JP4223824B2 - Polyester resin dispersion - Google Patents
Polyester resin dispersion Download PDFInfo
- Publication number
- JP4223824B2 JP4223824B2 JP2003033069A JP2003033069A JP4223824B2 JP 4223824 B2 JP4223824 B2 JP 4223824B2 JP 2003033069 A JP2003033069 A JP 2003033069A JP 2003033069 A JP2003033069 A JP 2003033069A JP 4223824 B2 JP4223824 B2 JP 4223824B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- crystalline polyester
- parts
- coating
- resin
- 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.)
- Expired - Fee Related
Links
- 229920001225 polyester resin Polymers 0.000 title claims description 226
- 239000004645 polyester resin Substances 0.000 title claims description 226
- 239000006185 dispersion Substances 0.000 title claims description 100
- 238000000576 coating method Methods 0.000 claims description 71
- 239000011248 coating agent Substances 0.000 claims description 67
- 239000007787 solid Substances 0.000 claims description 39
- -1 phosphoric acid compound Chemical class 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 239000011342 resin composition Substances 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 24
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 17
- 230000000630 rising effect Effects 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 description 38
- 238000003860 storage Methods 0.000 description 38
- 239000002245 particle Substances 0.000 description 34
- 238000001556 precipitation Methods 0.000 description 29
- 230000008719 thickening Effects 0.000 description 27
- 239000001993 wax Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000003973 paint Substances 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 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
- 238000010438 heat treatment Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 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
- 229920003987 resole Polymers 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 238000010409 ironing Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229920000297 Rayon Polymers 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 150000007519 polyprotic acids Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000010998 test method Methods 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
- 230000000694 effects Effects 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 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
- 239000000463 material Substances 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
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 240000007930 Oxalis acetosella Species 0.000 description 3
- 235000008098 Oxalis acetosella Nutrition 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
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 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
- 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
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-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
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-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
- 239000012164 animal wax Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000004203 carnauba wax Substances 0.000 description 2
- 235000013869 carnauba wax Nutrition 0.000 description 2
- 239000003054 catalyst Substances 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
- 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 235000011187 glycerol Nutrition 0.000 description 2
- 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 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
- 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
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- 235000003441 saturated fatty acids Nutrition 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
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- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 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
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
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- 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
- 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
- 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
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- 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
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- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 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
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- 239000008397 galvanized steel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 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
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- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 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
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- 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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Landscapes
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- Paints Or Removers (AREA)
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に関するものであり、該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、缶内面用皮膜に要求される、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、貯蔵安定性及びロール塗装性の優れたポリエステル樹脂分散液およびその製造方法を提供することであり、該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、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に特定リン酸系化合物を添加したものを有機溶剤中に分散することにより極めて貯蔵安定性のよいポリエステル樹脂分散液が得られることを見出し、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）、非結晶性ポリエステル樹脂（Ｂ）及び下記式（１）に示すリン酸系化合物（Ｃ）の混合物が有機溶剤（Ｄ）中に分散されてなるポリエステル樹脂分散液を提供するものである。
【００１１】
【化２】
Ｒ１、Ｒ２及びＲ３はそれぞれ同一又は異なって炭素数６以上の脂肪族もしくは芳香族炭化水素、又は−ＣｍＨ２ｍＯＣｎＨ２ｎ＋１を表し、ｍ及びｎは１以上の整数であって且つｍ＋ｎが６以上の整数である。
【００１３】
また、本発明は、上記結晶性ポリエステル樹脂（Ａ）、非結晶性ポリエステル樹脂（Ｂ）、リン酸系化合物（Ｃ）及び有機溶剤（Ｄ）を加熱、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。
【００１４】
また、本発明は、上記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。
【００１５】
さらに、本発明は、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。
【００１６】
以下、本発明についてさらに詳細に説明する。
【００１７】
【発明の実施の形態】
本発明のポリエステル樹脂分散液は、結晶性ポリエステル樹脂（Ａ）、非結晶性ポリエステル樹脂（Ｂ）及びリン酸系化合物（Ｃ）を有機溶剤（Ｄ）中に分散させてなるものである。
【００１８】
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。
【００１９】
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。
【００２０】
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。
【００２１】
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。
【００２２】
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。
【００２３】
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。
【００２４】
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。
【００２５】
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く、常温で有機溶剤に溶解するものをいう。
【００２６】
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じ物を使用することができる。
【００２７】
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又はなくすことができる。
【００２８】
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。
【００２９】
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）＝９５／５〜５／９５、特に６０／４０〜１０／９０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。
【００３０】
リン酸系化合物（Ｃ）
本発明のリン酸系化合物は下記式（１）に示す構造を持つものであり、ポリエステル樹脂分散時に界面活性剤として作用し、分散粒子径が細かくなるだけでなく、得られたポリエステル樹脂分散液の粒子同士の合一を妨げ、分散系を安定化させる働きを持つと考えられる。
【００３１】
【化３】
Ｒ１、Ｒ２及びＲ３はそれぞれ同一又は異なって炭素数６以上の脂肪族もしくは芳香族炭化水素、又は−ＣｍＨ２ｍＯＣｎＨ２ｎ＋１を表し、ｍ及びｎは１以上の整数であって且つｍ＋ｎが６以上の整数である。
【００３３】
上記リン酸系化合物（Ｃ）としては、例えば２−エチルヘキシルジフェニルホスフェート、トリス（２−エチルヘキシル）ホスフェート、トリス（ブトキシエチル）ホスフェート、トリフェニルホスフェート、トリクレジルホスフェートなどが挙げられる。
【００３４】
リン酸系化合物（Ｃ）の配合量としては、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０．１〜２０重量部、好ましくは１〜１５重量部の範囲内が得られるポリエステル樹脂分散液の貯蔵安定性の観点から適している。
【００３５】
有機溶剤（Ｄ）
本発明のポリエステル樹脂分散液の製造に用いられる有機溶剤（Ｄ）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（Ｄ）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く、例えばＮ−メチル−２−ピロリドン、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。
【００３６】
ポリエステル樹脂分散液の製造方法
結晶性ポリエステル樹脂（Ａ）、非結晶性ポリエステル樹脂（Ｂ）及びリン酸系化合物（Ｃ）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、析出することによりポリエステル樹脂分散液を得ることができる。
【００３７】
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、冷却速度が遅いほど析出したポリエステル粒子の径が大きくなり、分散液の安定性は低下する。その影響はポリエステル樹脂分散液又は該分散液を用いた被覆用組成物の貯蔵安定性の低下として主に現れるが、貯蔵安定性がそれほど低下しないものでも、ロール塗装のような強いシェアーがかかると分散粒子同志の融着などが起こったり、通常のロール塗装機では塗れない程の高粘度になって、うまく塗装できないという現象も現れる。ポリエステル樹脂分散液の安定性は、特に結晶性ポリエステル樹脂（Ａ）の昇温結晶開始温度から結晶性ポリエステル樹脂（Ａ）のガラス転移温度までの冷却速度が大きく寄与しており、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の冷却速度を２℃／分以上、好ましくは３〜１０℃／分で行うことにより貯蔵安定性及びロール塗装性の良いポリエステル樹脂分散液を得ることができる。
【００３８】
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。
【００３９】
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）及び非結晶性ポリエステル樹脂（Ｂ）が溶解された高温、好ましくは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の樹脂溶液を作成する。
【００４０】
高温樹脂溶液の製造手順には特に制限はなく、例えば
▲１▼有機溶剤（Ｄ）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▼有機溶剤（Ｄ）、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）を有機溶剤（Ｄ）に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。
【００４１】
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。
【００４２】
さらに、有機溶剤（Ｄ）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。
【００４３】
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。
【００４４】
また、リン酸系化合物（Ｃ）は冷却後に添加しても貯蔵安定性に効果は見られるが、冷却中又は冷却前に添加する方がポリエステル樹脂分散液の安定性におよぼす効果は大きく、特に冷却前に添加することが好ましい。
【００４５】
被覆用樹脂組成物
本発明の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る。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。
【００４６】
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。
【００４７】
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。
【００４８】
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。
【００４９】
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。
【００５０】
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。
【００５１】
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。
【００５２】
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。
【００５３】
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。
【００５４】
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。
【００５５】
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。
【００５６】
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。
【００５７】
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。
【００５８】
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。
【００５９】
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。
【００６０】
上記被覆用組成物には、さらに必要に応じて、その他の有機樹脂、添加剤（ワックス、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原料と組み合わせることができる。
【００６１】
本発明の被覆用樹脂組成物は、缶内外面用、プレコート鋼板用、自動車用等の塗料として好適に用いることができるが、特に缶内外面用に適している。
【００６２】
本発明の被覆用樹脂組成物を缶用として使用する場合には、缶状に成形された缶体の内面及び／又は外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中にワックスを添加するのが好ましい。
【００６３】
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。
【００６４】
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。
【００６５】
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。
【００６６】
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。
【００６７】
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、ラノリンワックス、蜜ろう等が挙げられ、植物系ワックスとしては、例えば、カルナバワックス、水ろう等が挙げられる。
【００６８】
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。
【００６９】
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。
【００７０】
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。
【００７１】
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。
【００７２】
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。
【００７３】
【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。
【００７４】
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℃）１２部及び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）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、シクロヘキサノン３１部とソルベッソ１００（エクソンモービル社製、芳香族系炭化水素溶剤）１５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℃）１８部を仕込み完全に溶解するまで攪拌し１６０℃まで冷却した。この溶液に２−エチルヘキシルジフェニルホスフェートを５部仕込み、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、固形分約３３％、粒子径約５μｍ、粘度２３０ｍＰａｓ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。
【００７５】
なお、ポリエステル樹脂分散液の粘度はコーンプレート型粘度計（トキメック社製、ＴＶ−２０形）を用い、標準ローターにて２０ｒｐｍ、２５℃の条件で測定した。
【００７６】
実施例２
実施例１において２−エチルヘキシルジフェニルホスフェートの替わりにＴＯＰ（大八化学工業社製、トリス（２−エチルヘキシル）ホスフェート）を使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度２００ｍＰａｓ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。
【００７７】
実施例３
実施例１において２−エチルヘキシルジフェニルホスフェートの替わりにＴＢＸＰ（大八化学工業社製、トリス（ブトキシエチル）ホスフェート）を使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度２００ｍＰａｓ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。
【００７８】
実施例４
実施例１において２−エチルヘキシルジフェニルホスフェートの替わりにＴＰＰ（大八化学工業社製、トリフェニルホスフェート）を使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度５００ｍＰａｓ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。
【００７９】
実施例５
実施例１において２−エチルヘキシルジフェニルホスフェートの替わりにＴＣＰ（大八化学工業社製、トリクレジルホスフェート）を使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度５５０ｍＰａｓ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。
【００８０】
実施例６
実施例１において配合量を、結晶性ポリエステル樹脂ＫＦ５１１を１８部、非結晶性ポリエステル樹脂ＧＫ８８０を１２部及び２−エチルヘキシルジフェニルホスフェートを１０部に変更する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度２８０ｍＰａｓ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。
【００８１】
実施例７
実施例１において配合量を、結晶性ポリエステル樹脂ＫＦ５１１を９部、非結晶性ポリエステル樹脂ＧＫ８８０を２１部及び２−エチルヘキシルジフェニルホスフェートを３部に変更する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度２５０ｍＰａｓ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。
【００８２】
実施例８
実施例１において配合量を、結晶性ポリエステル樹脂ＫＦ５１１を６部、非結晶性ポリエステル樹脂ＧＫ８８０を２４部、２−エチルヘキシルジフェニルホスフェートを３部に変更する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度２００ｍＰａｓ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。
【００８３】
実施例９
実施例１において配合量を、結晶性ポリエステル樹脂ＫＦ５１１を３部、非結晶性ポリエステル樹脂ＧＫ８８０を２７部、２−エチルヘキシルジフェニルホスフェートを３部に変更する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度１８０ｍＰａｓ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。
【００８４】
実施例１０
結晶性ポリエステル樹脂ＩＦＧ８Ｌ（カネボウ合繊社製、結晶性ポリエステル樹脂、Ｔｇ７２℃、Ｔｃ[昇温結晶開始温度]１７４℃、Ｔｍ[融点]２２６℃）１２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２１５℃まで加温しＩＦＧ８Ｌを完全に溶解した。次に加熱を止め、シクロヘキサノン３１部とソルベッソ１００を１５部滴下した後、非結晶性ポリエステル樹脂ＧＫ８８０を１８部仕込み完全に溶解するまで攪拌し１６０℃まで冷却した。この溶液に２−エチルヘキシルジフェニルホスフェートを５部仕込み、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、固形分約３３％、粒子径約５μｍ、粘度２３０ｍＰａｓ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ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００８５】
実施例１１
結晶性ポリエステル樹脂ＩＰ０５１（カネボウ合繊社製、結晶性ポリエステル樹脂、Ｔｇ７２℃、Ｔｃ[昇温結晶開始温度]１５６℃、Ｔｍ[融点]２５５℃）１２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２３０℃まで加温しＩＰ０５１を完全に溶解した。次に加熱を止め、シクロヘキサノン３１部とソルベッソ１００を１５部滴下した後、非結晶性ポリエステル樹脂ＧＫ８８０を１８部仕込み完全に溶解するまで攪拌し１６０℃まで冷却した。この溶液に２−エチルヘキシルジフェニルホスフェートを５部仕込み、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、固形分約３３％、粒子径約５μｍ、粘度２３０ｍＰａｓ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ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００８６】
実施例１２
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℃、Ｔｃ[昇温結晶開始温度]１９０℃、Ｔｍ[融点]２３０℃）１２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、シクロヘキサノン３１部とソルベッソ１００を１５部滴下した後、非結晶性ポリエステル樹脂ＧＫ８８０を１８部仕込み完全に溶解するまで攪拌し１６０℃まで冷却した。この溶液に２−エチルヘキシルジフェニルホスフェートを５部仕込み、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、固形分約３３％、粒子径約５μｍ、粘度２００ｍＰａｓ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ヶ月貯蔵しても沈殿や増粘はみられず安定であった。
【００８７】
実施例１３
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、ＵＥ３２０１（ユニチカ社製、非結晶性ポリエステル樹脂、Ｔｇ６５℃）を１８部使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度２５０ｍＰａｓ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。
【００８８】
実施例１４
実施例１において，Ｎ−メチル−２−ピロリドンを２４部の替わりに、ＤＢＥを１２部及びＮ−メチル−２−ピロリドンを１２部使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度２３０ｍＰａｓのポリエステル樹脂分散液Ｒ１４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。
【００８９】
実施例１５
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℃）１２部及びＤＢＥを２４部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、シクロヘキサノン１１部とソルベッソ１００を１５部滴下した後、非結晶性ポリエステル樹脂ＧＫ８８０を１８部仕込み完全に溶解するまで攪拌し１６０℃まで冷却した。この溶液に２−エチルヘキシルジフェニルホスフェートを５部仕込み、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、ＭＥＫを２０部仕込み、固形分約３３％、粒子径約５μｍ、粘度２２０ｍＰａｓのポリエステル樹脂分散液Ｒ１５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。
【００９０】
実施例１６
実施例１においてＤＢＥ２４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Ｒ１６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。
【００９１】
実施例１７
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、固形分約３３％、粒子径約５μｍ、粘度２３０ｍＰａｓのポリエステル樹脂分散液Ｒ１７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。
【００９２】
実施例１８
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、固形分約３３％、粒子径約５μｍ、粘度２３０ｍＰａｓのポリエステル樹脂分散液Ｒ１８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。
【００９３】
実施例１９
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、シクロヘキサノン３１部とソルベッソ１００（エクソンモービル社製、芳香族系炭化水素溶剤）１５部を滴下した後、非結晶性ポリエステル樹脂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）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。この溶液に２−エチルヘキシルジフェニルホスフェートを５部仕込み、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、固形分約３３％、粒子径約５μｍ、粘度１８０ｍＰａｓのポリエステル樹脂分散液Ｒ２８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。
【００９４】
実施例２０
実施例１９において、結晶性ポリエステル樹脂ＫＦ５１１を６部から１２部に、また、非結晶性ポリエステル樹脂ＸＡ−０６５３を２４部から１８部に変更する以外は実施例１９と同様にして製造を行い、固形分約３３％、粒子径約５μｍ、粘度１８０ｍＰａｓのポリエステル樹脂分散液Ｒ２９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。
【００９５】
比較例１
実施例１において２−エチルヘキシルジフェニルホスフェートを仕込まないこと以外は、実施例１と同様にして、固形分約３０％、粒子径約５μｍ、粘度９００ｍＰａｓのポリエステル樹脂分散液Ｒ１９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。
【００９６】
比較例２
実施例１において２−エチルヘキシルジフェニルホスフェートの替わりに、ＴＭＰ（大八化学工業社製、トリメチルホスフェート）を使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度８００ｍＰａｓのポリエステル樹脂分散液Ｒ２０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。
【００９７】
比較例３
実施例１において２−エチルヘキシルジフェニルホスフェートの替わりに、ＴＢＰ（大八化学工業社製、トリブチルホスフェート）を使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度７００ｍＰａｓのポリエステル樹脂分散液Ｒ２１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。
【００９８】
比較例４
実施例１において２−エチルヘキシルジフェニルホスフェート５部の替わりに、ＴＢＰ（大八化学工業社製、トリブチルホスフェート）を１５部使用する以外は実施例１と同様にして、固形分約３９％、粒子径約５μｍ、粘度６５０ｍＰａｓのポリエステル樹脂分散液Ｒ２２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。
【００９９】
比較例５
実施例１において２−エチルヘキシルジフェニルホスフェート５部の替わりに、２５部使用する以外は実施例１と同様にして、固形分約４４％、粒子径約５μｍ、粘度２００ｍＰａｓのポリエステル樹脂分散液Ｒ２３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。
【０１００】
比較例６
実施例１においてＫＦ５１１を１２部の替わりに２９部、非結晶性ポリエステル樹脂ＧＫ８８０を１８部の替わりに１部、２−エチルヘキシルジフェニルホスフェート５部の替わりに１０部使用する以外は実施例１と同様にして、固形分約３６％、粒子径約２０μｍ、粘度１２００ｍＰａｓのポリエステル樹脂分散液Ｒ２４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。
【０１０１】
比較例７
実施例１においてＫＦ５１１を１２部の替わりに１部、非結晶性ポリエステル樹脂ＧＫ８８０を１８部の替わりに２９部、２−エチルヘキシルジフェニルホスフェート５部の替わりに３部使用する以外は実施例１と同様にして、固形分約３２％、粒子径約５μｍ、粘度６５０ｍＰａｓのポリエステル樹脂分散液Ｒ２５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。
【０１０２】
比較例８
実施例１においてＫＦ５１１の替わりにＧＭ４００（東洋紡績社製、結晶性ポリエステル樹脂、Ｔｇ１９℃、Ｔｃ[昇温結晶開始温度]１５０℃未満、Ｔｍ[融点]１４３℃）を使用する以外は実施例１と同様にして、固形分約３３％、粒子径約５μｍ、粘度２５０ｍＰａｓのポリエステル樹脂分散液Ｒ２６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。
【０１０３】
比較例９
実施例１においてＫＦ５１１の替わりにＰＡ２００（三菱レイヨン社製、結晶性ポリエステル樹脂、Ｔｇ７５℃、Ｔｃ[昇温結晶開始温度]１４６℃未満、Ｔｍ[融点]２５５℃）を使用する以外は実施例１と同様にして、固形分約３３％、粒子径約２０μｍ、粘度３００ｍＰａｓのポリエステル樹脂分散液Ｒ２７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。
【０１０４】
被覆用樹脂組成物（缶内面用）
実施例２１〜４３、比較例１０〜１８
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。
【０１０５】
上記各缶内面被覆用樹脂組成物について下記試験方法に従ってロルコート適性（塗装性）を評価した。また、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、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。
【０１０６】
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。試験結果を後記表１に示す。
【０１０７】
試験方法
ロールコート適性；分散体組成物を、下記の条件を標準として、リバースロールコータを用いＮｏ．５０５２アルミ板に塗装し、下記の基準によって評価した。
・塗装条件：各ロールの周速比として、バックアップロール／コーティングロール／ピックアップロール＝１．０／１．０５／０．４
・膜厚：乾燥塗膜重量が１００ｃｍ２当たり約１２０ｍｇ
・焼付け：Ｎｏ．５０５２アルミ板が、２０秒で、２７０℃に達する条件
○：１００ｃｍ２当たり約１２０ｍｇの膜厚に均一に塗布できる。
△：膜厚が不均一となる。
×：ロールコーターでは、未塗装部が生じ、全面を塗装することが出来ない。
【０１０８】
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。
【０１０９】
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。
【０１１０】
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。
【０１１１】
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。
【０１１２】
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。
【０１１３】
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。
【０１１４】
【表１】
【表２】
表１における各注（＊１）〜（＊４）の原料は下記の内容のものである。
（＊１）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％。
（＊２）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％。
（＊３）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。
（＊４）ＮＡＣＵＲＥ５９２５：キング・インダストリイズ社製、ドデシルベンゼンスルホン酸のアミン中和溶液、有効成分２５％。
【０１１７】
被覆用樹脂組成物（潤滑金属板用）
実施例４４及び４５並びに比較例１９
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。
【０１１８】
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。
【０１１９】
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。
【０１２０】
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。
【０１２１】
【表３】
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。
【０１２３】
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。
【０１２４】
【表４】
表３における各注（＊５）及び（＊６）の原料は各々下記の内容のものである。
（＊５）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℃
（＊６）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℃
【０１２６】
【発明の効果】
本発明のポリエステル樹脂分散液は、溶剤に溶解しない結晶性ポリエステル樹脂を非結晶性ポリエステル樹脂と特定のリン酸系化合物により有機溶剤中に均一に分散させることができたものであり、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は、ロール塗装作業性にも優れたものであり、金属素材に塗装して得られる被膜は、付着性、加工性、香味収着性、耐レトルト性、耐腐食性などに優れた性能を示すことから、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]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester resin dispersion obtained by dispersing a crystalline polyester resin in an organic solvent, and relates to a coating resin composition using the polyester resin dispersion, and the coating resin composition The present invention relates to a can body obtained by using a can and a method for producing the can body.
[0002]
[Prior art and problems]
Conventionally, a resin containing a bisphenol A type epoxy resin has been often 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 exogenous endocrine disrupting chemical substances (environmental hormones), and therefore, development of a paint that does not elute bisphenol A from the coating film has been strongly desired.
[0003]
Polyester resin has been studied as an alternative to epoxy resin, but it is not easy to satisfy the strict coating performance such as hardness, adhesion, anticorrosion, and flavor retention required for the can inner surface coating, It has become important to master a highly crystalline polyester resin represented by PET resin.
[0004]
In addition, in recent years, from the post-coating method in which a metal plate is molded into a can and then coated, due to the reduction in manufacturing costs of resin-coated cans and the processing of press oil after molding, pre-coated metal It has been replaced by a pre-coating method in which a flat plate is molded into a can shape, and there is a demand for the use of a highly crystalline polyester resin having both hardness and workability for coatings.
[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, see Japanese Patent Application Laid-Open No. H10-133260, Japanese Patent Application Laid-Open No. H10-133260, and the like. It has become.
[0006]
However, in order to use film laminate, not only new capital investment is required, but film laminate method is inferior in workability compared to painting, so development of paint using such crystalline polyester resin However, crystalline polyester resins generally have low solubility in solvents, and there are problems such as crystal precipitation during storage. To apply crystalline polyester resins directly to paints, There were many problems. As one method for solving such a problem, an amorphous polyester resin soluble in an organic solvent and a crystalline polyester resin having a melting point of 90 to 180 ° C. are heated and melt-mixed and dissolved or dispersed in the organic solvent. A method is disclosed (see, for example, Patent Document 4). However, there is a limit in this method, and when a highly crystalline polyester resin having a melting point required for a paint for inner surfaces of cans exceeding 190 ° C. is used, crystals grow greatly during production or storage of the solution. There is a problem that the solution is greatly thickened or the particles settle and aggregate.
[0007]
An object of the present invention is to provide a polyester resin dispersion excellent in storage stability and roll coatability and a method for producing the same, and to provide a coating resin composition using the polyester resin dispersion. .
[0008]
[Patent Document 1]
JP-A-56-10451
[Patent Document 2]
JP 57-65463 A
[Patent Document 3]
JP-A 51-17788
[Patent Document 4]
JP-A-4-164957
[0009]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that by dispersing a crystalline polyester resin and an amorphous polyester resin with a specific phosphoric acid compound added in an organic solvent. It has been found that a polyester resin dispersion having good storage stability can be obtained, and the present invention has been completed.
[0010]
Thus, in the present invention, a mixture of a crystalline polyester resin (A), an amorphous polyester resin (B) and a phosphoric acid compound (C) represented by the following formula (1) is dispersed in an organic solvent (D). A polyester resin dispersion is provided.
[0011]
[Chemical formula 2]
R1, R2And R3Are the same or different and are each an aliphatic or aromatic hydrocarbon having 6 or more carbon atoms, or -CmH2mOCnH2n + 1M and n are integers of 1 or more and m + n is an integer of 6 or more.
[0013]
In the present invention, the crystalline polyester resin (A), the amorphous polyester resin (B), the phosphoric acid compound (C) and the organic solvent (D) are heated and dissolved, and then the resin solution is crystallized. Polyester resin dispersion, characterized by being rapidly cooled at a speed of 2 ° C. or more per minute from a temperature not lower than the temperature rising temperature of the crystalline polyester resin (A) to a temperature not higher than the glass transition temperature of the crystalline polyester resin (A) The manufacturing method of this is provided.
[0014]
Moreover, this invention provides the resin composition for coating | cover using the said polyester resin dispersion liquid.
[0015]
Furthermore, this invention provides the can body using the said resin composition for a coating | cover, and the manufacturing method of a can body.
[0016]
Hereinafter, the present invention will be described in more detail.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
The polyester resin dispersion of the present invention is obtained by dispersing a crystalline polyester resin (A), an amorphous polyester resin (B), and a phosphoric acid compound (C) in an organic solvent (D).
[0018]
Crystalline polyester resin (A)
The crystalline polyester resin which is the component (A) of the polyester resin dispersion is an esterified product of a polybasic acid component and a polyhydric alcohol component.
[0019]
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 acids, 1,6-hexanedicarboxylic acid, and the like, and lower alkyl esterified products of these acids are mainly used, and benzoic acid, crotonic acid, pt-butylbenzoic acid as necessary. A monobasic acid such as an acid, a tribasic or higher polybasic acid such as trimellitic anhydride, methylcyclohexeric carboxylic acid and pyromellitic anhydride are used in combination.
[0020]
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 trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol can be used in combination as necessary. These polyhydric alcohols can be used alone or in admixture of two or more. The esterification or transesterification reaction of both components can be carried out by a method known per se.
[0021]
The crystalline polyester resin mainly uses terephthalic acid and 2,6-naphthalenedicarboxylic acid as the acid component, and mainly uses ethylene glycol and 1,4-butanediol as the polyhydric alcohol component. In particular, a polyethylene terephthalate resin mainly using terephthalic acid and ethylene glycol is preferable.
[0022]
The crystalline polyester resin used in the present invention suitably has a melting point of 190 ° C. to 260 ° C., preferably 200 ° C. to 255 ° C., and a temperature rising crystal start temperature of 150 ° C. or higher, preferably 155 ° C. to 195 ° C. Yes. Temperature rise of crystalline polyester resin If the crystal start temperature is low, crystallization proceeds due to heat during retort sterilization and the film tends to whiten. If the melting point of the crystalline polyester resin is low, film sorption and barrier properties When the melting point is too high, the film forming property is lowered.
[0023]
The melting point of the crystalline polyester resin and the temperature rising start temperature were measured using a scanning scanning calorimeter (Shimadzu Corporation).
[0024]
Examples of commercially available crystalline polyester resins include IFG8L, TG7N10, IP051 (manufactured by Kanebo Gosei Co., Ltd.), KF-511 (manufactured by Mitsubishi Rayon Co., Ltd.), and the like.
[0025]
Amorphous polyester resin (B)
The non-crystalline polyester resin which is the component (B) of the polyester resin dispersion means a resin which does not have a clear melting point as measured by a scanning scanning calorimeter and dissolves in an organic solvent at room temperature.
[0026]
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 polyhydric alcohol component as raw materials are components of the crystalline polyester resin. The same materials as listed above can be used.
[0027]
For example, in the case of a polyethylene terephthalate resin, the crystallinity of the polyester resin can be obtained by partially replacing the acid component terephthalic acid with another acid component such as isophthalic acid, and the polyhydric alcohol ethylene glycol such as diethylene glycol. It can be reduced or eliminated by partially replacing the alcohol component.
[0028]
Examples of commercially available amorphous polyester resins include UE-3201, UE-3203, XA-0653 (above, manufactured by Unitika Ltd.), GK-880, GK-640 (above, manufactured by Toyobo Co., Ltd.) and the like. .
[0029]
The compounding ratio of the crystalline polyester resin (A) and the non-crystalline polyester resin (B) is (A) / (B) = 95/5 to 5/95, particularly 60/40 to 10/90 in weight ratio. The range is preferable from the viewpoint of retort resistance and corrosion resistance of the film obtained from the polyester resin dispersion.
[0030]
Phosphoric acid compound (C)
The phosphoric acid compound of the present invention has a structure represented by the following formula (1), and acts as a surfactant when the polyester resin is dispersed, so that not only the dispersed particle diameter becomes fine but also the obtained polyester resin dispersion It is thought that it has the function of preventing the coalescence of the particles and stabilizing the dispersion.
[0031]
[Chemical 3]
R1, R2And R3Are the same or different and are each an aliphatic or aromatic hydrocarbon having 6 or more carbon atoms, or -CmH2mOCnH2n + 1M and n are integers of 1 or more and m + n is an integer of 6 or more.
[0033]
Examples of the phosphoric acid compound (C) include 2-ethylhexyl diphenyl phosphate, tris (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, tricresyl phosphate, and the like.
[0034]
The blending amount of the phosphoric acid compound (C) is 0.1 to 20 parts by weight based on 100 parts by weight of the total solid content of the crystalline polyester resin (A) and the amorphous polyester resin (B), preferably It is suitable from the viewpoint of the storage stability of the polyester resin dispersion obtained in the range of 1 to 15 parts by weight.
[0035]
Organic solvent (D)
The organic solvent (D) used in the production of the polyester resin dispersion of the present invention can be used as long as it can dissolve the non-crystalline polyester resin, but 50% by weight or more in the organic solvent (D) From the viewpoint of production stability of the polyester resin dispersion, it is preferable that the organic solvent does not contain a hydroxyl group having a boiling point of 150 ° C. to 220 ° C., for example, ketone solvents such as N-methyl-2-pyrrolidone, isophorone, cyclohexanone, Examples include ester solvents such as DBE (manufactured by DuPont, mixed solvent of dimethyl adipate, dimethyl glutarate, dimethyl succinate).
[0036]
Method for producing polyester resin dispersion
After the crystalline polyester resin (A), the amorphous polyester resin (B) and the phosphoric acid compound (C) are heated and dissolved in an organic solvent, the resulting solution is cooled and the polyester resin crystallizes. A polyester resin dispersion can be obtained by precipitation.
[0037]
In general, cooling in a tank or the like is a slow cooling of about 0.1 to 1 ° C. per minute, but when a polyester resin having a high melting point and a high crystallinity is used, it is precipitated as the cooling rate is low. The diameter of the polyester particles increases and the stability of the dispersion decreases. The effect mainly appears as a decrease in storage stability of the polyester resin dispersion or the coating composition using the dispersion, but even if the storage stability does not decrease so much, a strong share such as roll coating is applied. There are also phenomena such as fusion of dispersed particles, or the fact that the viscosity becomes so high that it cannot be applied with a normal roll coating machine, resulting in poor coating. In particular, the stability of the polyester resin dispersion is greatly influenced by the cooling rate from the temperature rising crystallization start temperature of the crystalline polyester resin (A) to the glass transition temperature of the crystalline polyester resin (A). By carrying out the cooling rate from 2 ° C./min or higher, preferably 3 to 10 ° C./min, from the temperature higher than the temperature rising crystal starting temperature of (A) to the temperature lower than the glass transition temperature of the crystalline polyester resin (A). A polyester resin dispersion having good storage stability and roll coatability can be obtained.
[0038]
As a manufacturing apparatus, an apparatus for heating and dissolving the polyester resin and an apparatus capable of rapidly cooling the solution may be used.
[0039]
Production of the polyester resin dispersion is first performed at a high temperature at which the crystalline polyester resin (A) and the amorphous polyester resin (B) are dissolved in the solvent, preferably the temperature rising crystallization temperature of the crystalline polyester resin (A). A resin solution having the above temperature is prepared.
[0040]
There are no particular restrictions on the procedure for producing the high temperature resin solution, for example
(1) A method in which an organic solvent (D) and a pellet-like crystalline polyester resin (A) are mixed, heated and dissolved with stirring, and then the amorphous polyester resin (B) is added.
(2) A method in which an organic solvent (D), an amorphous polyester resin (B) and a crystalline polyester resin (A) are mixed and then heated and dissolved.
(3) A method of gradually adding the crystalline polyester resin (A) to a solution of the heated amorphous polyester resin (B) dissolved in the organic solvent (D),
and so on. The dissolution of the crystalline polyester resin (A) does not necessarily need to be raised to the melting point temperature of the resin in the organic solvent, and is as low as possible within the range where there is no problem in workability if the temperature is higher than the temperature rising temperature of the resin. This is more preferable in order to avoid decomposition of the polyester resin due to heat. Similarly, in order to avoid decomposition of the resin, the addition of the non-crystalline polyester resin (B) is preferably late, and the production method (1) is particularly preferred.
[0041]
After the polyester resin is dissolved, it is cooled as soon as possible according to the cooling conditions of the present invention. When heating, melting, and cooling are all performed in the same device (for example, a tank), it is necessary to use a device with excellent cooling performance or select a place that meets the above cooling conditions by reducing the amount charged. is there. In addition, the cooling process can be rapidly cooled separately from the heating and dissolving apparatus, for example, a method of bringing the heated and dissolved polyester resin solution into a precooled tank or a tube with a cooling apparatus. Can do.
[0042]
Furthermore, a part of the organic solvent (D) is used for cooling, and can be used as an auxiliary means for cooling by adding at the time of cooling.
[0043]
If it cools to the temperature below the glass transition temperature of crystalline polyester resin (A), there will be no restriction | limiting in particular in the subsequent cooling rate.
[0044]
Further, even if the phosphoric acid compound (C) is added after cooling, an effect on storage stability is seen, but the effect on the stability of the polyester resin dispersion is greater when added during or before cooling. It is preferable to add it before cooling.
[0045]
Resin composition for coating
The polyester resin dispersion of the present invention can be used alone, but the retort resistance, adhesion, flavor and the like are further improved by combining a resin other than the polyester resin such as a resol type phenol resin, amino resin, and epoxy resin. be able to. Of these, resol type phenol resins and epoxy resins are preferred.
[0046]
The resol type phenol resin is used as a cross-linking agent for a polyester resin. When the resol type phenol resin is used, the crystalline polyester resin (A) and the non-crystalline polyester resin (B) constituting the polyester resin dispersion are used. ), In particular, the amorphous polyester resin (B) preferably has a hydroxyl value of about 5 to 100 mgKOH / g, preferably about 10 to 50 mgKOH / g.
[0047]
In addition, the resol type phenolic resin is a part of the methylol group of the methylolated phenol resin obtained by introducing a methylol group by heating and condensing a phenol component and formaldehyde in the presence of a reaction catalyst. Those obtained by alkyl etherification are preferred.
[0048]
In the production of the resol-type phenol resin crosslinking agent, a bifunctional phenol compound, a trifunctional phenol compound, a tetrafunctional or higher functional phenol compound, or the like can be used as the phenol component that is a starting material.
[0049]
Examples of the bifunctional phenol compound used for the production of 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. The trifunctional phenol compound includes phenol, m-cresol, m-ethylphenol, 3,5-xylenol, m-methoxyphenol, and the like. Examples of the compound include bisphenol A and bisphenol F. These phenol compounds may be used alone or in combination of two or more.
[0050]
Examples of formaldehydes used in the production of the resol type phenol resin include formaldehyde, paraformaldehyde, trioxane, and the like, which can be used alone or in combination of two or more.
[0051]
As the alcohol used for alkyl etherifying a part of the methylol group of the methylolated phenol resin, a monohydric alcohol having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, can be suitably used. Suitable monohydric alcohols include methanol, ethanol, n-propanol, n-butanol, isobutanol and the like.
[0052]
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 amorphous polyester resin (B). The range of the part is suitable from the viewpoint of balance between curability and workability.
[0053]
An acid catalyst can be added to the coating composition as necessary to accelerate the curing reaction. Specific examples include acid catalysts such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, phosphoric acid, and amine neutralized products of these acids. Among these, the sulfonic acid compound or an amine neutralized product of the sulfonic acid compound is preferable.
[0054]
The compounding amount of the acid catalyst is determined based on the physical properties of the resulting coating film, and the like (for example, in the case of an amine neutralized product of a sulfonic acid compound, the amount of the remaining sulfonic acid compound obtained by removing the amine from the neutralized product) ) Based on a total solid content of 100 parts by weight of the crystalline polyester resin (A) and the non-crystalline polyester resin (B), preferably 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight. Is suitable.
[0055]
When the polyester resin contains a carboxyl group, the epoxy resin effectively acts as a crosslinking agent. However, when the polyester resin does not have a carboxyl group, the polyester resin reinforcing material or the resol type phenol is used. Effectively acts as a film-forming component by crosslinking with the resin.
[0056]
Addition of an epoxy resin improves hardness, adhesion, retort resistance, and the like, but among these, a novolac type epoxy resin is preferable because it does not contain bisphenol A which is suspected of an environmental hormone. Examples of the novolak type epoxy resin include various novolak type epoxy resins such as a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and a phenol glyoxal type epoxy resin having a large number of epoxy groups in the molecule. Of these, a phenol novolac type epoxy resin and a cresol novolac type epoxy resin that can easily balance the coating film performance are preferable.
[0057]
When an epoxy resin is used as a crosslinking agent for a polyester resin, at least one of a crystalline polyester resin (A) and an amorphous polyester resin (B) constituting the polyester resin dispersion, particularly an amorphous polyester resin (B ) Has 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 amorphous polyester resin (B). The range is suitable from the viewpoint of balance between curability and workability.
[0058]
Moreover, when using an epoxy resin as a crosslinking agent of a polyester resin, in order to accelerate | stimulate hardening reaction, a basic catalyst can be added as needed. Specific examples include tertiary amines such as choline chloride, nicotinamide, choline tartrate, aqueous choline, and dimethylethanolamine. Of these, choline chloride and nicotinamide are preferred.
[0059]
The blending amount of the basic catalyst is 0.01 to 0.01 based on the total solid content of 100 parts by weight of the crystalline polyester resin (A) and the amorphous polyester resin (B) from the viewpoint of the physical properties of the resulting coating film. 5 parts by weight, preferably 0.05 to 1 part by weight is suitable.
[0060]
The coating composition may further include other organic resins, additives (waxes, antifoaming agents, leveling agents, anti-aggregation agents, etc.), pigments (organic pigments, inorganic pigments, glitter pigments, constitutions, if necessary). Pigments, rust preventive pigments, etc.) and organic solvents can be combined with commonly known raw materials.
[0061]
The coating resin composition of the present invention can be suitably used as a paint for can inner and outer surfaces, precoated steel sheets, automobiles, and the like, but is particularly suitable for can inner and outer surfaces.
[0062]
When the coating resin composition of the present invention is used for a can, the inner surface and / or the outer surface of the can body formed into a can shape may be painted using a spray or the like, but a planar metal plate After coating and drying using a known coating method such as a roll coater or curtain flow coater, the coated metal plate may be cut and formed into a can shape to produce a can body. When the latter production method is used, it is preferable to add a wax to the coating resin composition in order to suppress generation of scratches during conveyance and molding.
[0063]
The wax is added to adjust the dynamic friction coefficient of the resulting film, and the softening point of the wax is 30 ° C. or more, preferably 33 to 150 ° C. in order to adjust the dynamic friction coefficient at high temperatures. For example, waxes such as fatty acid ester wax, which is an esterified product of a polyol compound and a fatty acid, silicon wax, fluorine wax, polyolefin wax, animal wax, plant wax and the like can be mentioned.
[0064]
Examples of the polyol compound used as a raw material for 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. Among these, a polyol compound having three or more hydroxyl groups in one molecule is preferable, and among them, polyglycerol, trimethylolpropane, and pentaerythritol are preferable.
[0065]
Examples of the fatty acid that is the other raw material of the fatty acid ester wax include saturated or unsaturated fatty acids, preferably fatty acids 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, arachidic acid, behenic acid, serotic acid, montanic acid and melicic acid; Mention may be made of unsaturated fatty acids such as acids, undecylenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, cetoleic acid, erucic acid, ricanoic acid, ricinoleic acid, arachidonic acid. The fatty acid ester wax is preferably one in which at least 1/3 of the number of hydroxyl groups of the polyol compound is esterified with a fatty acid.
[0066]
Examples of the silicon-based wax include BYK-300, BYK-320, BYK-330 [above, manufactured by BYK Chemie), Silwet L-77, same L-720, same L-7602 [more, Nippon Konica Co., Ltd.], Paintad 29, 32, M [above, manufactured by Dow Corning], Shin-Etsu Silicone KF-96 [manufactured by Shin-Etsu Chemical Co., Ltd.], etc. Examples thereof include Rock Wax SST-1MG, SST-3, Fluoroslip 231 [above, manufactured by Shamrock Chemicals], POLYFLUO 120, 150, 400 [Micro Powders].
[0067]
Polyolefin waxes include, for example, Shamrock wax S-394, S-395 (above, manufactured by Shamrock Chemicals), Hoechst wax PE-520, PE-521 (above, manufactured by Hoechst), Mitsui High Wax [ Manufactured by Mitsui Petrochemical Co., Ltd.], and animal waxes such as lanolin wax and beeswax, and plant waxes such as carnauba wax and water wax.
[0068]
The wax can be used alone or in combination of two or more, and the amount added is 0.1 to 5 parts by weight, preferably based on 100 parts by weight of the total solid content of the resin components in the coating resin composition. Is preferably in the range of 0.5 to 2 parts by weight.
[0069]
As a coating amount when the coating composition is used for the inner surface of the can, a dry coating amount is 50 to 180 mg / 100 cm.2, Preferably 85-150mg / 100cm2It is preferable that it is the range of these. The baking condition of the coating film is usually about 15 seconds to about 30 minutes under the condition that the maximum temperature reached by the metal plate is about 190 to 300 ° C.
[0070]
Examples of the material of the can include metals such as untreated steel plate, tin-plated steel plate, galvanized steel plate, chrome-plated steel plate, phosphate-treated steel plate, chromate-treated steel plate, untreated aluminum plate, and chromate-treated aluminum plate. Materials can be listed.
[0071]
In the method for producing a can body in which the coating composition of the present invention is coated on a metal flat plate, dried, then cut and molded into a can shape, the inner surface of the shaped can body is further sprayed on the inner surface of the can body May be painted. As the paint for the inner surface of the can, conventionally known ones can be used, and the coating composition of the present invention can be used. Thus, by further coating the paint for the inner surface of the can after being molded into a can shape, scratches and the like made during molding can be protected, and retort resistance and the like can be greatly improved. Further, in the case of further coating the paint for the inner surface of the can after molding, it is preferable from the economical aspect to keep the coating film thickness on the metal flat plate of the coating resin composition of the present invention low. From the viewpoint of lubricity, the dry coating amount is 10 to 85 mg / 100 cm.2, Especially 15-60mg / 100cm2The degree is suitable.
[0072]
The above-mentioned paint for the inner surface of the can applied after molding can be used without particular limitation such as a solvent-type paint and a water-based paint, and the film thickness thereof may be thin enough to repair a scratched part.
[0073]
【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.
[0074]
Manufacture of polyester resin dispersion
Example 1
Crystalline polyester resin KF511 (manufactured by Mitsubishi Rayon Co., Ltd., crystalline polyester resin, Tg 60 ° C., Tc [temperature rising crystal start temperature] 156 ° C., Tm [melting point] 214 ° C.) and DBE (manufactured by DuPont, dimethyl adipate, 24 parts of a mixed solvent of dimethyl glutarate and dimethyl succinate) was charged into a four-necked flask equipped with a cooling tube and purged with nitrogen gas, and heated to about 200 ° C. with a mantle heater while stirring with a stirring blade to completely remove KF511. Dissolved. Next, after heating was stopped and 31 parts of cyclohexanone and 15 parts of Solvesso 100 (Axon Mobil Corporation, aromatic hydrocarbon solvent) were added dropwise, amorphous polyester resin GK880 (Toyobo Co., Ltd., amorphous polyester resin, (Tg84 ° C.) 18 parts were charged and stirred until completely dissolved and cooled to 160 ° C. This solution was charged with 5 parts of 2-ethylhexyldiphenyl phosphate, cooled at a rate of 5 ° C./min from a cooling start temperature of 160 ° C. to a cooling end temperature of 55 ° C., and a polyester having a solid content of about 33%, a particle size of about 5 μm, and a viscosity of 230 mPas. Resin dispersion R1 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0075]
The viscosity of the polyester resin dispersion was measured using a cone-plate viscometer (TV-20 model, manufactured by Tokimec Co., Ltd.) with a standard rotor at 20 rpm and 25 ° C.
[0076]
Example 2
In Example 1, except that TOP (manufactured by Daihachi Chemical Industry Co., Ltd., tris (2-ethylhexyl) phosphate) is used in place of 2-ethylhexyl diphenyl phosphate, the same as Example 1, except that the solid content is about 33% and the particle size A polyester resin dispersion R2 having a viscosity of about 5 μm and a viscosity of 200 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0077]
Example 3
In Example 1, TBXP (manufactured by Daihachi Chemical Industry Co., Ltd., tris (butoxyethyl) phosphate) was used instead of 2-ethylhexyl diphenyl phosphate in the same manner as in Example 1 except that the solid content was about 33% and the particle size was about A polyester resin dispersion R3 having a viscosity of 5 μm and a viscosity of 200 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0078]
Example 4
In Example 1, except that TPP (manufactured by Daihachi Chemical Industry Co., Ltd., triphenyl phosphate) is used instead of 2-ethylhexyl diphenyl phosphate, the solid content was about 33%, the particle size was about 5 μm, and the viscosity was the same. A 500 mPas polyester resin dispersion R4 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0079]
Example 5
In Example 1, except that TCP (manufactured by Daihachi Chemical Industry Co., Ltd., tricresyl phosphate) is used instead of 2-ethylhexyldiphenyl phosphate, the solid content is about 33%, the particle size is about 5 μm, A polyester resin dispersion R5 having a viscosity of 550 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0080]
Example 6
In Example 1, the solid content was changed in the same manner as in Example 1 except that the crystalline polyester resin KF511 was changed to 18 parts, the amorphous polyester resin GK880 was changed to 12 parts, and 2-ethylhexyldiphenyl phosphate was changed to 10 parts. A polyester resin dispersion R6 having about 33%, a particle size of about 5 μm, and a viscosity of 280 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0081]
Example 7
In Example 1, the blending amount was changed to 9 parts of the crystalline polyester resin KF511, 21 parts of the non-crystalline polyester resin GK880 and 3 parts of 2-ethylhexyl diphenyl phosphate, and the solid content was the same as in Example 1. A polyester resin dispersion R7 having about 33%, a particle size of about 5 μm, and a viscosity of 250 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0082]
Example 8
In Example 1, the solid content was changed in the same manner as in Example 1 except that the crystalline polyester resin KF511 was changed to 6 parts, the amorphous polyester resin GK880 was changed to 24 parts, and 2-ethylhexyldiphenyl phosphate was changed to 3 parts. A polyester resin dispersion R8 having about 33%, a particle size of about 5 μm, and a viscosity of 200 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0083]
Example 9
In Example 1, the blending amount was changed to 3 parts of crystalline polyester resin KF511, 27 parts of non-crystalline polyester resin GK880, and 3 parts of 2-ethylhexyl diphenyl phosphate. A polyester resin dispersion R9 having about 33%, a particle size of about 5 μm, and a viscosity of 180 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0084]
Example 10
Crystalline polyester resin IFG8L (manufactured by Kanebo Gosei Co., Ltd., crystalline polyester resin, Tg 72 ° C., Tc [temperature rising crystallization start temperature] 174 ° C., Tm [melting point] 226 ° C.) 12 parts and N-methyl-2-pyrrolidone 24 parts The flask was charged into a four-necked flask equipped with a cooling tube and purged with nitrogen gas, and heated to about 215 ° C. with a mantle heater while stirring with a stirring blade to completely dissolve IFG8L. Next, the heating was stopped, and 31 parts of cyclohexanone and 15 parts of Solvesso 100 were dropped. Then, 18 parts of amorphous polyester resin GK880 was charged and stirred until completely dissolved, and then cooled to 160 ° C. This solution was charged with 5 parts of 2-ethylhexyldiphenyl phosphate, cooled at a rate of 5 ° C./min from a cooling start temperature of 160 ° C. to a cooling end temperature of 55 ° C., and a polyester having a solid content of about 33%, a particle size of about 5 μm, and a viscosity of 230 mPas. Resin dispersion R10 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0085]
Example 11
Crystalline polyester resin IP051 (manufactured by Kanebo Gosei Co., Ltd., crystalline polyester resin, Tg 72 ° C., Tc [temperature rising crystallization start temperature] 156 ° C., Tm [melting point] 255 ° C.) 12 parts and N-methyl-2-pyrrolidone 24 parts The mixture was charged in a four-necked flask with a nitrogen tube substituted with a cooling tube, and heated to about 230 ° C. with a mantle heater while stirring with a stirring blade to completely dissolve IP051. Next, the heating was stopped, and 31 parts of cyclohexanone and 15 parts of Solvesso 100 were dropped. Then, 18 parts of amorphous polyester resin GK880 was charged and stirred until completely dissolved, and then cooled to 160 ° C. This solution was charged with 5 parts of 2-ethylhexyldiphenyl phosphate, cooled at a rate of 5 ° C./min from a cooling start temperature of 160 ° C. to a cooling end temperature of 55 ° C., and a polyester having a solid content of about 33%, a particle size of about 5 μm, and a viscosity of 230 mPas. Resin dispersion R11 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0086]
Example 12
Crystalline polyester resin TG7N10 (manufactured by Kanebo Gosei Co., Ltd., crystalline polyester resin, Tg 79 ° C., Tc [temperature rising crystallization start temperature] 190 ° C., Tm [melting point] 230 ° C.) 12 parts and N-methyl-2-pyrrolidone 24 parts The mixture was charged into a four-necked flask with a nitrogen tube replaced with a cooling tube 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 31 parts of cyclohexanone and 15 parts of Solvesso 100 were dropped. Then, 18 parts of amorphous polyester resin GK880 was charged and stirred until completely dissolved, and then cooled to 160 ° C. This solution was charged with 5 parts of 2-ethylhexyl diphenyl phosphate, cooled at a rate of 5 ° C./min from a cooling start temperature of 160 ° C. to a cooling end temperature of 55 ° C., and a polyester having a solid content of about 33%, a particle size of about 5 μm, and a viscosity of 200 mPas. Resin dispersion R12 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0087]
Example 13
In Example 1, instead of the non-crystalline polyester resin GK880, the solid content was about 33% in the same manner as in Example 1 except that 18 parts of UE3201 (manufactured by Unitika, non-crystalline polyester resin, Tg 65 ° C.) was used. A polyester resin dispersion R13 having a particle diameter of about 5 μm and a viscosity of 250 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0088]
Example 14
In Example 1, instead of 24 parts of N-methyl-2-pyrrolidone, the solid content was about 33, as in Example 1, except that 12 parts of DBE and 12 parts of N-methyl-2-pyrrolidone were used. %, A particle diameter of about 5 μm, and a viscosity of 230 mPas polyester resin dispersion R14 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0089]
Example 15
Crystalline polyester resin KF511 (manufactured by Mitsubishi Rayon Co., Ltd., crystalline polyester resin, Tg 60 ° C., Tc [temperature rising crystallization start temperature] 156 ° C., Tm [melting point] 214 ° C.) 12 parts and DBE 24 parts with a condenser The gas-substituted four-necked flask was charged 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, 11 parts of cyclohexanone and 15 parts of Solvesso 100 were dropped, and then 18 parts of amorphous polyester resin GK880 was charged and stirred until completely dissolved, and then cooled to 160 ° C. This solution is charged with 5 parts of 2-ethylhexyl diphenyl phosphate, cooled at a rate of 5 ° C./min from a cooling start temperature of 160 ° C. to a cooling end temperature of 55 ° C., and charged with 20 parts of MEK, with a solid content of about 33% and a particle size of about A polyester resin dispersion R15 having a viscosity of 5 μm and a viscosity of 220 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0090]
Example 16
A polyester resin dispersion R16 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 DBE in Example 1. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0091]
Example 17
In Example 1, except that the cooling start temperature from 160 ° C. to the cooling end temperature of 55 ° C. was cooled at a rate of 3 ° C./minute, the same as in Example 1, the solid content was about 33%, the particle size was about 5 μm, and the viscosity was 230 mPas. A polyester resin dispersion R17 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0092]
Example 18
A polyester resin dispersion R18 having a solid content of about 33%, a particle size of about 5 μm, and a viscosity of 230 mPas was obtained in the same manner as in Example 1 except that the cooling start temperature was changed to 180 ° C. in Example 1. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0093]
Example 19
Crystalline polyester resin KF511 (manufactured by Mitsubishi Rayon Co., Ltd., crystalline polyester resin, Tg 60 ° C., Tc [temperature rising crystal start temperature] 156 ° C., Tm [melting point] 214 ° C.) 6 parts and N-methyl-2-pyrrolidone 24 parts A four-necked flask with a nitrogen tube replaced with a cooling tube was charged 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 after 31 parts of cyclohexanone and 15 parts of Solvesso 100 (exxon mobile, aromatic hydrocarbon solvent) were added dropwise, amorphous polyester resin XA-0653 (manufactured by Unitika, non-crystalline polyester resin) , Tg 58 ° C., acid value 20 mg KOH / g) 24 parts were charged and stirred until completely dissolved, and then cooled to 160 ° C. This solution was charged with 5 parts of 2-ethylhexyl diphenyl phosphate, cooled at a rate of 5 ° C./min from a cooling start temperature of 160 ° C. to a cooling end temperature of 55 ° C., and a polyester having a solid content of about 33%, a particle size of about 5 μm, and a viscosity of 180 mPas. Resin dispersion R28 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0094]
Example 20
In Example 19, the production was carried out in the same manner as in Example 19 except that the crystalline polyester resin KF511 was changed from 6 parts to 12 parts, and the non-crystalline polyester resin XA-0653 was changed from 24 parts to 18 parts. A polyester resin dispersion R29 having a solid content of about 33%, a particle size of about 5 μm, and a viscosity of 180 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0095]
Comparative Example 1
A polyester resin dispersion R19 having a solid content of about 30%, a particle size of about 5 μm, and a viscosity of 900 mPas was obtained in the same manner as in Example 1 except that 2-ethylhexyl diphenyl phosphate was not charged in Example 1. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0096]
Comparative Example 2
In Example 1, instead of 2-ethylhexyl diphenyl phosphate, TMP (manufactured by Daihachi Chemical Industry Co., Ltd., trimethyl phosphate) was used in the same manner as in Example 1 except that the solid content was about 33%, the particle size was about 5 μm, and the viscosity. An 800 mPas polyester resin dispersion R20 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0097]
Comparative Example 3
In Example 1, instead of 2-ethylhexyl diphenyl phosphate, TBP (manufactured by Daihachi Chemical Industry Co., Ltd., tributyl phosphate) was used in the same manner as in Example 1 except that the solid content was about 33%, the particle size was about 5 μm, and the viscosity was A 700 mPas polyester resin dispersion R21 was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0098]
Comparative Example 4
In Example 1, instead of 5 parts of 2-ethylhexyl diphenyl phosphate, 15 parts of TBP (manufactured by Daihachi Chemical Industry Co., Ltd., tributyl phosphate) was used in the same manner as in Example 1 except that the solid content was about 39% and the particle size A polyester resin dispersion R22 having a viscosity of about 5 μm and a viscosity of 650 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0099]
Comparative Example 5
A polyester resin dispersion R23 having a solid content of about 44%, a particle size of about 5 μm, and a viscosity of 200 mPas was obtained in the same manner as in Example 1 except that 25 parts were used instead of 5 parts of 2-ethylhexyldiphenyl phosphate in Example 1. It was. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0100]
Comparative Example 6
Example 1 Same as Example 1 except that 29 parts of KF511 are used instead of 12 parts, 1 part of amorphous polyester resin GK880 is used instead of 18 parts, and 10 parts of 2-ethylhexyldiphenyl phosphate are used instead of 5 parts. Thus, a polyester resin dispersion R24 having a solid content of about 36%, a particle size of about 20 μm, and a viscosity of 1200 mPas was obtained. When the polyester resin dispersion was stored at 20 ° C. for 1 month, a precipitate was observed.
[0101]
Comparative Example 7
Example 1 Example 1 with the exception of using 1 part KF511 instead of 12 parts, 29 parts amorphous polyester resin GK880 instead of 18 parts, and 3 parts instead of 5 parts 2-ethylhexyldiphenyl phosphate. Thus, a polyester resin dispersion R25 having a solid content of about 32%, a particle size of about 5 μm, and a viscosity of 650 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0102]
Comparative Example 8
Example 1 except that GM400 (manufactured by Toyobo Co., Ltd., crystalline polyester resin, Tg 19 ° C., Tc [temperature rising crystal start temperature] less than 150 ° C., Tm [melting point] 143 ° C.) is used instead of KF511 in Example 1. In the same manner as above, a polyester resin dispersion R26 having a solid content of about 33%, a particle size of about 5 μm, and a viscosity of 250 mPas was obtained. The polyester resin dispersion was stable with no precipitation or thickening even after storage at 20 ° C. for 1 month.
[0103]
Comparative Example 9
Example 1 except that PA200 (manufactured by Mitsubishi Rayon Co., Ltd., crystalline polyester resin, Tg 75 ° C., Tc [temperature rising crystal start temperature] less than 146 ° C., Tm [melting point] 255 ° C.) is used instead of KF511 in Example 1. In the same manner as above, a polyester resin dispersion R27 having a solid content of about 33%, a particle size of about 20 μm, and a viscosity of 300 mPas was obtained. When the polyester resin dispersion was stored at 20 ° C. for 1 month, a precipitate was observed.
[0104]
Coating resin composition (for inner surface of can)
Examples 21-43, Comparative Examples 10-18
Each raw material was mix | blended with the container which has a stirrer according to the compounding table shown in Table 1 below, and each can inner surface coating resin composition was created.
[0105]
The above-mentioned resin composition for coating the inner surface of each can was evaluated for roll coat suitability (paintability) according to the following test method. In addition, each can inner surface coating resin composition, 5052 aluminum plate dry coating weight 100cm2Each bar was coated with a bar coater so as to be 120 mg, and baked and dried in 20 seconds under the condition of reaching 270 ° C. to prepare each coated plate.
[0106]
About each coating board obtained with the preparation method of the said coating board, the coating surface state, adhesiveness, workability, fragrance | flavor sorption property, retort resistance, and corrosion resistance were evaluated in accordance with the following test method. The test results are shown in Table 1 below.
[0107]
Test method
Roll coat suitability: The dispersion composition was tested using a reverse roll coater with the following conditions as standard. A 5052 aluminum plate was painted and evaluated according to the following criteria.
・ Coating conditions: Peripheral speed ratio of each roll, backup roll / coating roll / pickup roll = 1.0 / 1.05 / 0.4
・ Film thickness: Dry coating weight is 100cm2About 120mg per
・ Baking: No. Conditions for 5052 aluminum plate to reach 270 ° C in 20 seconds
○: 100 cm2It can be uniformly applied to a film thickness of about 120 mg per unit.
Δ: The film thickness is non-uniform.
X: In a roll coater, an unpainted part arises and the whole surface cannot be painted.
[0108]
Coating surface state: 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.
X: Large unevenness is observed on the entire coated surface.
[0109]
Adhesiveness: When using a knife on the paint film on the painted plate, make 11 cuts in the vertical and horizontal directions with a width of about 1.5 mm, close contact with 24 mm wide cellophane adhesive tape, and peel strongly The coating film of the gobang eyes was observed and evaluated according to the following criteria.
A: No separation is observed.
○: Slight peeling is observed.
Δ: Considerable peeling.
X: Remarkable peeling is recognized.
[0110]
Workability: A 180-degree fold is provided at the bottom of the paint plate with the coating surface facing outward, and using a special goby fold type DuPont impact tester, the contact surface is flat and the weight is 1 kg of iron. The length of the cracks in the coating film at the bent portion produced 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.
[0111]
Perfume sorption property: A coated plate is immersed in a solution obtained by dispersing 30 mg / l of d-limonene solution in deionized water with 1 g / l of S-1170 (Mitsubishi Chemical Sucrose Fatty Acid Ester), at 35 ° C. for 1 month Stored. After storage, d-limonene sorbed on the coating film was extracted with diethyl ether over a period of 20 ° C. for 1 week, and the sorption 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 the coating film weight.
X: 1.6 mg or more per 120 mg of coating film weight.
[0112]
Retort resistance: The coated plate was immersed in deionized water at 125 ° C. for 35 minutes in an autoclave and pulled up, and then the whitening state of the coating film was observed and evaluated according to the following criteria.
○: Slight whitening is observed in the coating film.
(Triangle | delta): Considerable whitening is recognized by the coating film.
X: Remarkable whitening is observed in the coating film.
[0113]
Corrosion resistance: Dip a coated plate coated with tape or the like in 10% pine juice in a container that can be sealed tightly so that the back surface will not corrode. The state of was observed and evaluated according to the following criteria.
○: Corrosion is not recognized.
Δ: Corrosion is considerably observed.
X: Corrosion is remarkable.
[0114]
[Table 1]
[Table 2]
The raw materials of each note (* 1) to (* 4) in Table 1 have the following contents.
(* 1) VALCAM 29-101: manufactured by BTL SPECIALTY RESINS, xylenol / formaldehyde type phenol resin, solid content 100%.
(* 2) Cymel 303: Mitsui Cytec, methylated melamine resin, solid content 100%.
(* 3) ECN1273: manufactured by Asahi Kasei Epoxy Corporation, orthocresol novolac type epoxy resin, epoxy equivalent 220.
(* 4) NACURE5925: manufactured by King Industries, an amine neutralized solution of dodecylbenzenesulfonic acid, active ingredient 25%.
[0117]
Coating resin composition (for lubricating metal plate)
Examples 44 and 45 and Comparative Example 19
Each raw material was blended in a container having a stirrer in accordance with a blending table shown in Table 3 below to prepare each coating resin composition.
[0118]
Creating a test plate
On each surface of an aluminum plate (aluminum alloy 3004 having a thickness of 0.30 mm), each coating resin composition shown in Table 3 below has a dry film thickness of 50 mg / 100 cm.2Then, the aluminum plate was heated under the condition that the temperature of the aluminum plate reached 270 ° C. in 25 seconds to obtain each coated plate.
[0119]
The obtained coated plate was evaluated for drawing ironing workability and corrosion resistance by the following test methods. The obtained results are shown in Table 3 below.
[0120]
Test method
Drawing and ironing workability: After forming each coated plate obtained in the above into a cylindrical shape, using a thin metal plate deep drawing tester type 142 manufactured by Eriksen Co., Ltd. The processing was performed in order in five stages, and finally the drawing and ironing process with a drawing rate of about 37% and a drawing rate of about 60% was performed.
[0121]
[Table 3]
The draw ironing workability at that time was evaluated according to the following criteria.
○: Can be molded.
X: Destruction of the material occurs, and molding cannot be performed until the end.
[0123]
Corrosion resistance: For each coated plate, blank punching, cupping, ironing (ironing) processing and trimming by a D & I machine were sequentially performed to form a can having a can height of 125 mm and an outer diameter of 65 mm. On the inner surface side of the can, 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 so that the dry film thickness was about 1 to 2 μm. Baking was performed at a temperature of 60 ° C. for 60 seconds. Further, a 2-piece can was finally made by flanging so that the aluminum lid could be tightened by a flanging machine. The two-piece can was hot-packed with 10% pine juice at 98 ° C, then wrapped with an aluminum lid, stored at 35 ° C for 1 month, opened, and observed for internal corrosion. Evaluation was made according to the criteria.
○: Corrosion is not recognized.
Δ: Slight corrosion is observed.
X: Corrosion is remarkable.
[0124]
[Table 4]
The raw materials of each note (* 5) and (* 6) in Table 3 are as follows.
(* 5) CRODALAN SWL: manufactured by Croder Japan, purified lanolin wax, solid content 100%, softening point 30-38 ° C
(* 6) HI-DISPER F-10PC: manufactured by Gifu Shellac Manufacturing Co., Ltd., carnauba wax, solid content 10%, softening point 81-86 ° C
[0126]
【The invention's effect】
The polyester resin dispersion of the present invention was obtained by uniformly dispersing a crystalline polyester resin that does not dissolve in a solvent into an organic solvent with an amorphous polyester resin and a specific phosphoric acid compound. The storage stability of the polyester resin dispersion is also extremely excellent. In addition, the coating composition using the polyester resin dispersion is excellent in roll coating workability, and the coating obtained by coating a metal material has adhesion, workability, flavor sorption, Since it exhibits excellent performance in retort resistance, corrosion resistance and the like, it is particularly suitable as a resin composition for coating the inner surface of a can.
Claims (10)
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| JP2003033069A JP4223824B2 (en) | 2002-02-13 | 2003-02-12 | Polyester resin dispersion |
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| JP2003033069A JP4223824B2 (en) | 2002-02-13 | 2003-02-12 | Polyester resin dispersion |
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| JP4906373B2 (en) * | 2006-03-14 | 2012-03-28 | 関西ペイント株式会社 | Can coating composition |
| JP5326207B2 (en) * | 2006-12-15 | 2013-10-30 | 東洋紡株式会社 | Coating composition, laminate and flexible flat cable |
| WO2011019840A1 (en) * | 2009-08-11 | 2011-02-17 | Valspar Sourcing, Inc. | Polymer particles and coating compositions formulated from the polymer particles |
| JP6224388B2 (en) * | 2013-01-15 | 2017-11-01 | 北海製罐株式会社 | Method for producing resin-coated metal sheet |
| CA2904501A1 (en) * | 2013-03-15 | 2014-09-18 | Akzo Nobel Coatings International B.V. | Coating compositions having hydroxyl phenyl functional polymers |
| JP6696712B2 (en) * | 2016-01-06 | 2020-05-20 | 関西ペイント株式会社 | Coating composition for cans |
| 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 |
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