脂と融点９０〜１８０℃の結晶性ポリエステル樹脂を加熱して溶融混合し、有機溶剤中に溶解または分散する方法が開示されている（例えば特許文献４等参照。）。しかしながら、該方法では限界があり、缶内面用塗料などに必要な融点が１９０℃を超えるような結晶性の高いポリエステル樹脂を用いた場合には製造時又は溶液貯蔵時に結晶が大きく成長してしまい、溶液が大きく増粘又は粒子が沈降して凝集するという問題がある。
【０００７】
本発明の目的は、結晶性ポリエステル樹脂を用いた製造安定性および貯蔵安定性の優れたポリエステル樹脂分散液の製造方法を提供することである。
【０００８】
【特許文献１】
特開昭５６−１０４５１号公報
【特許文献２】
特開昭５７−６５４６３号公報
【特許文献３】
特開昭５１−１７９８８号公報
【特許文献４】
特開平４−１６４９５７号公報
【０００９】
【課題を解決するための手段】
本発明者らは、上記の目的を達成すべく鋭意研究を行った結果、ポリエステル樹脂溶液を冷却して結晶を析出させる工程において、結晶性ポリエステル樹脂の昇温結晶開始温度からガラス転移温度まで、樹脂溶液を急速に冷却させることにより、細かくて安定なポリエステル樹脂分散液が製造できることを見出し、本発明を完成するに至った。
【００１０】
かくして本発明は、結晶性ポリエステル樹脂（Ａ）及び非結晶性ポリエステル樹脂（Ｂ）を有機溶剤（Ｃ）中に加熱、溶解させた後、該樹脂溶液を結晶性ポリエステル樹脂（Ａ）の昇温結晶開始温度以上の温度から結晶性ポリエステル樹脂（Ａ）のガラス転移温度以下の温度まで毎分２℃以上のスピードで急冷することを特徴とするポリエステル樹脂分散液の製造方法を提供するものである。
【００１１】
本発明はまた、上記製造方法により得られるポリエステル樹脂分散液を用いた被覆用樹脂組成物を提供するものである。
【００１２】
本発明はさらに、上記被覆用樹脂組成物を用いた缶体、及び缶体の製造方法を提供するものである。
【００１３】
以下、本発明についてさらに詳細に説明する。
【００１４】
【発明の実施の形態】
本発明のポリエステル樹脂分散液の製造方法は、有機溶剤中に結晶性ポリエステル樹脂及び非結晶性ポリエステル樹脂が溶解された高温の樹脂溶液を急冷して結晶性ポリエステル樹脂の結晶を析出させるものである。
【００１５】
結晶性ポリエステル樹脂（Ａ）
ポリエステル樹脂分散液の（Ａ）成分である結晶性ポリエステル樹脂は、多塩基酸成分と多価アルコール成分とのエステル化物からなるものである。
【００１６】
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、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、２，６−ナフタレンジカルボン酸、１，６−ヘキサンジカルボン酸などから選ばれる１種以上の二塩基酸及びこれらの酸の低級アルキルエステル化物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。
【００１７】
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、プロピレングリコール、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、ブチルエチルプロパンジオール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又はエステル交換反応は、それ自体既知の方法によって行うことができる。
【００１８】
結晶性ポリエステル樹脂は、上記原料の内、酸成分としてテレフタル酸及び２，６−ナフタレンジカルボン酸を主に使用し、多価アルコール成分としてエチレングリコール及び１，４−ブタンジオールを主に使用することにより得ることができるが、特にテレフタル酸とエチレングリコールを主に用いたポリエチレンテレフタレート系樹脂が好適である。
【００１９】
本発明で使用する結晶性ポリエステル樹脂は、融点が１９０℃〜２６０℃、好ましくは２００℃〜２５５℃、昇温結晶開始温度が１５０℃以上、好ましくは１５５℃〜１９５℃の範囲内のものが適している。結晶性ポリエステル樹脂の昇温結晶開始温度が低いとレトルト殺菌時の熱で結晶化が進み膜が白化する傾向にあり、また、結晶性ポリエステル樹脂の融点が低いと皮膜の収着性及びバリア性が低下し、融点が高過ぎると造膜性が低下する。
【００２０】
なお、結晶性ポリエステル樹脂の融点および昇温結晶開始温度の測定は示査走査型熱量計（島津製作所）を用いて行った。
【００２１】
結晶性ポリエステル樹脂の市販品としては、例えばＩＦＧ８Ｌ、ＴＧ７Ｎ１０、ＩＰ０５１（以上、カネボウ合繊社製）、ＫＦ−５１１（三菱レイヨン社製）などが挙げられる。
【００２２】
非結晶性ポリエステル樹脂（Ｂ）
ポリエステル樹脂分散液の（Ｂ）成分である非結晶性ポリエステル樹脂は、示査走査型熱量計による測定において明確な融点がないものであり、常温で有機溶剤に溶解しやすい。
【００２３】
非結晶性ポリエステル樹脂は結晶性ポリエステル樹脂と同様、多塩基酸成分と多価アルコール成分を反応させることにより得られ、原料となる多塩基酸成分及び多価アルコール成分は上記結晶性ポリエステル樹脂の成分として列挙したものと同様のものを使用することができる。
【００２４】
ポリエステル樹脂の結晶性は、例えばポリエチレンテレフタレート樹脂の場合、酸成分であるテレフタル酸をイソフタル酸など他の酸成分に一部置き換えていくことにより、また、多価アルコールであるエチレングリコールをジエチレングリコールなど他のアルコール成分に一部置き換えていくことにより低下させ、なくすことができる。
【００２５】
非結晶性ポリエステル樹脂の市販品としては、例えばＵＥ−３２０１、ＵＥ−３２０３、ＸＡ−０６５３（以上、ユニチカ社製）、ＧＫ−８８０、ＧＫ−６４０（以上、東洋紡績社製）などが挙げられる。
【００２６】
結晶性ポリエステル樹脂（Ａ）と非結晶性ポリエステル樹脂（Ｂ）との配合比率は、重量比で（Ａ）／（Ｂ）＝６０／４０〜５／９５、特に４０／６０〜１０／９０の範囲内が、ポリエステル樹脂分散液から得られる皮膜の耐レトルト性、耐食性などの点から好ましい。
【００２７】
有機溶剤（Ｃ）
本発明のポリエステル樹脂分散液の製造方法に用いられる有機溶剤（Ｃ）は上記非結晶性ポリエステル樹脂を溶解できるものであれば使用することができるが、有機溶剤（Ｃ）中の５０重量％以上は、沸点が１５０℃〜２２０℃の水酸基を含有しない有機溶剤、特にＮ−メチル−２−ピロリドンであることがポリエステル樹脂分散液の製造安定性の面から好ましい。
【００２８】
Ｎ−メチル−２−ピロリドン以外の沸点が１５０℃〜２２０℃の水酸基を含有しない有機溶剤としては、例えばイソホロン、シクロヘキサノン等のケトン系溶剤、ＤＢＥ（デュポン社製、アジピン酸ジメチル、グルタール酸ジメチル、コハク酸ジメチルの混合溶剤）等のエステル系溶剤などが挙げられる。
【００２９】
ポリエステル樹脂分散液の製造方法
（Ａ）結晶性ポリエステル樹脂及び（Ｂ）非結晶性ポリエステル樹脂を有機溶剤中に加熱、溶解させた後、得られる溶液を冷却していくとポリエステル樹脂が結晶化し、析出する。一般にタンクなどで製造される場合における冷却は毎分０．１〜１℃程度のゆっくりしたものであるが、融点が高く、結晶性の高いポリエステル樹脂を用いた場合、析出したポリエステル粒子の径が大きくなり、分散液の貯蔵性や分散液使用塗料から得られる塗膜の平滑性が著しく低下してしまう。
【００３０】
本発明の製造方法は上記問題を解決したものであり、結晶性ポリエステル樹脂（Ａ）の昇温結晶開始温度以上の温度から結晶性ポリエステル樹脂（Ａ）のガラス転移温度以下の温度まで毎分２℃以上のスピードで急冷することが重要となる。
【００３１】
製造装置としては、ポリエステル樹脂を加熱、溶解する装置と、溶液を急冷できる装置があればよい。
【００３２】
ポリエステル樹脂分散液の製造は、まず、溶剤中に結晶性ポリエステル樹脂（Ａ）と非結晶性ポリエステル樹脂（Ｂ）が溶解された高温の樹脂溶液を作成する。樹脂溶液の製造手順には特に制限はなく、例えば
▲１▼溶剤とペレット状の結晶性ポリエステル樹脂（Ａ）を混合し、攪拌しながら加熱、溶解し、その後非結晶性ポリエステル樹脂（Ｂ）を添加する方法。
▲２▼溶剤、非結晶性ポリエステル樹脂（Ｂ）及び結晶性ポリエステル樹脂（Ａ）を全て混合した後、加温、溶解する方法、
▲３▼加温した非結晶性ポリエステル樹脂（Ｂ）を溶解した溶液中に結晶性ポリエステル樹脂（Ａ）を徐々に添加する方法、
などがある。結晶性ポリエステル樹脂（Ａ）の溶解は、有機溶剤の中では必ずしも樹脂の融点温度まで上げる必要はなく、樹脂の昇温結晶開始温度より高い温度であれば作業性に問題のない範囲でできるだけ低い方が、熱によるポリエステル樹脂の分解を避けるためには好適である。同様に樹脂の分解を避けるため非結晶性ポリエステル樹脂（Ｂ）の添加は遅い方が好ましく、上記▲１▼の製造方法が特に好ましい。
【００３３】
ポリエステル樹脂の溶解後はできるだけ速やかに本発明の冷却条件に従って冷却する。同一装置（例えばタンク）内で加熱、溶解及び冷却を全て行う場合には、冷却性能に非常に優れた装置を用いるか、仕込み量を減らして上記冷却条件に合うところを選択することが必要である。また、冷却工程を加熱、溶解装置とは別にして急冷させる方法を取ることもでき、例えば、あらかじめ冷却したタンクや冷却装置付き管内に加熱、溶解したポリエステル樹脂溶液を搬入する方法などを挙げることができる。
【００３４】
さらに、有機溶剤（Ｃ）の一部を冷却に廻し、冷却時に添加することで冷却の補助的手段として利用することもできる。
【００３５】
結晶性ポリエステル樹脂（Ａ）のガラス転移温度以下の温度まで冷却したら、それ以後の冷却速度に特に制限はない。
【００３６】
上記のようにして得られたポリエステル樹脂分散液は単独で、もしくは他の有機樹脂、架橋剤、添加剤（硬化触媒、潤滑性付与剤、消泡剤、レベリング剤、凝集防止剤など）、顔料（有機顔料、無機顔料、光輝性顔料、体質顔料、防錆顔料など）、有機溶剤など通常公知の被覆組成物用原料と組み合わせることにより、硬度、加工性、密着性、耐食性などに優れた被覆用組成物を得ることができ、中でも缶内面被覆用として特に優れた性能を発揮する。以下、本発明方法で得られたポリエステル樹脂分散液を使用した被覆用樹脂組成物について説明する。
【００３７】
被覆用樹脂組成物
本発明方法で得られたポリエステル樹脂分散液は単独で用いることもできるが、レゾール型フェノール樹脂、アミノ樹脂、エポキシ樹脂などポリエステル樹脂以外の樹脂を組み合わせることにより耐レトルト性、密着性、フレーバー性などをさらに向上させることができ、組み合わせる樹脂としては中でもレゾール型フェノール樹脂及びエポキシ樹脂が好ましい。
【００３８】
上記レゾール型フェノール樹脂はポリエステル樹脂の架橋剤として用いるものであり、該レゾール型フェノール樹脂を用いる場合には、ポリエステル樹脂分散液を構成する結晶性ポリエステル樹脂（Ａ）及び非結晶性ポリエステル樹脂（Ｂ）の少なくとも一方、特に非結晶性ポリエステル樹脂（Ｂ）が水酸基価５〜１００ｍｇＫＯＨ／ｇ、好ましくは１０〜５０ｍｇＫＯＨ／ｇ程度の水酸基を持っていることが好ましい。
【００３９】
また、レゾール型フェノール樹脂は、特に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ものが好ましい。
【００４０】
レゾール型フェノール樹脂架橋剤の製造においては、出発原料である上記フェノール成分として、２官能性フェノール化合物、３官能性フェノール化合物、４官能性以上のフェノール化合物などを使用することができる。
【００４１】
レゾール型フェノール樹脂架橋剤の製造に用いられる２官能性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、３官能性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などが挙げられ、４官能性フェノール化合物としては、ビスフェノールＡ、ビスフェノールＦなどを挙げることができる。これらのフェノール化合物は１種で、又は２種以上混合して使用することができる。
【００４２】
レゾール型フェノール樹脂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。
【００４３】
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。
【００４４】
レゾール型フェノール樹脂の配合量は、結晶性ポリエステル樹脂（Ａ）と非結晶性ポリエステル樹脂（Ｂ）との合計固形分量１００重量部に基いて０．５〜２０重量部、好ましくは５〜１５重量部の範囲内が硬化性と加工性とのバランスの観点から適している。
【００４５】
上記被覆用組成物には硬化反応を促進するため酸触媒を必要に応じて添加することができる。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、燐酸などの酸触媒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。
【００４６】
酸触媒の配合量は、得られる塗膜の物性などの点から、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）として結晶性ポリエステル樹脂（Ａ）と非結晶性ポリエステル樹脂（Ｂ）との合計固形分量１００重量部に基いて０．１〜５重量部、好ましくは０．５〜２重量部の範囲内が適している。
【００４７】
上記エポキシ樹脂は、ポリエステル樹脂がカルボキシル基を含有している場合にはその架橋剤として有効に作用するが、ポリエステル樹脂がカルボキシル基を持っていない場合にもポリエステル樹脂の補強材又は上記レゾール型フェノール樹脂と架橋することによる造膜成分として有効に作用する。
【００４８】
エポキシ樹脂を添加することで硬度、密着性、耐レトルト性などが向上するが、中でもノボラック型エポキシ樹脂が環境ホルモンの疑いをもたれているビスフェノールＡを含有していないため好ましい。ノボラック型エポキシ樹脂としては、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、分子内に多数のエポキシ基を有するフェノールグリオキザール型エポキシ樹脂などの各種のノボラック型エポキシ樹脂を挙げることができる。なかでも塗膜性能のバランスを取り易いフェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂が好適である。
【００４９】
エポキシ樹脂をポリエステル樹脂の架橋剤として使用する場合には、ポリエステル樹脂分散液を構成する結晶性ポリエステル樹脂（Ａ）及び非結晶性ポリエステル樹脂（Ｂ）の少なくとも一方、特に非結晶性ポリエステル樹脂（Ｂ）が酸価５〜３０ｍｇＫＯＨ／ｇ、好ましくは１０〜２０ｍｇＫＯＨ／ｇとなる程度のカルボキシル基を持っていることが好ましい。エポキシ樹脂の配合量は、結晶性ポリエステル樹脂（Ａ）と非結晶性ポリエステル樹脂（Ｂ）との合計固形分量１００重量部に基いて０．５〜２０重量部、好ましくは２〜１０重量部の範囲内が硬化性と加工性とのバランスの観点から適している。
【００５０】
また、エポキシ樹脂をポリエステル樹脂の架橋剤として使用する場合には、硬化反応を促進するため塩基性触媒を必要に応じて添加することができる。例えば塩化コリン、ニコチン酸アミド、酒石酸コリン、コリン水溶液、ジメチルエタノールアミンなどの３級アミンなどを具体例として挙げることができる。なかでも塩化コリン及びニコチン酸アミドが好適である。
【００５１】
塩基性触媒の配合量は、得られる塗膜の物性などの点から、結晶性ポリエステル樹脂（Ａ）と非結晶性ポリエステル樹脂（Ｂ）との合計固形分量１００重量部に基いて０．０１〜５重量部、好ましくは０．０５〜１重量部の範囲内が適している。
【００５２】
本発明の被覆用樹脂組成物は、缶状に成形された缶体の内面にスプレー等を用いて塗装してもよいが、平面状の金属板にロールコーター、カーテンフローコーター等の公知の塗装方法を用いて塗装、乾燥させた後、該塗装金属板を切断し、缶状に成形加工して缶体を作成してもよい。後者の製造方法を用いる場合、搬送や成形加工時の傷の発生を抑えるため被覆用樹脂組成物にワックスを添加してもよい。
【００５３】
ワックスは得られる皮膜の動摩擦係数を調整するために添加されるものであり、高温時の動摩擦係数を調整するためワックスの軟化点としては３０℃以上、好ましくは３３〜１５０℃の範囲内にあるものが適しており、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、ポリオレフィンワックス、動物系ワックス、植物系ワックスなどのワックス類を挙げることができる。
【００５４】
上記脂肪酸エステルワックスの原料となるポリオール化合物としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，３−又は１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、グリセリン、ジ又はそれ以上のポリグリセリン、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトールなどを挙げることができる。これらのうち、１分子中に３個以上の水酸基を有するポリオール化合物が好ましく、中でもポリグリセリン、トリメチロールプロパン、ペンタエリスリトールが好適である。
【００５５】
上記脂肪酸エステルワックスのもう一方の原料となる脂肪酸としては、飽和又は不飽和の脂肪酸を挙げることができ、炭素原子数６〜３２の脂肪酸であることが好ましい。好適な脂肪酸の具体例としては、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキン酸、ベヘン酸、セロチン酸、モンタン酸、メリシン酸などの飽和脂肪酸；カプロレイン酸、ウンデシレン酸、パルミトレイン酸、オレイン酸、リノール酸、リノレン酸、エレオステアリン酸、セトレイン酸、エルカ酸、リカン酸、リシノール酸、アラキドン酸などの不飽和脂肪酸を挙げることができる。脂肪酸エステルワックスとしては、上記ポリオール化合物の水酸基の数の少なくとも１／３が脂肪酸でエステル化されたものが好ましい。
【００５６】
シリコン系ワックスとしては、例えば、ＢＹＫ−３００、ＢＹＫ−３２０、ＢＹＫ−３３０［以上、ＢＹＫＣｈｅｍｉｅ（ビックケミー）社製］、シルウェットＬ−７７、同Ｌ−７２０、同Ｌ−７６０２［以上、日本コニカー（株）製］、ペインタッド２９、同３２、同Ｍ［以上、ダウコーニング社製］、信越シリコーンＫＦ−９６［信越化学社製］等が挙げられ、また、フッ素系ワックスとしては、例えば、シャムロックワックスＳＳＴ−１ＭＧ、同ＳＳＴ−３、同フルオロスリップ２３１［以上、シャムロックケミカルズ社製］、ＰＯＬＹＦＬＵＯ（ポリフルオ）１２０、同１５０、同４００［マイクロパウダーズ社］等が挙げられる。
【００５７】
ポリオレフインワックスとしては、例えば、シャムロックワックスＳ−３９４、同Ｓ−３９５［以上、シャムロックケミカルズ社製］、ヘキストワックスＰＥ−５２０、同ＰＥ−５２１［以上、ヘキスト社製］、三井ハイワックス［三井石油化学工業社製］等が挙げられ、さらに、動物系ワックスとしては、例えば、ラノリン、蜜ろう等が挙げられ、植物系ワックスとしては、例えば、カルナウバワックス、水ろう等が挙げられる。
【００５８】
ワックスは１種で又は２種以上組み合わせて用いることができ、その添加量は、被覆用樹脂組成物中の樹脂成分の固形分合計量１００重量部に基いて０．１〜５重量部、好ましくは０．５〜２重量部の範囲内が適している。
【００５９】
被覆用組成物を缶内面用に使用する場合の塗布量としては、乾燥塗布量で５０〜１８０ｍｇ／１００ｃｍ２、好ましくは８５〜１５０ｍｇ／１００ｃｍ２の範囲であることが好ましい。塗膜の焼付け条件は、通常、金属板の最高到達温度が、約１９０〜３００℃の温度となる条件で約１５秒〜約３０分間程度である。
【００６０】
上記缶の素材としては、例えば無処理鋼板、錫メッキ鋼板、亜鉛メッキ鋼板、クロムメッキ鋼板、リン酸塩処理鋼板、クロム酸塩処理鋼板、無処理アルミニウム板、クロム酸塩処理アルミニウム板などの金属素材を挙げることができる。
【００６１】
本発明の被覆用組成物を金属平板に塗装、乾燥させた後、切断、缶状に成形加工する缶体の製造方法においては、成形された缶体の内面にさらにスプレー等で缶内面用塗料を塗装してもよい。該缶内面用塗料としては、従来公知のものを用いることができ、また、本発明の被覆用組成物を用いてもさしつかえない。このように缶状に成型後に缶内面用塗料をさらに塗装することにより、成形時等にできた傷等を保護することができ、耐レトルト性等を大幅に向上させることができる。また、成型後に缶内面用塗料をさらに塗装する場合には、本発明の被覆用樹脂組成物の金属平板への塗装膜厚を低く抑えることが経済性の面から好ましく、経済性と塗膜の潤滑性の観点から乾燥塗布量で１０〜８５ｍｇ／１００ｃｍ２、特に１５〜６０ｍｇ／１００ｃｍ２程度が適している。
【００６２】
上記、成型後に塗装する缶内面用塗料は溶剤型塗料、水性塗料等特に制限なく用いることができ、その膜厚は傷部を補修できる程度の薄いものでよい。
【００６３】
【実施例】
以下、実施例及び比較例を挙げて、本発明をより具体的に説明する。なお、以下、「部」及び「％」はいずれも重量基準によるものとする。
【００６４】
ポリエステル樹脂分散液の製造
実施例１
結晶性ポリエステル樹脂ＫＦ５１１（三菱レイヨン社製、結晶性ポリエステル樹脂、Ｔｇ６０℃、Ｔｃ［昇温結晶開始温度］１５６℃、Ｔｍ［融点］２１４℃）６部及びＮ−メチル−２−ピロリドン２４部を冷却管をつけた窒素ガス置換した４つ口フラスコに仕込み、攪拌翼により攪拌しながらマントルヒーターで約２００℃まで加温しＫＦ５１１を完全に溶解した。次に加熱を止め、ＤＢＥ（デュポン社製、アジピン酸ジメチル、グルタール酸ジメチル、コハク酸ジメチルの混合溶剤）４６部を滴下した後、非結晶性ポリエステル樹脂ＧＫ８８０（東洋紡績社製、非結晶性ポリエステル樹脂、Ｔｇ８４℃）２４部を仕込み完全に溶解するまで攪拌し１６０℃まで冷却した。この溶液を冷却開始温度１６０℃から冷却終了温度５５℃まで５℃／分の速度で冷却し、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ１を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００６５】
実施例２
実施例１において冷却開始温度１６０℃から冷却終了温度５５℃までを３℃／分の速度で冷却する以外は実施例１と同様にして、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ２を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００６６】
実施例３
実施例１において冷却開始温度を１８０℃にする以外は実施例１と同様にして、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ３を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００６７】
実施例４
実施例１においてＤＢＥの替わりにイソホロンを使用する以外は実施例１と同様にして、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ４を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００６８】
実施例５
実施例１においてＤＢＥ４６部の替わりにＤＢＥ２３部及びソルベッソ１００（エクソンモービル社製、芳香族系炭化水素溶剤）２３部を使用する以外は実施例１と同様にして、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ５を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００６９】
実施例６
実施例１においてＤＢＥ４６部の替わりにＤＢＥ１１部及びメチルエチルケトン３５部を使用する以外は実施例１と同様にして、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ６を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００７０】
実施例７
実施例１においてＮ−メチル−２−ピロリドン２４部の替わりにイソホロン２４部を使用する以外は実施例１と同様にして、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ７を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００７１】
実施例８
結晶性ポリエステル樹脂ＴＧ７Ｎ１０（カネボウ合繊社製、結晶性ポリエステル樹脂、Ｔｇ７９℃、Ｔｃ１９０℃、Ｔｍ２３０℃）６部及びＮ−メチル−２−ピロリドン２４部を冷却管をつけた窒素ガス置換した４つ口フラスコに仕込み、攪拌翼により攪拌しながらマントルヒーターで約２２０℃まで加温しＴＧ７Ｎ１０を完全に溶解した。次に加熱を止め、ＤＢＥ４６部を滴下した後、非結晶性ポリエステル樹脂ＵＥ３２０１（ユニチカ社製、非結晶性ポリエステル樹脂、Ｔｇ６５℃）２４部を仕込み完全に溶解するまで攪拌し１９５℃まで冷却した。この溶液を冷却開始温度１９５℃から冷却終了温度７５℃まで５℃／分の速度で冷却し、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ８を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００７２】
実施例９
結晶性ポリエステル樹脂ＫＦ５１１を１７部、非結晶性ポリエステル樹脂ＵＥ３２０３（ユニチカ社製、非結晶性ポリエステル樹脂、Ｔｇ６０℃）１３部、Ｎ−メチル−２−ピロリドン２４部及びＤＢＥ４６部を冷却管をつけた窒素ガス置換した４つ口フラスコに仕込み、攪拌翼により攪拌しながらマントルヒーターで１９０℃まで加温し樹脂が溶解するまで攪拌した。この溶液を冷却開始温度１９０℃から冷却終了温度５５℃まで４℃／分の速度で冷却し、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ９を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００７３】
実施例１０
実施例１において非結晶性ポリエステル樹脂ＧＫ８８０の替わりにＸＡ−０６５３（ユニチカ社製、非結晶性ポリエステル樹脂、Ｔｇ５８℃、酸価２０ｍｇＫＯＨ／ｇ）を使用する以外は実施例１と同様にして、固形分３０％、粒子径約５μｍのポリエステル樹脂分散液Ｒ１３を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００７４】
比較例１
実施例１において冷却開始温度１６０℃から冷却終了温度５５℃までを１℃／分の速度で冷却する以外は実施例１と同様にして、固形分３０％、粒子径約２０μｍのポリエステル樹脂分散液Ｒ１０を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵すると沈殿物がみられた。
【００７５】
比較例２
実施例１において冷却開始温度１６０℃から冷却終了温度５５℃までを、１６０℃から８０℃まで５℃／分、８０℃から５５℃までを１℃／分の速度で冷却する以外は実施例１と同様にして、固形分３０％、粒子径約１０μｍのポリエステル樹脂分散液Ｒ１１を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵すると沈殿物がみられた。
【００７６】
比較例３
実施例１において冷却開始温度１６０℃から冷却終了温度５５℃までを、１６０℃から１２０℃まで１℃／分、１２０℃から５５℃までを５℃／分の速度で冷却する以外は実施例１と同様にして、固形分３０％、粒子径約１５μｍのポリエステル樹脂分散液Ｒ１２を得た。ポリエステル樹脂分散液は２０℃で１ヶ月貯蔵すると沈殿物がみられた。
【００７７】
比較例４
実施例１において結晶性ポリエステル樹脂ＫＦ５１１の配合量を６部から２１部へ、また、非結晶性ポリエステル樹脂ＧＫ８８０の配合量を２４部から９部に変更する以外は実施例１と同様にして製造したところ、ペースト状となり、分散液は得られなかった。
【００７８】
被覆用樹脂組成物（缶内面用）
実施例１１〜２２及び比較例５〜９
攪拌機を有する容器に後記表１に示す配合表に従って各原料を配合し、各缶内面被覆用樹脂組成物を作成した。
【００７９】
塗装板の作成方法
上記各缶内面被覆用樹脂組成物を、Ｎｏ．５０５２アルミ板に乾燥塗膜重量が１００ｃｍ２当たり１２０ｍｇとなるようにバーコータ塗装し、アルミ板が２０秒で２７０℃に達する条件で焼き付け乾燥させ各塗装板を作成した。
【００８０】
上記塗装板の作成方法で得た各塗装板について、塗面状態、付着性、加工性、香料収着性、耐レトルト性、耐腐食性について下記試験方法に従って評価した。
【００８１】
試験方法
塗面状態；塗装板の塗面を目視観察し、下記の基準によって評価した。
○：塗面全面が滑らか。
△：塗面全面に僅かに凹凸がみられる。
×：塗面全面に大きな凹凸がみられる。
【００８２】
付着性；塗装板の塗膜にナイフを使用して約１．５ｍｍの幅で縦、横それぞれ１１本の切り目をゴバン目に入れ、２４ｍｍ幅のセロハン粘着テープを密着させ、強く剥離した時のゴバン目部の塗膜を観察し、以下の基準により評価した。
◎：全く剥離が認められない。
○：僅かな剥離が認められる。
△：かなりの剥離が認められる。
×：著しい剥離が認められる。
【００８３】
加工性；塗装板の下部に塗膜面を外側にして１８０度折曲げ部を設け、特殊ハゼ折り型デュポン衝撃試験機を用いて、この折曲げ部に接触面が平らな重さ１ｋｇの鉄の錘を高さ５０ｃｍから落下させた時に生ずる折曲げ部分の塗膜の亀裂の長さを測定し、以下の基準で評価した。
○：５ｍｍ未満。
△：５ｍｍ以上で１０ｍｍ未満。
×：１０ｍｍ以上。
【００８４】
香料収着性；脱イオン水中に、ｄ−リモネン溶液３０ｍｇ／ｌをＳ−１１７０（三菱化学社製ショ糖脂肪酸エステル）１ｇ／ｌで分散した液に塗装板を浸漬し、３５℃で１ヶ月貯蔵した。貯蔵後、塗膜に収着したｄ−リモネンを、２０℃−１週間かけてジエチルエーテルで抽出し、ガスクロマトグラフィーにより収着量を測定して、以下の基準で評価した。
○：塗膜重量１２０ｍｇ当たり０．６ｍｇ未満。
△：塗膜重量１２０ｍｇ当たり０．６ｍｇ以上１．６ｍｇ未満。
×：塗膜重量１２０ｍｇ当たり１．６ｍｇ以上。
【００８５】
耐レトルト性：塗装板をオートクレーブ中、１２５℃の脱イオン水に３５分間浸漬し引上げた後、塗膜の白化状態を観察し以下の基準により評価した。
○：塗膜に僅かな白化が認められる。
△：塗膜にかなりの白化が認められる。
×：塗膜に著しい白化が認められる。
【００８６】
耐腐食性：密栓できる容器に入れた１０％パインジュース中に、裏面が腐食しないようにテープ等で被覆した塗装板を浸漬し、密栓して３５℃で１ケ月間保存後、塗面の腐食の状態を観察し、以下の基準により評価した。
○：腐食が認められない。
△：腐食がかなり認められる。
×：腐食が著しい。
【００８７】
【表１】
表１における各注（＊１）〜（＊５）の原料は各々下記の内容のものである。
（＊１）３０％ＧＫ−８８０：非結晶性ポリエステル樹脂ＧＫ−８８０ ３０部をＮ−メチル−２−ピロリドン２４部とＤＢＥ４６部との混合溶剤に加熱、溶解したもの。
（＊２）３０％エピコート１００９：エピコート１００９（ジャパンエポキシレジン社製、ビスフェノールＡ型エポキシ樹脂、エポキシ当量３，５００、数平均分子量約３，７５０）３０部をメチルエチルケトン４５部及びブチルセロソルブ２５部の混合溶剤に加温溶解したもの。
（＊３）バルカム２９−１０１：ＢＴＬ ＳＰＥＣＩＡＬＴＹ ＲＥＳＩＮＳ社製、キシレノール／ホルムアルデヒド型フェノール樹脂、固形分１００％。
（＊４）サイメル３０３：三井サイテック社製、メチル化メラミン樹脂、固形分１００％。
（＊５）ＥＣＮ１２７３：旭化成エポキシ社製、オルソクレゾールノボラック型エポキシ樹脂、エポキシ当量２２０。
【００８９】
被覆用樹脂組成物（潤滑金属板用）
実施例２３及び２４並びに比較例１０
攪拌機を有する容器に後記表３に示す配合表に従って各原料を配合し、各被覆用樹脂組成物を作成した。
【００９０】
試験用塗板の作成
アルミニウム板（板厚０．３０ｍｍのアルミニウム合金３００４）の両面に、後記表３に示す各被覆用樹脂組成物を乾燥膜厚が５０ｍｇ／１００ｃｍ２となるように塗装した後、アルミニウム板温度が２７０℃に２５秒で達する条件で加熱し各塗装板を得た。
【００９１】
得られた塗装板について以下に示す試験方法により絞りしごき加工性及び耐腐食性を評価した。得られた結果を後記表３に示す。
【００９２】
試験方法
絞りしごき加工性：上記で得られた各塗装板を筒状に成形後、エリクセン社製金属薄板深絞り試験機１４２型を使用し、ブランク径８２ｍｍから下記表２に示す加工条件で１段〜５段に順を追って処理し、最終的に絞り率約３７％、しごき率約６０％の絞りしごき加工を施した。
【００９３】
【表２】
その際の絞りしごき加工性を以下の基準で評価した。
○：成形加工できる。
×：素材の破壊などが生じ、最後まで、成形加工できない。
【００９５】
耐腐食性：各塗装板について、ブランク打ち抜き、カッピング、Ｄ＆Ｉマシンによる絞りしごき（アイロニング）加工及びトリミングを順次施し、缶高さ１２５ｍｍ、外径６５ｍｍの缶を成形した。この缶の内面側に、エアレススプレー装置を用い、ＳＪ−６８３９−００９（関西ペイント社製、缶内面用塩化ビニル系塗料）を、乾燥膜厚が約１〜２μｍになるように塗装し、２００℃に６０秒間保持の条件で焼き付けた。さらに、フランジングマシンにより、アルミ蓋を巻き締められるようにフランジ加工を行い最終的に、２ピース缶を作成した。この２ピース缶に１０％のパインジュースを９８℃でホットパック充填した後アルミ蓋の巻締めを行い、３５℃で１ヶ月間保存した後開缶し、内面の腐食状態を観察し、以下の基準により評価した。
○：腐食が認められない。
△：腐食が僅かに認められる。
×：腐食が著しい。
【００９６】
【表３】
表３における各注（＊６）及び（＊７）の原料は各々下記の内容のものである。
（＊６）ＣＲＯＤＡＬＡＮ ＳＷＬ：クローダージャパン社製、精製ラノリンワックス、固形分１００％、軟化点３０〜３８℃
（＊７）ＨＩ−ＤＩＳＰＥＲ Ｆ−１０ＰＣ：岐阜セラック製造所社製、カルナバワックス、固形分１０％、軟化点８１〜８６℃
【００９８】
【発明の効果】
本発明のポリエステル樹脂分散液の製造方法を用いることにより、溶剤に溶解しない結晶性ポリエステル樹脂を溶剤に均一に分散させることができ、得られたポリエステル樹脂分散液の貯蔵安定性も極めて優れている。また、該ポリエステル樹脂分散液を用いた被覆用組成物を金属素材に塗装することにより、付着性、加工性、香味収着性、レトルト白化性、耐腐食性などに優れた性能を示し、特に缶内面被覆用樹脂組成物として適したものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a polyester resin dispersion obtained by dispersing a crystalline polyester resin in an organic solvent, and relates to a resin composition for coating using a polyester resin dispersion obtained by the production method. The present invention relates to a can body obtained by using the resin composition for coating and a method for producing the can body.
[0002]
[Prior art and its problems]
Conventionally, a resin containing a bisphenol A type epoxy resin has often been used as a resin for coating the inner surface of a can. However, in recent years, bisphenol A has been cited as one of the extrinsic endocrine disrupting chemicals (environmental hormones), and there has been a strong demand for the development of a paint in which bisphenol A does not elute from the coating film.
[0003]
Polyester resin has been studied as a substitute for epoxy resin, but it is not easy to satisfy the strict coating performance such as hardness, adhesion, anticorrosion, flavor retention required for coating for inner surface of can, It has become important to master high crystalline polyester resins such as PET resins.
[0004]
In recent years, from the problem of reducing the manufacturing cost of resin-coated can bodies and the treatment of press oil after molding, from the post-coating method in which a metal plate is formed into a can shape and then coating is performed, a pre-coated metal The precoat method of forming a flat plate into a can shape has been replaced by the use of a highly crystalline polyester resin having both hardness and workability as a paint.
[0005]
As a method of using a crystalline polyester resin, the use of a polyester film has been studied. For example, a method of thermally laminating a biaxially stretched thermoplastic film directly or via an adhesive to a metal plate ( For example, Japanese Unexamined Patent Application Publications Nos. H11-187, and H10-207, and a method of hot-melting a resin and directly extruding and laminating the metal on a metal plate (see, for example, H2, and the like) are disclosed. Has been
[0006]
However, the use of film lamination not only requires new capital investment, but the film lamination method is inferior in workability compared to painting, so the development of paints using such crystalline polyester resin has been developed. However, crystalline polyester resins generally have low solubility in solvents, and also have problems such as precipitation of crystals during storage. Had many problems. As one method for solving such a problem, a non-crystalline polyester resin soluble in an organic solvent and a crystalline polyester resin having a melting point of 90 to 180 ° C. are melted and mixed by heating and dissolved or dispersed in an organic solvent. A method is disclosed (for example, refer to Patent Document 4 and the like). However, there is a limit in this method, and when a highly crystalline polyester resin having a melting point of more than 190 ° C., which is necessary for a paint for the inner surface of a can, is used, crystals grow greatly during production or storage of a solution. However, there is a problem that the solution is greatly thickened or particles settle and aggregate.
[0007]
An object of the present invention is to provide a method for producing a polyester resin dispersion having excellent production stability and storage stability using a crystalline polyester resin.
[0008]
[Patent Document 1]
JP-A-56-10451
[Patent Document 2]
JP-A-57-65463
[Patent Document 3]
JP-A-51-17988
[Patent Document 4]
JP-A-4-164957
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, in the step of cooling the polyester resin solution to precipitate crystals, from the temperature rising temperature of the crystalline polyester resin to the glass transition temperature, It has been found that a fine and stable polyester resin dispersion can be produced by rapidly cooling the resin solution, and the present invention has been completed.
[0010]
Thus, according to the present invention, after heating and dissolving the crystalline polyester resin (A) and the non-crystalline polyester resin (B) in the organic solvent (C), the resin solution is heated to the temperature of the crystalline polyester resin (A). It is intended to provide a method for producing a polyester resin dispersion characterized by rapidly cooling at a speed of 2 ° C. or more per minute from a temperature not lower than the crystallization starting temperature to a temperature not higher than the glass transition temperature of the crystalline polyester resin (A). .
[0011]
The present invention also provides a coating resin composition using the polyester resin dispersion obtained by the above production method.
[0012]
The present invention further provides a can using the resin composition for coating, and a method for producing the can.
[0013]
Hereinafter, the present invention will be described in more detail.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The method for producing a polyester resin dispersion of the present invention is to rapidly cool a high-temperature resin solution in which a crystalline polyester resin and an amorphous polyester resin are dissolved in an organic solvent to precipitate crystals of the crystalline polyester resin. .
[0015]
Crystalline polyester resin (A)
The crystalline polyester resin, which is the component (A) of the polyester resin dispersion, comprises an esterified product of a polybasic acid component and a polyhydric alcohol component.
[0016]
Examples of the polybasic acid component include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride, and 2,6-naphthalenedicarboxylic acid. One or more dibasic acids selected from an acid, 1,6-hexanedicarboxylic acid and the like, and lower alkyl esters of these acids are mainly used, and if necessary, benzoic acid, crotonic acid, pt-butylbenzoic acid A monobasic acid such as an acid, a tribasic or higher polybasic acid such as trimellitic anhydride, methylcyclohexentricarboxylic acid, and pyromellitic anhydride are used in combination.
[0017]
Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, and butylethylpropane. Dihydric alcohols such as diols are mainly used, and if necessary, trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol can be used in combination. These polyhydric alcohols can be used alone or in combination of two or more. Esterification or transesterification of both components can be carried out by a method known per se.
[0018]
The crystalline polyester resin mainly uses terephthalic acid and 2,6-naphthalenedicarboxylic acid as acid components, and mainly uses ethylene glycol and 1,4-butanediol as polyhydric alcohol components. In particular, a polyethylene terephthalate-based resin mainly using terephthalic acid and ethylene glycol is preferable.
[0019]
The crystalline polyester resin used in the present invention has a melting point of 190 ° C. to 260 ° C., preferably 200 ° C. to 255 ° C., and a temperature rising crystallization starting temperature of 150 ° C. or more, preferably 155 ° C. to 195 ° C. Are suitable. Temperature rise of crystalline polyester resin If the crystallization start temperature is low, crystallization proceeds due to heat during retort sterilization and the film tends to whiten, and if the melting point of the crystalline polyester resin is low, the sorption and barrier properties of the film If the melting point is too high, the film-forming properties will be reduced.
[0020]
The measurement of the melting point of the crystalline polyester resin and the temperature at which the temperature of the crystal began to rise was measured using a scanning calorimeter (Shimadzu Corporation).
[0021]
Commercially available crystalline polyester resins include, for example, IFG8L, TG7N10, IP051 (all manufactured by Kanebo Gosen), KF-511 (Mitsubishi Rayon).
[0022]
Amorphous polyester resin (B)
The non-crystalline polyester resin, which is the component (B) of the polyester resin dispersion, has no clear melting point as measured by a differential scanning calorimeter, and is easily dissolved in an organic solvent at room temperature.
[0023]
The non-crystalline polyester resin is obtained by reacting a polybasic acid component and a polyhydric alcohol component in the same manner as the crystalline polyester resin, and the polybasic acid component and the polyhydric alcohol component as raw materials are the components of the crystalline polyester resin. The same ones as listed above can be used.
[0024]
For example, in the case of a polyethylene terephthalate resin, the crystallinity of the polyester resin can be changed by partially replacing the terephthalic acid as an acid component with another acid component such as isophthalic acid, and changing the polyhydric alcohol ethylene glycol into diethylene glycol or the like. Can be reduced and eliminated by partially replacing the alcohol component.
[0025]
Commercially available non-crystalline polyester resins include, for example, UE-3201, UE-3203, XA-0653 (all manufactured by Unitika), GK-880, GK-640 (all manufactured by Toyobo Co., Ltd.) and the like. .
[0026]
The compounding ratio of the crystalline polyester resin (A) and the non-crystalline polyester resin (B) is (A) / (B) = 60 / 40-5 / 95 by weight ratio, particularly 40 / 60-10 / 90. The range is preferred from the viewpoint of the retort resistance, corrosion resistance, and the like of the film obtained from the polyester resin dispersion.
[0027]
Organic solvent (C)
The organic solvent (C) used in the method for producing a polyester resin dispersion of the present invention can be used as long as it can dissolve the above-mentioned non-crystalline polyester resin, but 50% by weight or more in the organic solvent (C). Is preferably an organic solvent having a boiling point of 150 ° C. to 220 ° C. and containing no hydroxyl group, especially N-methyl-2-pyrrolidone from the viewpoint of the production stability of the polyester resin dispersion.
[0028]
Examples of the organic solvent having a boiling point of 150 ° C. to 220 ° C. and containing no hydroxyl group other than N-methyl-2-pyrrolidone include ketone solvents such as isophorone and cyclohexanone, DBE (manufactured by DuPont, dimethyl adipate, dimethyl glutarate, Ester solvents such as dimethyl succinate).
[0029]
Method for producing polyester resin dispersion
After heating and dissolving (A) the crystalline polyester resin and (B) the non-crystalline polyester resin in an organic solvent, as the resulting solution is cooled, the polyester resin crystallizes and precipitates. In general, cooling in the case of manufacturing in a tank or the like is slow at a rate of about 0.1 to 1 ° C. per minute, but when a polyester resin having a high melting point and high crystallinity is used, the diameter of precipitated polyester particles is reduced. As a result, the storability of the dispersion and the smoothness of the coating film obtained from the paint using the dispersion are significantly reduced.
[0030]
The production method of the present invention has solved the above-mentioned problem, and has a temperature of not less than the temperature at which the temperature of the crystalline polyester resin (A) rises from the crystallization start temperature to the temperature not more than the glass transition temperature of the crystalline polyester resin (A). It is important to quench at a speed of at least ℃.
[0031]
As the production apparatus, an apparatus for heating and dissolving the polyester resin and an apparatus for rapidly cooling the solution may be used.
[0032]
In the production of the polyester resin dispersion, first, a high-temperature resin solution in which the crystalline polyester resin (A) and the non-crystalline polyester resin (B) are dissolved in a solvent is prepared. There are no particular restrictions on the production procedure of the resin solution, for example,
{Circle around (1)} A method in which a solvent and a pellet-like crystalline polyester resin (A) are mixed, heated and dissolved while stirring, and then a non-crystalline polyester resin (B) is added.
{Circle around (2)} a method in which the solvent, the non-crystalline polyester resin (B) and the crystalline polyester resin (A) are all mixed and then heated and dissolved;
(3) a method in which the crystalline polyester resin (A) is gradually added to a solution in which the heated amorphous polyester resin (B) is dissolved,
and so on. The dissolution of the crystalline polyester resin (A) does not necessarily need to be raised to the melting point of the resin in the organic solvent, and is as low as possible within a range that does not cause a problem in workability as long as the temperature is higher than the temperature at which the resin starts to be heated. It is more preferable to avoid the decomposition of the polyester resin due to heat. Similarly, the addition of the non-crystalline polyester resin (B) is preferably slow in order to avoid decomposition of the resin, and the production method (1) is particularly preferable.
[0033]
After dissolving the polyester resin, it is cooled as quickly as possible according to the cooling conditions of the present invention. When heating, melting, and cooling are all performed in the same device (eg, tank), it is necessary to use a device having excellent cooling performance, or to select a place that meets the above-mentioned cooling conditions by reducing the charging amount. is there. In addition, the cooling step can be performed by heating and quenching separately from the dissolving device, and for example, a method of transferring the heated and dissolved polyester resin solution into a pre-cooled tank or a tube with a cooling device can be mentioned. Can be.
[0034]
Further, a part of the organic solvent (C) is sent to cooling and added at the time of cooling, so that it can be used as an auxiliary means for cooling.
[0035]
After cooling to a temperature below the glass transition temperature of the crystalline polyester resin (A), there is no particular limitation on the cooling rate thereafter.
[0036]
The polyester resin dispersion obtained as described above may be used alone or with another organic resin, a crosslinking agent, an additive (a curing catalyst, a lubricity imparting agent, an antifoaming agent, a leveling agent, an anti-agglomeration agent), a pigment. Coatings with excellent hardness, processability, adhesion, corrosion resistance, etc. by combining with commonly known coating composition raw materials such as organic pigments, inorganic pigments, brilliant pigments, extender pigments, rust preventive pigments, and organic solvents. For use in coating the inner surface of a can. Hereinafter, a coating resin composition using the polyester resin dispersion obtained by the method of the present invention will be described.
[0037]
Resin composition for coating
The polyester resin dispersion obtained by the method of the present invention can be used alone, but by combining a resin other than a polyester resin such as a resol type phenol resin, an amino resin, and an epoxy resin, retort resistance, adhesion, flavor properties, and the like. Can be further improved, and among these resins, a resol-type phenol resin and an epoxy resin are preferable.
[0038]
The resole type phenol resin is used as a crosslinking agent for the polyester resin. When the resole type phenol resin is used, the crystalline polyester resin (A) and the non-crystalline polyester resin (B ), In particular, the non-crystalline polyester resin (B) preferably has a hydroxyl value of about 5 to 100 mgKOH / g, preferably about 10 to 50 mgKOH / g.
[0039]
In addition, the resole type phenol resin, particularly, a phenol component and formaldehydes are heated in the presence of a reaction catalyst to cause a condensation reaction to introduce a methylol group. Those obtained by alkyl etherification are preferred.
[0040]
In the production of the resol-type phenolic resin cross-linking agent, a bifunctional phenol compound, a trifunctional phenol compound, a tetrafunctional or higher phenol compound, or the like can be used as the starting phenol component.
[0041]
Examples of the bifunctional phenol compound used for producing the resol type phenol resin crosslinking agent include o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, 2,5-xylenol and the like. Examples of the trifunctional phenol compound include phenol, m-cresol, m-ethylphenol, 3,5-xylenol, and m-methoxyphenol, and a tetrafunctional phenol compound. Examples of the compound include bisphenol A and bisphenol F. These phenol compounds can be used alone or in combination of two or more.
[0042]
The formaldehyde used in the production of the resole type phenol resin includes formaldehyde, paraformaldehyde, trioxane and the like, and they can be used alone or in combination of two or more.
[0043]
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, preferably 1 to 4 carbon atoms can be suitably used. Suitable monohydric alcohols include methanol, ethanol, n-propanol, n-butanol, isobutanol and the like.
[0044]
The compounding amount of the resol type phenol resin is 0.5 to 20 parts by weight, preferably 5 to 15 parts by weight based on 100 parts by weight of the total solid content of the crystalline polyester resin (A) and the non-crystalline polyester resin (B). The range of the part is suitable from the viewpoint of the balance between curability and workability.
[0045]
An acid catalyst can be added to the coating composition as needed to accelerate the curing reaction. For example, specific examples include acid catalysts such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and phosphoric acid, and amine neutralized products of these acids. Among them, the above-mentioned sulfonic acid compounds or amine neutralized sulfonic acid compounds are preferred.
[0046]
The amount of the acid catalyst is determined based on the amount of the acid (for example, in the case of an amine neutralized sulfonic acid compound, the amount of the remaining sulfonic acid compound obtained by removing the amine from the neutralized product) in view of the physical properties of the obtained coating film. ) Is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight based on 100 parts by weight of the total solid content of the crystalline polyester resin (A) and the non-crystalline polyester resin (B). Are suitable.
[0047]
The epoxy resin effectively acts as a cross-linking agent when the polyester resin contains a carboxyl group, but also when the polyester resin does not have a carboxyl group, the reinforcing material of the polyester resin or the resol-type phenol It effectively acts as a film-forming component by crosslinking with a resin.
[0048]
Addition of an epoxy resin improves hardness, adhesion, retort resistance and the like, but among them, a novolak type epoxy resin is preferable because it does not contain bisphenol A which is suspected of being an environmental hormone. Examples of the novolak epoxy resin include various novolak epoxy resins such as a phenol novolak epoxy resin, a cresol novolak epoxy resin, and a phenol glyoxal epoxy resin having a large number of epoxy groups in a molecule. Among them, a phenol novolak type epoxy resin and a cresol novolak type epoxy resin which are easy to balance the coating film performance are preferable.
[0049]
When the epoxy resin is used as a crosslinking agent for the polyester resin, at least one of the crystalline polyester resin (A) and the non-crystalline polyester resin (B) constituting the polyester resin dispersion, particularly the non-crystalline polyester resin (B ) Preferably has a carboxyl group of an acid value of 5 to 30 mgKOH / g, preferably 10 to 20 mgKOH / g. The compounding amount of the epoxy resin is 0.5 to 20 parts by weight, preferably 2 to 10 parts by weight based on 100 parts by weight of the total solid content of the crystalline polyester resin (A) and the non-crystalline polyester resin (B). The range is suitable from the viewpoint of the balance between curability and workability.
[0050]
When an epoxy resin is used as a crosslinking agent for a polyester resin, a basic catalyst can be added as necessary to accelerate the curing reaction. Specific examples thereof include choline chloride, nicotinamide, choline tartrate, aqueous choline, and tertiary amines such as dimethylethanolamine. Among them, choline chloride and nicotinamide are preferred.
[0051]
The blending amount of the basic catalyst is from 0.01 to 100 parts by weight based on the total solid content of the crystalline polyester resin (A) and the non-crystalline polyester resin (B) from the viewpoint of the physical properties of the obtained coating film. 5 parts by weight, preferably in the range of 0.05 to 1 part by weight, is suitable.
[0052]
The resin composition for coating of the present invention may be applied to the inner surface of a can body formed into a can shape by using a spray or the like, but a known coating method such as a roll coater or a curtain flow coater may be applied to a flat metal plate. After coating and drying by the method, the coated metal plate may be cut and formed into a can to form a can. When the latter manufacturing method is used, wax may be added to the coating resin composition in order to suppress the occurrence of scratches during transportation and molding.
[0053]
Wax is added to adjust the dynamic friction coefficient of the obtained film, and the softening point of the wax is 30 ° C. or more, preferably 33 to 150 ° C. to adjust the dynamic friction coefficient at high temperature. Suitable waxes include, for example, waxes such as fatty acid ester wax, which is an esterified product of a polyol compound and a fatty acid, silicon-based wax, fluorine-based wax, polyolefin wax, animal-based wax, and plant-based wax.
[0054]
Examples of the polyol compound serving as a raw material of the fatty acid ester wax include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and glycerin. , Di or higher polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like. Of these, polyol compounds having three or more hydroxyl groups in one molecule are preferable, and polyglycerin, trimethylolpropane, and pentaerythritol are particularly preferable.
[0055]
The fatty acid used as the other raw material of the fatty acid ester wax may be a saturated or unsaturated fatty acid, and is preferably a fatty acid having 6 to 32 carbon atoms. Specific examples of suitable fatty acids include saturated fatty acids such as caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, cerotic acid, montanic acid, mericinic acid; Unsaturated fatty acids such as acids, undecylenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, setreic acid, erucic acid, ricanoic acid, ricinoleic acid, and arachidonic acid can be mentioned. As the fatty acid ester wax, one in which at least 1/3 of the number of hydroxyl groups of the polyol compound is esterified with a fatty acid is preferable.
[0056]
Examples of the silicon-based wax include BYK-300, BYK-320, BYK-330 [manufactured by BYK Chemie (BIC Chemie)], Silwet L-77, L-720, L-7602 [manufactured by Nippon Konica Corporation. Co., Ltd.], Paintad 29, 32, M (above, manufactured by Dow Corning), Shin-Etsu Silicone KF-96 (Shin-Etsu Chemical Co., Ltd.) and the like. Rockwax SST-1MG, SST-3, FluoroSlip 231 (both manufactured by Shamrock Chemicals), POLYFLUO (Polyfluo) 120, 150, and 400 (Micro Powders).
[0057]
Examples of the polyolefin wax include shamrock wax S-394 and shamrock S-395 (all manufactured by Shamrock Chemicals), Hoechst wax PE-520 and PE-521 (all manufactured by Hoechst), Mitsui High Wax [ Manufactured by Mitsui Petrochemical Industry Co., Ltd.], and animal waxes include, for example, lanolin and beeswax, and vegetable waxes include, for example, carnauba wax and water wax.
[0058]
The wax can be used alone or in combination of two or more, and the amount of the wax added is preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total solid content of the resin component in the coating resin composition. Is suitably in the range of 0.5 to 2 parts by weight.
[0059]
The coating amount when the coating composition is used for the inner surface of a can is 50 to 180 mg / 100 cm in dry application amount.2, Preferably 85 to 150 mg / 100 cm2Is preferably within the range. The baking condition of the coating film is usually about 15 seconds to about 30 minutes under conditions where the maximum temperature of the metal plate is about 190 to 300 ° C.
[0060]
Examples of the material of the can include metals such as untreated steel sheets, tin-plated steel sheets, galvanized steel sheets, chromium-plated steel sheets, phosphate-treated steel sheets, chromate-treated steel sheets, untreated aluminum sheets, and chromate-treated aluminum sheets. Materials can be mentioned.
[0061]
In a method for producing a can body in which the coating composition of the present invention is applied to a flat metal plate, dried, cut, and formed into a can shape, the inner surface of the formed can body is further coated with a paint for can inner surface by spraying or the like. May be painted. As the paint for the inner surface of the can, a conventionally known paint can be used, and the coating composition of the present invention can be used. Thus, by further applying the paint for the inner surface of the can after molding into a can, it is possible to protect the scratches and the like generated during the molding and the like, and it is possible to greatly improve the retort resistance and the like. In addition, when further coating the paint for the inner surface of the can after molding, it is preferable from the viewpoint of economics to suppress the coating film thickness of the coating resin composition of the present invention on a metal flat plate from the viewpoint of economics, and the economics and the coating film From the viewpoint of lubricity, 10 to 85 mg / 100 cm in dry application amount2, Especially 15-60mg / 100cm2The degree is suitable.
[0062]
The paint for the inner surface of the can to be applied after the above-mentioned molding can be used without any particular limitation, such as a solvent-based paint or a water-based paint, and its film thickness may be thin enough to repair a damaged part.
[0063]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. Hereinafter, both “parts” and “%” are based on weight.
[0064]
Production of polyester resin dispersion
Example 1
6 parts of a crystalline polyester resin KF511 (manufactured by Mitsubishi Rayon Co., Ltd., crystalline polyester resin, Tg 60 ° C., Tc [heating temperature to start crystallization] 156 ° C., Tm [melting point] 214 ° C.) and 24 parts of N-methyl-2-pyrrolidone The mixture was charged into a four-necked flask equipped with a condenser and purged with nitrogen gas, and heated to about 200 ° C. with a mantle heater while stirring with a stirring blade to completely dissolve KF511. Next, the heating was stopped and 46 parts of DBE (a mixed solvent of dimethyl adipate, dimethyl glutarate, and dimethyl succinate, manufactured by DuPont) was dropped, and then an amorphous polyester resin GK880 (a non-crystalline polyester manufactured by Toyobo Co., Ltd.) 24 parts of resin (Tg: 84 ° C.) were charged and stirred until completely dissolved, followed by cooling to 160 ° C. This solution was cooled at a rate of 5 ° C./min from a cooling start temperature of 160 ° C. to a cooling end temperature of 55 ° C. to obtain a polyester resin dispersion R1 having a solid content of 30% and a particle diameter of about 5 μm. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0065]
Example 2
A polyester resin dispersion having a solid content of 30% and a particle size of about 5 μm in the same manner as in Example 1 except that the cooling from the cooling start temperature of 160 ° C. to the cooling end temperature of 55 ° C. is performed at a rate of 3 ° C./min. R2 was obtained. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0066]
Example 3
A polyester resin dispersion R3 having a solid content of 30% and a particle diameter of about 5 μm was obtained in the same manner as in Example 1 except that the cooling start temperature was changed to 180 ° C. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0067]
Example 4
A polyester resin dispersion R4 having a solid content of 30% and a particle size of about 5 μm was obtained in the same manner as in Example 1 except that isophorone was used instead of DBE in Example 1. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0068]
Example 5
In the same manner as in Example 1 except that 23 parts of DBE and 23 parts of Solvesso 100 (manufactured by ExxonMobil Co., Ltd., aromatic hydrocarbon solvent) were used instead of 46 parts of DBE, the solid content was 30% and the particle size was about 30%. A 5 μm polyester resin dispersion R5 was obtained. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0069]
Example 6
A polyester resin dispersion R6 having a solid content of 30% and a particle diameter of about 5 μm was obtained in the same manner as in Example 1, except that 11 parts of DBE and 35 parts of methyl ethyl ketone were used instead of 46 parts of DBE. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0070]
Example 7
A polyester resin dispersion R7 having a solid content of 30% and a particle size of about 5 μm was obtained in the same manner as in Example 1, except that 24 parts of isophorone was used instead of 24 parts of N-methyl-2-pyrrolidone. . Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0071]
Example 8
6 parts of a crystalline polyester resin TG7N10 (manufactured by Kanebo Gosen Co., Ltd., crystalline polyester resin, Tg 79 ° C., Tc 190 ° C., Tm 230 ° C.) and 4 parts of N-methyl-2-pyrrolidone with nitrogen gas replaced with a cooling pipe and four ports The TG7N10 was charged into a flask and heated to about 220 ° C. with a mantle heater while stirring with a stirring blade to completely dissolve TG7N10. Next, the heating was stopped, and 46 parts of DBE was dropped, and 24 parts of a non-crystalline polyester resin UE3201 (manufactured by Unitika Ltd., non-crystalline polyester resin, Tg 65 ° C) was charged and stirred until completely dissolved, followed by cooling to 195 ° C. This solution was cooled at a rate of 5 ° C./min from a cooling start temperature of 195 ° C. to a cooling end temperature of 75 ° C. to obtain a polyester resin dispersion R8 having a solid content of 30% and a particle diameter of about 5 μm. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0072]
Example 9
17 parts of crystalline polyester resin KF511, 13 parts of non-crystalline polyester resin UE3203 (a non-crystalline polyester resin, manufactured by Unitika Ltd., Tg 60 ° C.), 24 parts of N-methyl-2-pyrrolidone and 46 parts of DBE were fitted with a cooling tube. The mixture was charged into a four-necked flask purged with nitrogen gas, heated to 190 ° C. with a mantle heater while stirring with a stirring blade, and stirred until the resin was dissolved. This solution was cooled at a rate of 4 ° C./min from a cooling start temperature of 190 ° C. to a cooling end temperature of 55 ° C. to obtain a polyester resin dispersion R9 having a solid content of 30% and a particle diameter of about 5 μm. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0073]
Example 10
A solid was prepared in the same manner as in Example 1 except that XA-0653 (a non-crystalline polyester resin, Tg 58 ° C, acid value 20 mgKOH / g, manufactured by Unitika Ltd.) was used instead of the non-crystalline polyester resin GK880 in Example 1. A polyester resin dispersion R13 having a particle size of about 5 μm with a particle size of 30% was obtained. Even when the polyester resin dispersion was stored at 20 ° C. for one month, no precipitation or thickening was observed, and the polyester resin dispersion was stable.
[0074]
Comparative Example 1
A polyester resin dispersion having a solid content of 30% and a particle diameter of about 20 μm in the same manner as in Example 1 except that the temperature from the cooling start temperature of 160 ° C. to the cooling end temperature of 55 ° C. is cooled at a rate of 1 ° C./min. R10 was obtained. When the polyester resin dispersion was stored at 20 ° C. for one month, a precipitate was observed.
[0075]
Comparative Example 2
Example 1 Example 1 was repeated except that the cooling start temperature was 160 ° C. to the cooling end temperature 55 ° C., the cooling was from 160 ° C. to 80 ° C. at 5 ° C./min, and the cooling from 80 ° C. to 55 ° C. was 1 ° C./min. In the same manner as in the above, a polyester resin dispersion R11 having a solid content of 30% and a particle diameter of about 10 μm was obtained. When the polyester resin dispersion was stored at 20 ° C. for one month, a precipitate was observed.
[0076]
Comparative Example 3
Example 1 Example 1 was repeated except that the cooling start temperature was 160 ° C. to the cooling end temperature 55 ° C., the cooling rate was 160 ° C. to 120 ° C. at a rate of 1 ° C./min, and the cooling temperature from 120 ° C. to 55 ° C. was 5 ° C./min. In the same manner as in the above, a polyester resin dispersion R12 having a solid content of 30% and a particle diameter of about 15 μm was obtained. When the polyester resin dispersion was stored at 20 ° C. for one month, a precipitate was observed.
[0077]
Comparative Example 4
Produced in the same manner as in Example 1 except that the amount of the crystalline polyester resin KF511 was changed from 6 parts to 21 parts and the amount of the non-crystalline polyester resin GK880 was changed from 24 parts to 9 parts. As a result, a paste was obtained, and no dispersion was obtained.
[0078]
Resin composition for coating (for inner surface of can)
Examples 11 to 22 and Comparative Examples 5 to 9
Each raw material was blended in a container having a stirrer according to a blending table shown in Table 1 below to prepare a resin composition for coating the inner surface of each can.
[0079]
How to make a painted plate
Each of the above-mentioned resin compositions for coating the inner surface of a can, Dry film weight is 100cm on 5052 aluminum plate2Each was coated with a bar coater so as to give a coating weight of 120 mg and baked and dried under the condition that the aluminum plate reached 270 ° C. in 20 seconds to prepare each coated plate.
[0080]
Each coated plate obtained by the above-described method for preparing a coated plate was evaluated for the coated surface condition, adhesion, workability, perfume sorption, retort resistance, and corrosion resistance according to the following test methods.
[0081]
Test method
Coating surface condition: The coating surface of the coated plate was visually observed and evaluated according to the following criteria.
：: The entire coated surface is smooth.
Δ: Slight irregularities are observed on the entire coated surface.
×: Large irregularities are observed on the entire coated surface.
[0082]
Adhesiveness: When using a knife to make a coating film on a painted plate with a knife of about 1.5 mm in width and 11 cuts in each of vertical and horizontal directions, a 24 mm width cellophane adhesive tape is adhered and strongly peeled off. The coating film at the goban eye was observed and evaluated according to the following criteria.
A: No peeling was observed.
：: Slight peeling is observed.
Δ: considerable peeling is observed.
X: Remarkable peeling is observed.
[0083]
Workability: A 180-degree bent part with the coating surface outside at the lower part of the coated plate, and a 1kg iron with a flat contact surface on this bent part using a special goby fold type Dupont impact tester The length of the crack in the coating film at the bent portion generated when the weight was dropped from a height of 50 cm was measured and evaluated according to the following criteria.
：: less than 5 mm.
Δ: 5 mm or more and less than 10 mm.
X: 10 mm or more.
[0084]
Perfume sorption property: The coated plate is immersed in a solution of 30 mg / l of d-limonene solution dispersed in deionized water at 1 g / l of S-1170 (sucrose fatty acid ester manufactured by Mitsubishi Chemical Corporation) at 35 ° C. for 1 month Stored. After storage, d-limonene sorbed on the coating film was extracted with diethyl ether at 20 ° C. for one week, and the sorbed amount was measured by gas chromatography, and evaluated according to the following criteria.
：: Less than 0.6 mg per 120 mg of coating film weight.
Δ: 0.6 mg or more and less than 1.6 mg per 120 mg of coating film weight.
X: 1.6 mg or more per 120 mg of coating film weight.
[0085]
Retort resistance: After the coated plate was immersed in deionized water at 125 ° C. for 35 minutes and pulled up in an autoclave, the whitening state of the coating film was observed and evaluated according to the following criteria.
：: slight whitening is observed in the coating film.
Δ: considerable whitening is observed in the coating film.
X: Remarkable whitening is observed in the coating film.
[0086]
Corrosion resistance: Immerse a coated plate coated with tape or the like in 10% pine juice in a container that can be sealed to prevent corrosion on the back surface, seal and store at 35 ° C for one month, then corrosion of the painted surface Was observed and evaluated according to the following criteria.
：: No corrosion was observed.
Δ: Corrosion is considerably observed.
X: Corrosion is remarkable.
[0087]
[Table 1]
The raw materials of each note (* 1) to (* 5) in Table 1 have the following contents.
(* 1) 30% GK-880: 30% of non-crystalline polyester resin GK-880 heated and dissolved in a mixed solvent of 24 parts of N-methyl-2-pyrrolidone and 46 parts of DBE.
(* 2) 30% Epicoat 1009: 30 parts of Epicoat 1009 (manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 3,500, number average molecular weight about 3,750) mixed with 45 parts of methyl ethyl ketone and 25 parts of butyl cellosolve Heated and dissolved in a solvent.
(* 3) Balcum 29-101: manufactured by BTL SPECIALTY RESINS, xylenol / formaldehyde type phenol resin, solid content 100%.
(* 4) Cymel 303: manufactured by Mitsui Cytec, methylated melamine resin, solid content 100%.
(* 5) ECN1273: Orthocresol novolak type epoxy resin manufactured by Asahi Kasei Epoxy Co., epoxy equivalent 220.
[0089]
Resin composition for coating (for lubricating metal plate)
Examples 23 and 24 and Comparative Example 10
Each raw material was blended in a container having a stirrer according to the blending table shown in Table 3 below to prepare each coating resin composition.
[0090]
Preparation of test painted plate
On both surfaces of an aluminum plate (aluminum alloy 3004 having a plate thickness of 0.30 mm), each coating resin composition shown in Table 3 described below was dried at a film thickness of 50 mg / 100 cm.2Then, the coating was heated under the condition that the temperature of the aluminum plate reached 270 ° C. in 25 seconds to obtain each coated plate.
[0091]
The obtained coated plate was evaluated for drawing and ironing workability and corrosion resistance by the following test methods. The results obtained are shown in Table 3 below.
[0092]
Test method
Drawing and ironing processability: After forming each coated plate obtained above into a cylindrical shape, using a metal sheet deep drawing tester type 142 manufactured by Ericssen Co., Ltd., from a blank diameter of 82 mm under the processing conditions shown in Table 2 below, from 1 step to The processing was performed sequentially in five stages, and finally a drawing and ironing process with a drawing ratio of about 37% and a drawing rate of about 60% was performed.
[0093]
[Table 2]
The draw and ironability at that time was evaluated based on the following criteria.
：: Formable.
×: Destruction of the material occurs, and molding cannot be performed until the end.
[0095]
Corrosion resistance: Each coated plate was subjected to blank punching, cupping, drawing and ironing (ironing) by a D & I machine, and trimming in order to form a can having a can height of 125 mm and an outer diameter of 65 mm. Using an airless spray device, SJ-6839-009 (manufactured by Kansai Paint Co., Ltd., vinyl chloride paint for the inner surface of the can) was applied to the inner surface of the can so that the dry film thickness was about 1 to 2 μm. It was baked at 60 ° C. for 60 seconds. Further, the aluminum cover was subjected to flange processing by a flanging machine so that the aluminum lid could be tightened, and finally a two-piece can was produced. This 2-piece can was hot-packed with 98% pine juice at 98 ° C, then the aluminum lid was tightened, stored at 35 ° C for 1 month, opened and observed the corrosion state of the inner surface. The evaluation was based on criteria.
：: No corrosion was observed.
Δ: Corrosion is slightly observed.
X: Corrosion is remarkable.
[0096]
[Table 3]
The raw materials of each note (* 6) and (* 7) in Table 3 have the following contents.
(* 6) CRODALAN SWL: Clauder Japan, refined lanolin wax, solid content 100%, softening point 30-38 ° C
(* 7) HI-DISPER F-10PC: manufactured by Gifu Shellac Mfg. Co., Ltd., carnauba wax, solid content 10%, softening point 81-86 ° C
[0098]
【The invention's effect】
By using the method for producing a polyester resin dispersion of the present invention, a crystalline polyester resin that does not dissolve in a solvent can be uniformly dispersed in a solvent, and the storage stability of the obtained polyester resin dispersion is extremely excellent. . In addition, by coating the coating composition using the polyester resin dispersion liquid on a metal material, adhesion, processability, flavor sorption, retort whitening, excellent performance such as corrosion resistance, particularly exhibiting performance It is suitable as a resin composition for coating the inner surface of a can.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003015482A JP4223820B2 (en) | 2002-01-28 | 2003-01-24 | Method for producing polyester resin dispersion |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002017847 | 2002-01-28 | ||
| JP2002123275 | 2002-04-25 | ||
| JP2003015482A JP4223820B2 (en) | 2002-01-28 | 2003-01-24 | Method for producing polyester resin dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004002671A true JP2004002671A (en) | 2004-01-08 |
| JP4223820B2 JP4223820B2 (en) | 2009-02-12 |
Family
ID=30449095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003015482A Expired - Fee Related JP4223820B2 (en) | 2002-01-28 | 2003-01-24 | Method for producing polyester resin dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4223820B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246603A (en) * | 2006-03-14 | 2007-09-27 | Kansai Paint Co Ltd | Can coating composition |
| JP2008150442A (en) * | 2006-12-15 | 2008-07-03 | Toyobo Co Ltd | Coating composition, laminate and flexible flat cable |
| KR100888664B1 (en) * | 2006-06-16 | 2009-03-13 | 간사이 페인트 가부시키가이샤 | Both-side coated steel for can |
| JP2009120641A (en) * | 2007-11-12 | 2009-06-04 | Unitika Ltd | Copolyester resin pellet and method for producing the same |
| WO2013111814A1 (en) * | 2012-01-27 | 2013-08-01 | Dic株式会社 | Coating composition, can coating containing same, and can inner surface coating metal material coated with said can coating |
| JP2021123718A (en) * | 2020-02-03 | 2021-08-30 | 東洋製罐グループホールディングス株式会社 | Coating composition, coated metal plate, drawn and ironed can, and method for manufacturing the same |
-
2003
- 2003-01-24 JP JP2003015482A patent/JP4223820B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007246603A (en) * | 2006-03-14 | 2007-09-27 | Kansai Paint Co Ltd | Can coating composition |
| KR100888664B1 (en) * | 2006-06-16 | 2009-03-13 | 간사이 페인트 가부시키가이샤 | Both-side coated steel for can |
| JP2008150442A (en) * | 2006-12-15 | 2008-07-03 | Toyobo Co Ltd | Coating composition, laminate and flexible flat cable |
| JP2009120641A (en) * | 2007-11-12 | 2009-06-04 | Unitika Ltd | Copolyester resin pellet and method for producing the same |
| WO2013111814A1 (en) * | 2012-01-27 | 2013-08-01 | Dic株式会社 | Coating composition, can coating containing same, and can inner surface coating metal material coated with said can coating |
| CN104080867A (en) * | 2012-01-27 | 2014-10-01 | Dic株式会社 | Coating composition, can coating containing same, and coating metal material for can inner surface coating coated with the can coating |
| JP2021123718A (en) * | 2020-02-03 | 2021-08-30 | 東洋製罐グループホールディングス株式会社 | Coating composition, coated metal plate, drawn and ironed can, and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4223820B2 (en) | 2009-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104379687B (en) | Coating composition and the coated metal plate, canister and metal cover for being coated with the coating composition | |
| JP4091266B2 (en) | Lubricated steel plate with excellent drawing and ironing workability | |
| EP1273626B1 (en) | Aqueous resin composition, aqueous coating material containing the composition, coating provided by the material, and metal plate coated with the material | |
| RU2557624C2 (en) | Water dispersion of polymers | |
| WO2013111814A1 (en) | Coating composition, can coating containing same, and can inner surface coating metal material coated with said can coating | |
| JP5611697B2 (en) | Resin composition | |
| CN103619718A (en) | Phosphorus-containing acid acidified polyester and coating composition containing it | |
| JP2008018713A (en) | Double-side coated steel plate for can | |
| JP6257385B2 (en) | Paint composition | |
| KR100852477B1 (en) | Can coating composition | |
| JP3872892B2 (en) | Paint composition | |
| JP6253553B2 (en) | Paint composition | |
| JP6242000B2 (en) | Coating composition and metal can | |
| JP4223820B2 (en) | Method for producing polyester resin dispersion | |
| JP4223824B2 (en) | Polyester resin dispersion | |
| JP5766416B2 (en) | Resin composition for paint | |
| JP2003246006A (en) | Coated metal sheet for can | |
| JP3453091B2 (en) | Paint composition | |
| JP2011246717A (en) | Powder coating compositions, mid-gloss range coatings, related methods and substrates | |
| JP2002201411A (en) | Coating composition | |
| JP2023066362A (en) | Coating composition | |
| WO2023100402A1 (en) | Coating composition | |
| JP4554502B2 (en) | Paint for canned outer surface | |
| JP7808748B2 (en) | Polyester resin dispersions, coatings, can ends, and can bodies | |
| JP7525078B1 (en) | Aqueous dispersion of polyester resin, coating material, method for manufacturing can end, and method for manufacturing can body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060123 |
|
| A977 | Report on retrieval |
Effective date: 20080822 Free format text: JAPANESE INTERMEDIATE CODE: A971007 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20080902 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081023 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081118 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Effective date: 20081120 Free format text: JAPANESE INTERMEDIATE CODE: A61 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 3 Free format text: PAYMENT UNTIL: 20111128 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 3 Free format text: PAYMENT UNTIL: 20111128 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111128 Year of fee payment: 3 |
|
| LAPS | Cancellation because of no payment of annual fees |