JP5159034B2 - Cap coating composition - Google Patents
Cap coating composition Download PDFInfo
- Publication number
- JP5159034B2 JP5159034B2 JP2005305175A JP2005305175A JP5159034B2 JP 5159034 B2 JP5159034 B2 JP 5159034B2 JP 2005305175 A JP2005305175 A JP 2005305175A JP 2005305175 A JP2005305175 A JP 2005305175A JP 5159034 B2 JP5159034 B2 JP 5159034B2
- Authority
- JP
- Japan
- Prior art keywords
- coating composition
- parts
- cap
- mass
- melamine 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.)
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- 239000008199 coating composition Substances 0.000 title claims description 36
- 229920001225 polyester resin Polymers 0.000 claims description 39
- 239000004645 polyester resin Substances 0.000 claims description 39
- 229920000877 Melamine resin Polymers 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 33
- -1 fatty acid ester Chemical class 0.000 claims description 32
- 239000004640 Melamine resin Substances 0.000 claims description 29
- 229920000098 polyolefin Polymers 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 22
- 239000000194 fatty acid Substances 0.000 claims description 22
- 229930195729 fatty acid Natural products 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 32
- 229920003270 Cymel® Polymers 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 150000007519 polyprotic acids Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 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 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-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
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 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
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 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
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- WHKKNVAGWPTSRS-UHFFFAOYSA-N 2-dodecylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(CCCCCCCCCCCC)=CC=C21 WHKKNVAGWPTSRS-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- GNBPEYCZELNJMS-UHFFFAOYSA-N 2-methylbutane-1,3-diol Chemical compound CC(O)C(C)CO GNBPEYCZELNJMS-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- HJJZIMFAIMUSBW-UHFFFAOYSA-N 3-methylbutane-1,2-diol Chemical compound CC(C)C(O)CO HJJZIMFAIMUSBW-UHFFFAOYSA-N 0.000 description 1
- OGLLAZUAZSIDFE-UHFFFAOYSA-N 3-methylpentane-1,2-diol Chemical compound CCC(C)C(O)CO OGLLAZUAZSIDFE-UHFFFAOYSA-N 0.000 description 1
- RLWWHEFTJSHFRN-UHFFFAOYSA-N 3-methylpentane-2,3-diol Chemical compound CCC(C)(O)C(C)O RLWWHEFTJSHFRN-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920003275 CYMEL® 325 Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001072282 Limnanthes Species 0.000 description 1
- 235000018330 Macadamia integrifolia Nutrition 0.000 description 1
- 240000000912 Macadamia tetraphylla Species 0.000 description 1
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- 229930195725 Mannitol Natural products 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000002744 anti-aggregatory effect Effects 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
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- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
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- 125000001841 imino group Chemical group [H]N=* 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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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000010466 nut oil Substances 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
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- FIWHJQPAGLNURC-UHFFFAOYSA-N oxiran-2-ylmethyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OCC1CO1 FIWHJQPAGLNURC-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005029 tin-free steel Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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Images
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、金属製素材との密着性、加工性、耐食性、キャップの開栓性及びライナーとの付着性に優れた塗膜を形成するキャップ用塗料組成物及びキャップに関する。 The present invention relates to a cap coating composition and a cap that form a coating film excellent in adhesion to a metal material, workability, corrosion resistance, cap openability, and adhesion to a liner.
清涼飲料水等に用いられる図1の金属キャップは、金属板に塗料組成物を塗装して加熱乾燥して塗膜被覆金属板とした後、キャップ形状に成形加工し、さらに内容物の密閉性を高めるために、キャップ裏にポリエチレンシート(「ライナー」と称する、図1の5参照)を圧着している。 The metal cap shown in FIG. 1 used for soft drinks, etc. is coated with a coating composition on a metal plate, heat-dried to form a coating-coated metal plate, then molded into a cap shape, and the contents are sealed. In order to increase the resistance, a polyethylene sheet (referred to as “liner”, see 5 in FIG. 1) is pressure-bonded to the back of the cap.
上記塗膜被覆金属板は、厳しい「絞り」や「しごき」加工が加えられ、被覆されている塗膜には柔軟性や素材金属との密着性のほかに、キャップの側面部ではキャップの開栓性に関わり、キャップ天面部では、ライナーとの付着性が求められる。
従来、ライナーと金属製王冠との接着方法に関する発明で、エポキシ系樹脂組成物をプライマーとして用いたポリオレフィンライナーと金属製王冠との接着方法が開示されている(特許文献1)。しかし、特許文献1のエポキシ系樹脂組成物のプライマーを塗装してなる塗膜は、ライナーとの付着性が不十分であった。
The above-mentioned coated metal sheet is subjected to severe “drawing” and “squeezing” processing. In addition to flexibility and adhesion to the metal, the coated coating is open on the side of the cap. The cap top surface portion is required to have adhesiveness to the liner.
Conventionally, an invention relating to a method for bonding a liner and a metal crown, and a method for bonding a polyolefin liner and a metal crown using an epoxy resin composition as a primer has been disclosed (Patent Document 1). However, the coating film formed by coating the primer of the epoxy resin composition of
他に、ベース塗装を有する金属板基材に、ビスフェノール型エポキシ樹脂、該エポキシ樹脂の硬化剤、極性基含有ポリオレフィン樹脂粒子、およびフッ素樹脂または反応性シリコーン化合物で変性した融点90℃以上のワックスを有機溶媒中に溶解もしくは分散せしめてなるポリオレフィン接着性塗料を塗布、硬化させてなる塗装金属板を、該塗装面が内面となるように成形加工したキャップに関する発明が開示されている(特許文献2)。しかし、特許文献2のポリオレフィン接着性塗料を塗装してなる塗膜は、キャップの開栓性が不十分であった。
In addition, a wax having a melting point of 90 ° C. or more modified with a bisphenol type epoxy resin, a curing agent for the epoxy resin, a polar group-containing polyolefin resin particle, and a fluororesin or a reactive silicone compound is applied to a metal plate substrate having a base coating. An invention relating to a cap obtained by forming and processing a coated metal plate obtained by applying and curing a polyolefin adhesive paint dissolved or dispersed in an organic solvent so that the painted surface becomes an inner surface is disclosed (Patent Document 2). ). However, the coating film formed by applying the polyolefin adhesive paint of
本発明の目的は、金属製素材との密着性、加工性、耐食性、キャップ開栓性及びライナーとの付着性に優れた塗膜を形成するキャップ用塗料組成物及びキャップを提供することである。 An object of the present invention is to provide a cap coating composition and a cap that form a coating film excellent in adhesion to a metal material, processability, corrosion resistance, cap opening, and adhesion to a liner. .
本発明者らは上記課題を解決するため鋭意研究した結果、水酸基含有ポリエステル樹脂(A)70〜95質量部とメラミン樹脂(B)5〜30質量部の固形分合計100質量部に対して、酸化ポリオレフィン(C)を1〜15質量部及び脂肪酸エステル(D)を0.5〜10質量部を含有することを特徴とするキャップ用塗料組成物が、上記課題の解決に極めて有用であることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the inventors of the present invention have a solid content of 70 to 95 parts by mass of the hydroxyl group-containing polyester resin (A) and 5 to 30 parts by mass of the melamine resin (B). A cap coating composition characterized by containing 1 to 15 parts by mass of oxidized polyolefin (C) and 0.5 to 10 parts by mass of fatty acid ester (D) is extremely useful for solving the above-mentioned problems. As a result, the present invention has been completed.
本発明のキャップ用塗料組成物によって、金属製素材との密着性、加工性、耐食性、キャップ開栓性及びライナーとの付着性に優れた塗膜を形成できる。 The coating composition for a cap of the present invention can form a coating film excellent in adhesion with a metal material, processability, corrosion resistance, cap opening and adhesion to a liner.
本発明のキャップ用塗料組成物は、水酸基含有ポリエステル樹脂(A)70〜95質量部とメラミン樹脂(B)5〜30質量部の固形分合計100質量部に対して、酸化ポリオレフィン(C)を1〜10質量部含有し、さらに脂肪酸エステル(D)を0.5〜10部含有するものである。 The cap coating composition of the present invention comprises oxidized polyolefin (C) with respect to a total solid content of 70 to 95 parts by mass of the hydroxyl group-containing polyester resin (A) and 5 to 30 parts by mass of the melamine resin (B). It contains 1 to 10 parts by mass, and further contains 0.5 to 10 parts of fatty acid ester (D).
水酸基含有ポリエステル樹脂(A):
ポリエステル樹脂は、多塩基酸と多価アルコールとのエステル化反応により調製することができる。多塩基酸は1分子中に2個以上のカルボキシル基を有する化合物であり、例えば、無水フタル酸、イソフタル酸、テレフタル酸、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロトリメリット酸、テトラヒドロフタル酸、メチルヘキサヒドロフタル酸、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、無水マレイン酸等の二塩基酸;二塩基酸の低級アルキルエステル;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価以上の多塩基酸又は無水物などが挙げられ、これらの中、1分子中に1もしくは2個の4〜6員環程度の脂環式構造と少なくとも2個以上のカルボキシル基を有する脂環式多塩基酸、例えば、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロトリメリット酸、テトラヒドロフタル酸、メチルヘキサヒドロフタル酸及びそれらの無水物が挙げられる。この中でもシクロヘキサン−1,4−ジカルボン酸が好ましい。また、必要に応じて、上記多塩基酸に、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を、分子量調整などの目的で、上記多塩基酸を、例えば、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と併用することができる。更に、ヤシ油脂肪酸、脱水ひまし油脂肪酸等の油脂肪酸を併用することも可能である。
Hydroxyl-containing polyester resin (A):
The polyester resin can be prepared by an esterification reaction between a polybasic acid and a polyhydric alcohol. A polybasic acid is a compound having two or more carboxyl groups in one molecule. For example, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydrotriphthalic acid. Dibasic acids such as merit acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride; lower alkyl of dibasic acid Esters: Trivalent or higher polybasic acids such as trimellitic anhydride, methylcyclohexeric carboxylic acid, pyromellitic anhydride, and anhydrides are included. Among these, 1 or 2 4 to 6 members per molecule Cycloaliphatic polysalt having a ring-like alicyclic structure and at least two or more carboxyl groups Acid, for example, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, hexahydroterephthalic trimellitic acid, tetrahydrophthalic acid, methyl hexahydrophthalic acid and their anhydrides. Of these, cyclohexane-1,4-dicarboxylic acid is preferred. If necessary, the polybasic acid may be a monobasic acid such as benzoic acid, crotonic acid, or pt-butylbenzoic acid, and the polybasic acid may be used, for example, for the purpose of adjusting the molecular weight. , Crotonic acid, and monobasic acids such as pt-butylbenzoic acid. Further, oil fatty acids such as coconut oil fatty acid and dehydrated castor oil fatty acid can be used in combination.
多価アルコールは、1分子中に2個以上の水酸基を有する化合物であり、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリメチレングリコール、テトラエチレングリコール、トリエチレングリコール、ジプロピレングリコール、1,4−ブタンジオール、1,3−ブタンジオール、2,3−ブタンジオール、1,2−ブタンジオール、3−メチル−1,2−ブタンジオール、2−ブチル−2−エチル−1,3−プロパンジオール、1,2−ペンタンジオール、1,5−ペンタンジオール、1,4−ペンタンジオール、2,4−ペンタンジオール、2,3−ジメチルトリメチレングリコール、テトラメチレングリコール、3−メチル−4,3−ペンタンジオール、3−メチル−4,5−ペンタンジオール、2,2,4−トリメチル−1,3−ペンタンジオール、1,6−ヘキサンジオール、1,5−ヘキサンジオール、1,4−ヘキサンジオール、2,5−ヘキサンジオール、ネオペンチルグリコール、ヒドロキシピバリン酸、ネオペンチルグリコールエステルなどの2価アルコール;これらの2価アルコールにε−カプロラクトンなどのラクトン類を付加したポリラクトンジオール;ビス(ヒドロキシエチル)テレフタレートなどのエステルジオール類;ビスフェノールAのアルキレンオキサイド付加物、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコールなどのポリエーテルジオール類;グリセリン、トリメチロールプロパン、トリメチロールエタン、ジグリセリン、トリグリセリン、1,2,6−ヘキサントリオール、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、マンニットなどの3価以上のアルコール;これらの3価以上のアルコールにε−カプロラクトンなどのラクトン類を付加させたポリラクトンポリオール類;1,4−シクロヘキサンジメタノール、トリシクロデカンジメタノール、水添ビスフェノールA、水添ビスフェノールF等の脂環族多価アルコールなどが挙げられる。また、プロピレンオキサイド及びブチレンオキサイドなどのα−オレフィンエポキシド、「カージュラE10」(商品名、ジャパンエポキシレジン社製、合成高分岐飽和脂肪酸のグリシジルエステル)などのモノエポキシ化合物などを酸と反応させて、これらの化合物をポリエステル樹脂に導入しても良い。 The polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule. For example, ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4- Butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentane Diol, 3-methyl-4,5-pentanediol, 2 2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, hydroxypivalic acid, neo Dihydric alcohols such as pentyl glycol esters; polylactone diols obtained by adding lactones such as ε-caprolactone to these dihydric alcohols; ester diols such as bis (hydroxyethyl) terephthalate; alkylene oxide adducts of bisphenol A, polyethylene Polyether diols such as glycol, polypropylene glycol and polybutylene glycol; glycerin, trimethylolpropane, trimethylolethane, diglycerin, triglycerin, 1,2,6-hexanetrio , Pentaerythritol, dipentaerythritol, sorbitol, mannitol and other trihydric alcohols; polylactone polyols obtained by adding lactones such as ε-caprolactone to these trihydric or higher alcohols; 1,4-cyclohexane Examples include alicyclic polyhydric alcohols such as dimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F. In addition, a monoepoxy compound such as an α-olefin epoxide such as propylene oxide and butylene oxide, “Cardura E10” (trade name, manufactured by Japan Epoxy Resin Co., Ltd., a glycidyl ester of a synthetic highly branched saturated fatty acid) and the like are reacted with an acid. These compounds may be introduced into the polyester resin.
ポリエステル樹脂の反応については、それ自体既知の方法によって行うことができ、例えば、前記多塩基酸成分と多価アルコール成分とを、多塩基酸成分中のカルボキシル基に対して、多価アルコール成分中の水酸基が過剰になるようにして180〜250℃程度の温度で重縮合させることによって得ることができる。 The reaction of the polyester resin can be performed by a method known per se. For example, the polybasic acid component and the polyhydric alcohol component are mixed in the polyhydric alcohol component with respect to the carboxyl group in the polybasic acid component. It can be obtained by polycondensation at a temperature of about 180 to 250 ° C. so that the hydroxyl group of the compound becomes excessive.
また、前記多塩基酸成分と多価アルコール成分とから水酸基を有するポリエステル樹脂を得た後、このポリエステル樹脂の水酸基に、マレイン酸、無水マレイン酸、無水フタル酸、無水トリメリット酸などの多塩基酸を反応させることによって樹脂中にカルボキシル基を導入したポリエステル樹脂であってもよい。 水酸基含有ポリエステル樹脂(A)の数平均分子量(注1)としては、500〜50,000、好ましくは1,000〜20,000、水酸基価としては1〜100mgKOH/g、好ましくは3〜50mgKOH/g、酸価1〜200mgKOH/g、好ましくは1〜50mgKOH/gを有することができる。 Further, after obtaining a polyester resin having a hydroxyl group from the polybasic acid component and the polyhydric alcohol component, a polybasic group such as maleic acid, maleic anhydride, phthalic anhydride, or trimellitic anhydride is added to the hydroxyl group of the polyester resin. The polyester resin which introduce | transduced the carboxyl group in resin by making an acid react may be sufficient. The number average molecular weight (Note 1) of the hydroxyl group-containing polyester resin (A) is 500 to 50,000, preferably 1,000 to 20,000, and the hydroxyl value is 1 to 100 mgKOH / g, preferably 3 to 50 mgKOH / g, an acid value of 1 to 200 mg KOH / g, preferably 1 to 50 mg KOH / g.
(注1)数平均分子量:JIS K 0124−83に準じて行ない、分離カラムにTSK GEL4000HXL+G3000HXL+G2500HXL+G2000HXL(東ソー(株)製)を用いて40℃で流速1.0ml/分、溶離液にGPC用テトラヒドロフランを用いて、RI屈折計で得られたクロマトグラムとポリスチレンの検量線から計算により求めた。 (Note 1) Number average molecular weight: Measured according to JIS K 0124-83, using TSK GEL4000H XL + G3000H XL + G2500H XL + G2000H XL (manufactured by Tosoh Corporation) as a separation column at a flow rate of 1.0 ml / min, Using GPC tetrahydrofuran as the eluent, it was obtained by calculation from the chromatogram obtained with the RI refractometer and the calibration curve of polystyrene.
メラミン樹脂(B):
メラミン樹脂としては、例えば、メチロール化メラミンのメチロール基の一部又は全部を炭素数1〜8の1価アルコール、例えば、メチルアルコール、エチルアルコール、n−プロピルアルコール、i−プロピルアルコール、n−ブチルアルコール、i−ブチルアルコール、2−エチルブタノール、2−エチルヘキサノール等で、エーテル化した部分エーテル化又はフルエーテル化メラミン樹脂があげられる。
Melamine resin (B):
As the melamine resin, for example, a part or all of the methylol group of methylolated melamine is a monohydric alcohol having 1 to 8 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl. Examples include partially etherified or fully etherified melamine resins etherified with alcohol, i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.
これらは、メチロール基がすべてエーテル化されているか、又は部分的にエーテル化され、メチロール基やイミノ基が残存しているものも使用できる。メチルエーテル化メラミン、エチルエーテル化メラミン、ブチルエーテル化メラミン等のアルキルエーテル化メラミンを挙げることができ、1種のみ、又は必要に応じて2種以上を併用してもよい。なかでもメチロール基の少なくとも一部又は全部をアルキルエーテル化したメチルエーテル化メラミン樹脂が好適である。 These may be used in which all methylol groups are etherified or partially etherified so that methylol groups or imino groups remain. Examples include alkyl etherified melamines such as methyl etherified melamine, ethyl etherified melamine, and butyl etherified melamine, and only one kind may be used or two or more kinds may be used in combination. Of these, methyl etherified melamine resins in which at least a part or all of methylol groups are alkyl etherified are preferred.
このような条件を満たすメラミン樹脂の市販品としては、例えば「サイメル202」、「サイメル232」、「サイメル235」、「サイメル238」、「サイメル254」、「サイメル266」、「サイメル267」、「サイメル272」、「サイメル285」、「サイメル301」、「サイメル303」、「サイメル325」、「サイメル327」、「サイメル350」、「サイメル370」、「サイメル701」、「サイメル703」、「サイメル736」、「サイメル738」、「サイメル771」、「サイメル1141」、「サイメル1156」、「サイメル1158」等(以上、日本サイテック社製)、「ユーバン120」、「ユーバン20HS」、「ユーバン2021」、「ユーバン2028」、「ユーバン2061」等(以上、三井化学社製)、および「メラン522」等(日立化成社製)の商品名で市販されている。 Examples of commercially available melamine resins satisfying such conditions include “Cymel 202”, “Cymel 232”, “Cymel 235”, “Cymel 238”, “Cymel 254”, “Cymel 266”, “Cymel 267”, “Cymel 272”, “Cymel 285”, “Cymel 301”, “Cymel 303”, “Cymel 325”, “Cymel 327”, “Cymel 350”, “Cymel 370”, “Cymel 701”, “Cymel 703”, “Cymel 736”, “Cymel 738”, “Cymel 771”, “Cymel 1141”, “Cymel 1156”, “Cymel 1158” and the like (manufactured by Nippon Cytec Co., Ltd.), “Uban 120”, “Uban 20HS”, “ “Uban 2021,” “Uban 2028,” “Uban 2061,” etc. , Which is commercially available under the trade name manufactured by Mitsui Chemicals, Inc.), and "Melan 522" and the like (manufactured by Hitachi Chemical Co., Ltd.).
水酸基含有ポリエステル樹脂(A)とメラミン樹脂(B)の配合割合は、水酸基含有ポリエステル樹脂(A)とメラミン樹脂(B)の合計100質量部に対して、水酸基含有ポリエステル樹脂(A)が70〜95質量部、好ましくは75〜90質量部、メラミン樹脂(B)が5〜30質量部、好ましくは10〜25質量部の範囲内が硬化性の点から適している。また、硬化性促進のため、スルホン酸化合物、スルホン酸化合物のアミン中和物などの硬化触媒を配合してもよく、具体的には、ドデシルベンゼンスルホン酸、ジブチルベンゼンスルホン酸、ドデシルナフタレンスルホン酸、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などの高級アルキルアリールスルホン酸類及びこれらの塩類(例えば、アミン化合物、アンモニアなど)等のスルホン酸系化合物が挙げられる。 The mixing ratio of the hydroxyl group-containing polyester resin (A) and the melamine resin (B) is such that the hydroxyl group-containing polyester resin (A) is 70 to 70 parts by mass with respect to a total of 100 parts by mass of the hydroxyl group-containing polyester resin (A) and the melamine resin (B). From the viewpoint of curability, 95 parts by mass, preferably 75 to 90 parts by mass, and 5 to 30 parts by mass, preferably 10 to 25 parts by mass of the melamine resin (B) are suitable. In order to promote curability, a curing catalyst such as a sulfonic acid compound or an amine neutralized product of a sulfonic acid compound may be blended, and specifically, dodecylbenzenesulfonic acid, dibutylbenzenesulfonic acid, dodecylnaphthalenesulfonic acid. , Sulfonic acid compounds such as higher alkylaryl sulfonic acids such as dinonylnaphthalenesulfonic acid and dinonylnaphthalenedisulfonic acid, and salts thereof (for example, amine compounds and ammonia).
酸化ポリオレフィン(C):
本発明の本キャップ用塗料組成物は、金属製素材との密着性やキャップ開栓性及びライナーの付着性向上を目的として、酸化ポリオレフィン(C)を配合する。酸化ポリオレフィン(C)は、乾燥状態で粉砕したもの、あるいは溶剤中で加熱溶解させた後冷却して溶剤中に樹脂粒子を析出させた分散体で、樹脂粒子の最大粒子径は100μm以下、好ましくは50μm以下、酸価は0.5〜40mgKOH/g、融点は100〜140℃の範囲のものが挙げられる。具体的には、酸化ポリエチレン、エチレン−アクリル酸共重合物、カルボン酸グラフト変性ポリオレフィン等を例示できる。
Oxidized polyolefin (C):
The cap coating composition of the present invention is blended with the oxidized polyolefin (C) for the purpose of improving adhesion to a metal material, cap opening and liner adhesion. The oxidized polyolefin (C) is a dispersion obtained by pulverizing in a dry state, or a dispersion in which resin particles are precipitated by heating and dissolving in a solvent and then cooling, and the maximum particle size of the resin particles is preferably 100 μm or less. Of 50 μm or less, an acid value of 0.5 to 40 mg KOH / g, and a melting point of 100 to 140 ° C. Specific examples include polyethylene oxide, ethylene-acrylic acid copolymer, carboxylic acid graft-modified polyolefin, and the like.
この中でも、ライナーの付着性向上の為には酸化ポリエチレンが好ましい。具体的には、ペトロライトE−2020(東洋ペトロライト社製、酸化ポリエチレン、酸価22mgKOH/g、融点116℃)、4202E(三井化学社製、酸化ポリエチレン、酸価17mgKOH/g、融点100℃)、等が挙げられる。 Among these, polyethylene oxide is preferable for improving the adhesion of the liner. Specifically, Petrolite E-2020 (manufactured by Toyo Petrolite, polyethylene oxide, acid value 22 mg KOH / g, melting point 116 ° C.), 4202E (Mitsui Chemicals, polyethylene oxide, acid value 17 mg KOH / g, melting point 100 ° C. ), And the like.
酸化ポリオレフィン(C)の配合量としては、水酸基含有ポリエステル樹脂(A)とメラミン樹脂(B)の合計100質量部に対して、酸化ポリオレフィン(C)を1〜15質量部、好ましくは2〜10質量部、さらに好ましくは4〜8質量部を含有することが、密着性とライナーとの付着性向上の為によい。酸化ポリオレフィン(C)が1質量部未満では、ライナーとの接着性が低下し、15質量部を越えるとライナーの付着性のさらなる向上効果がないばかりか、塗膜外観を損なう。 The blending amount of the oxidized polyolefin (C) is 1 to 15 parts by mass, preferably 2 to 10 parts by mass of the oxidized polyolefin (C) with respect to 100 parts by mass in total of the hydroxyl group-containing polyester resin (A) and the melamine resin (B). It is preferable to contain 4 parts by mass, more preferably 4 to 8 parts by mass, for improving adhesion and adhesion to the liner. If the oxidized polyolefin (C) is less than 1 part by mass, the adhesiveness to the liner is lowered, and if it exceeds 15 parts by mass, the effect of further improving the adhesion of the liner is not obtained, and the appearance of the coating film is impaired.
キャップ用塗料組成物中に、酸化ポリオレフィン(C)を配合する方法としては、方法(1):水酸基含有ポリエステル樹脂(A)、メラミン樹脂(B)、酸化ポリオレフィン(C)及び脂肪酸エステル(D)を混合して塗料組成物とする方法。
方法(2):水酸基含有ポリエステル樹脂(A)及びメラミン樹脂(B)の一部を、酸化ポリオレフィン(C)と加熱混合して混合物とし、次に該混合物を水酸基含有ポリエステル樹脂(A)とメラミン樹脂(B)と混合してキャップ用塗料組成物とする方法、が挙げられる。
As a method of blending the oxidized polyolefin (C) in the cap coating composition, method (1): hydroxyl group-containing polyester resin (A), melamine resin (B), oxidized polyolefin (C) and fatty acid ester (D) A method of mixing the composition into a coating composition.
Method (2): A part of the hydroxyl group-containing polyester resin (A) and melamine resin (B) is heated and mixed with the oxidized polyolefin (C) to form a mixture, and then the hydroxyl group-containing polyester resin (A) and melamine are mixed. And a method of mixing with the resin (B) to obtain a cap coating composition.
上記の方法(2)を用いたキャップ用塗料組成物の方が、キャップ開栓性及びライナーの付着性向上の為にも好ましい。理由としては、水酸基含有ポリエステル樹脂(A)の水酸基が金属素材に密着し、かつ水酸基含有ポリエステル樹脂及びメラミン樹脂と酸化ポリオレフィン(C)が十分な密着性を保ったまま表層に配向する為、ライナーとの付着性向上に係る付着活性点が付与されるものと思われる。 The cap coating composition using the above method (2) is also preferred for improving cap opening and liner adhesion. The reason is that the hydroxyl group of the hydroxyl group-containing polyester resin (A) is in close contact with the metal material, and the hydroxyl group-containing polyester resin and melamine resin and the oxidized polyolefin (C) are oriented on the surface layer while maintaining sufficient adhesion. It is thought that the adhesion active point related to the improvement in adhesion is given.
脂肪酸エステル(D):
本発明のキャップ用塗料組成物は、キャップ開栓性を向上させる目的で脂肪酸エステル(D)を配合する。脂肪酸エステル(D)は、凝固点20℃以下、特に10℃以下であることがキャップ開栓性の為にも好ましい。
Fatty acid ester (D):
The fatty acid ester (D) is blended in the cap coating composition of the present invention for the purpose of improving the cap opening performance. The fatty acid ester (D) preferably has a freezing point of 20 ° C. or lower, particularly preferably 10 ° C. or lower for cap opening ability.
脂肪酸エステル(D)とは、ポリオール化合物と脂肪酸とのエステル化物で、例えば、椿油、マカデミアナッツ油、シア油、オリーブ油、メドウフォーム油などの植物油やグリセリンと脂肪酸の合成油などを挙げることができる。 The fatty acid ester (D) is an esterified product of a polyol compound and a fatty acid, and examples thereof include vegetable oils such as coconut oil, macadamia nut oil, shea oil, olive oil and meadow foam oil, and synthetic oils of glycerin and fatty acids.
その中でも、食缶用に適したものとしては酸化による変質の少ないもの、臭気のできるだけ少ないもの等を考慮して選択することができる。酸化されにくいという点からは、脂肪酸エステル中の不飽和二重結合含有量の目安となるヨウ素価が小さいものが好ましく、一般に不乾性油と呼ばれるヨウ素価が100以下、好ましくは50以下のものが適している。また、臭気の点からは植物性油や合成油が適しており、さらにそれらのよく精製されたものであることがより好ましい。酸化されにくく臭気の少ない代表的な脂肪酸エステルとしては、例えば、グリセリンと飽和脂肪酸の合成油、精製オリ−ブ油、精製椿油等を挙げることができる。 Among them, those suitable for food cans can be selected in consideration of those with little alteration due to oxidation and those with as little odor as possible. From the viewpoint that it is difficult to oxidize, those having a small iodine value that is a measure of the unsaturated double bond content in the fatty acid ester are preferable, and those generally referred to as non-drying oils have an iodine value of 100 or less, preferably 50 or less. Is suitable. From the viewpoint of odor, vegetable oils and synthetic oils are suitable, and more preferably those are well purified. Typical fatty acid esters that are not easily oxidized and have a low odor include, for example, synthetic oils of glycerin and saturated fatty acids, refined olive oil, refined cocoon oil, and the like.
脂肪酸エステル(D)の添加量としては、水酸基含有ポリエステル樹脂(A)とメラミン樹脂(B)の合計100質量部に対して、0.5〜10質量部、好ましくは1〜5質量部がよい。脂肪酸エステル(D)の添加量が、0.5質量部未満ではキャップ開栓性の向上に効果がなく、10質量部を越えると加工機にワックスの堆積が発生したり、塗装安定性を損なう。 As addition amount of fatty-acid ester (D), 0.5-10 mass parts with respect to a total of 100 mass parts of hydroxyl-containing polyester resin (A) and melamine resin (B), Preferably 1-5 mass parts is good. . If the added amount of the fatty acid ester (D) is less than 0.5 parts by mass, the effect of improving cap opening is not effective, and if it exceeds 10 parts by mass, wax deposits occur on the processing machine or the coating stability is impaired. .
さらに、従来から用いられている潤滑性付与剤を用いることもできる。例えば、シリコーン系ワックス、フッ素系ワックス、ポリオレフィン系ワックス、ラノリン系ワックス、モンタンワックス、パラフィンワックス、マイクロクリスタリンワックス、カルナウバろう等が挙げられ、中でもラノリン系ワックス、マイクロクリスタリンワックス及びカルナウバろうが好ましい。 Furthermore, conventionally used lubricity-imparting agents can also be used. Examples thereof include silicone wax, fluorine wax, polyolefin wax, lanolin wax, montan wax, paraffin wax, microcrystalline wax, carnauba wax and the like, and lanolin wax, microcrystalline wax and carnauba wax are preferable.
本発明のキャップ用塗料組成物には、さらに必要に応じて、ビスフェノールA型エポキシ樹脂、ノボラック型エポキシ樹脂、有機溶剤、着色顔料、体質顔料、防錆顔料、凝集防止剤、レベリング剤、消泡剤、紫外線吸収剤などを配合することができる。 In the cap coating composition of the present invention, bisphenol A type epoxy resin, novolak type epoxy resin, organic solvent, coloring pigment, extender pigment, rust preventive pigment, anti-aggregation agent, leveling agent, antifoaming are further included as necessary. An agent, an ultraviolet absorber, etc. can be blended.
上記有機溶剤としては、各成分を溶解ないし分散できるものが使用でき、具体的には、例えば、トルエン、キシレン、高沸点石油系炭化水素などの炭化水素系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、イソホロンなどのケトン系溶剤、酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテートなどのエステル系溶剤、メタノール、エタノール、ブタノールなどのアルコール系溶剤、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルなどのグリコールエーテル系溶剤などを挙げることができ、これらは単独で、あるいは2種以上を混合して使用することができる。 As the organic solvent, those capable of dissolving or dispersing each component can be used. Specifically, for example, hydrocarbon solvents such as toluene, xylene, high boiling petroleum hydrocarbons, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Ketone solvents such as isophorone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, alcohol solvents such as methanol, ethanol, butanol, ethylene glycol monoethyl ether, ethylene glycol Examples include glycol ether solvents such as monobutyl ether and diethylene glycol monobutyl ether, and these can be used alone or in admixture of two or more. That.
得られたキャップ用塗料組成物は、被塗物として金属板上又は金属板を加工した缶又はキャップの外面及び/又は内面に塗装し、焼き付けることによって缶又はキャップ被覆用として適した塗膜を形成することができる。 The obtained coating composition for a cap is coated on the outer surface and / or the inner surface of a can or cap processed on a metal plate or a metal plate as an object to be coated, and baked to form a coating film suitable for covering the can or cap. Can be formed.
上記缶又はキャップに用いる金属板としては、飲料缶、缶詰用缶、キャップ等に用いることができる金属板であればいずれも使用することができ、例えば、アルミニウム板、ティンフリースチール板、ブリキ板等を挙げることができる。上記の被塗物以外には、例えば、プラスチック、ガラス板などの種々の被塗物にも塗装することができる。 As the metal plate used for the can or cap, any metal plate can be used as long as it can be used for beverage cans, cans for cans, caps, etc. For example, aluminum plate, tin-free steel plate, tin plate Etc. In addition to the above-described objects to be coated, various objects to be coated such as plastics and glass plates can also be applied.
塗装は、ロールコータ塗装、スプレー塗装等の塗装方法によって、塗装膜厚が、乾燥膜厚で1〜20μm、好ましくは2〜10μmとなるように塗装する。塗膜の焼付け条件は、通常、金属板であれば、約120〜300℃、好ましくは150〜200℃の温度、約10秒〜30分間、好ましくは約15秒〜約15分間加熱乾燥して塗膜被覆した金属板としている。この塗膜被覆した金属板をキャップ形状に成型加工し、該塗膜被覆金属板上にポリエチレン製のライナーを圧着して、内容物の密着性を高めている。本塗料組成物を用いたライナー付着性(注14参照)は、20N以上、好ましくは40N以上、さらに好ましくは60N以上で、従来にない付着性を得ることができる。 The coating is performed by a coating method such as roll coater coating or spray coating so that the coating film thickness is 1 to 20 μm, preferably 2 to 10 μm in terms of dry film thickness. The baking condition for the coating is usually about 120 to 300 ° C., preferably 150 to 200 ° C. for about 10 seconds to 30 minutes, preferably about 15 seconds to about 15 minutes for a metal plate. It is a metal plate coated with a coating film. The metal plate coated with the coating film is molded into a cap shape, and a polyethylene liner is pressure-bonded onto the coating-coated metal plate to enhance the adhesion of the contents. The liner adhesion using this coating composition (see Note 14) is 20 N or more, preferably 40 N or more, more preferably 60 N or more, and an unprecedented adhesion can be obtained.
以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれにのみに限定されるものではない。なお、「部」及び「%」は、特にことわらない限り、「質量部」及び「質量%」である。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited only to this. “Parts” and “%” are “parts by mass” and “% by mass” unless otherwise specified.
ポリエステル樹脂(A)の製造
製造例1 ポリエステル樹脂溶液No.1の製造例
TP−290(日本合成社製、ポリエステル樹脂、数平均分子量17,000、水酸基価5.5mgKOH/g、酸価1.5mgKOH/g、ガラス転移温度10℃)を混合溶剤a(注2)にて希釈して、固形分40%のポリエステル樹脂溶液No.1を得た。
(注2)混合溶剤a:ソルベッソ150(エッソ石油社製、高沸点芳香族炭化水素系溶剤)/シクロヘキサノン=70/30
Manufacture of polyester resin (A)
Production Example 1 Polyester resin solution No. Production Example 1 1 TP-290 (manufactured by Nihon Gosei Co., Ltd., polyester resin, number average molecular weight 17,000, hydroxyl value 5.5 mgKOH / g, acid value 1.5 mgKOH / g, glass transition temperature 10 ° C.) mixed solvent a ( Note 2) diluted with polyester resin solution No. 40 having a solid content of 40%. 1 was obtained.
(Note 2) Mixed solvent a: Solvesso 150 (manufactured by Esso Petroleum Corporation, high-boiling aromatic hydrocarbon solvent) / cyclohexanone = 70/30
製造例2 ポリエステル樹脂溶液No.2の製造例
バイロンGK−880(東洋紡績社製、ポリエステル樹脂、数平均分子量22,000、水酸基価4.5mgKOH/g、酸価1.0mgKOH/g、ガラス転移温度84℃)を混合溶剤a(注2)にて希釈して、固形分40%のポリエステル樹脂溶液No.2を得た。
Production Example 2 Polyester resin solution No. Production Example 2 No. 2 Byron GK-880 (manufactured by Toyobo Co., Ltd., polyester resin, number average molecular weight 22,000, hydroxyl value 4.5 mgKOH / g, acid value 1.0 mgKOH / g, glass transition temperature 84 ° C.) mixed solvent a (Note 2) diluted with a polyester resin solution No. 40 having a solid content of 40%. 2 was obtained.
製造例3 ビニル樹脂溶液の製造例
P−440(三菱化学社製、ポリ塩化ビニル樹脂、重合度1,500)を混合溶剤b(注3)にて分散して、固形分40%のビニル樹脂溶液を得た。
(注3)混合溶剤b:ソルベッソ150/エチレングリコールモノブチルエーテル=50/50
Production Example 3 Production Example P-440 of a Vinyl Resin Solution (Mitsubishi Chemical Corporation, Polyvinyl Chloride Resin, Degree of Polymerization 1,500) Dispersed in Mixed Solvent b (Note 3) to give a vinyl resin with a solid content of 40% A solution was obtained.
(Note 3) Mixed solvent b: Solvesso 150 / ethylene glycol monobutyl ether = 50/50
製造例4 エポキシ樹脂溶液の製造例
ARALDITE ECN1299(旭チバ社製、エポキシ樹脂、エポキシ当量230)を混合溶剤a(注2)にて溶解して、固形分40%のエポキシ樹脂溶液を得た。
Production Example 4 Production Example of Epoxy Resin Solution ARALDITE ECN1299 (manufactured by Asahi Ciba, epoxy resin, epoxy equivalent 230) was dissolved in a mixed solvent a (Note 2) to obtain an epoxy resin solution having a solid content of 40%.
製造例5 変性ポリエチレン溶液の製造例
フラスコにて、TP−290(日本合成社製、水酸基含有ポリエステル樹脂)30部、サイメル303(日本サイテック社製、メチルエーテル化メラミン樹脂)20部(固形分20部)、ペトロライトE−2020(東洋ペトロライト社製、酸化ポリエチレン、酸価22mgKOH/g、融点116℃)50部、混合溶剤a(注2)を加えて、80℃にて1時間加熱混合して、固形分10%の変性ポリエチレン溶液を得た。
Production Example 5 Production Example of Modified Polyethylene Solution In a flask, 30 parts TP-290 (manufactured by Nippon Synthetic Co., Ltd., hydroxyl-containing polyester resin), 20 parts Cymel 303 (manufactured by Nippon Cytec Co., Ltd., methyl etherified melamine resin) (solid content 20) Part), Petrolite E-2020 (manufactured by Toyo Petrolite Co., Ltd., polyethylene oxide, acid value 22 mg KOH / g, melting point 116 ° C.) 50 parts, mixed solvent a (Note 2) was added, and heated and mixed at 80 ° C. for 1 hour. Thus, a modified polyethylene solution having a solid content of 10% was obtained.
実施例1
製造例1で得た固形分40%のポリエステル樹脂溶液No.1を200質量部(固形分80質量部)に、サイメル303(注4)20質量部(固形分20質量部)、ペトロライトE−2020(注6)5質量部、サンソフトNo.O-30B(注8)3質量部(固形分3質量部)及びNacure5925(注9)0.5質量部(固形分0.125質量部)を混合し、混合溶剤a(注2)を加えて固形分30%のキャップ塗料組成物No.1を得た。
(注4)サイメル303:日本サイテック社製、(完全)メチルエーテル化メラミン樹脂
(注5)サイメル370:日本サイテック社製、メチルエーテル化メラミン樹脂
(注6)ペトロライトE−2020:東洋ベトロライト社製、酸化ポリエチレン
(注7)4202E:三井化学社製製、酸化ポリエチレン
(注8)サンソフトNo.O-30B:太陽化学社製 、グリセリンと不飽和脂肪酸の合成油
(注9)Nacure5925:米国、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物である硬化触媒
Example 1
Polyester resin solution No. 40 having a solid content of 40% obtained in Production Example 1. 1 to 200 parts by mass (solid content 80 parts by mass), Cymel 303 (Note 4) 20 parts by mass (solid content 20 parts by mass), Petrolite E-2020 (Note 6) 5 parts by mass, Sunsoft No. O- 30B (Note 8) 3 parts by mass (
(Note 4) Cymel 303: Nippon Cytec Co., Ltd. (complete) Methyl etherified melamine resin (Note 5) Cymel 370: Nihon Cytec Co., Ltd., methyl etherified melamine resin (Note 6) Petrolite E-2020: Toyo Betrolite Co., Ltd. Manufactured by Polyethylene Oxide (Note 7) 4202E: Made by Mitsui Chemicals, Oxidized Polyethylene (Note 8) Sunsoft No.O-30B: Taiyo Kagaku, Synthetic oil of glycerin and unsaturated fatty acid (Note 9) Nacure 5925: USA Curing catalyst, neutralized by amines of dodecylbenzene sulfonic acid, manufactured by King Industries
実施例2
製造例2で得た固形分40%のポリエステル樹脂溶液No.2を200質量部(固形分80質量部)に、サイメル303(注4)20質量部(固形分20質量部)、ペトロライトE−2020(注6)5質量部、サンソフトNo.O-30B(注8)3質量部(固形分3質量部)及びNacure5925(注9)0.5質量部(固形分0.125質量部)を混合し、混合溶剤a(注2)を加えて固形分30質量%のキャップ用塗料組成物No.2を得た。
Example 2
Polyester resin solution No. 40 having a solid content of 40% obtained in Production Example 2. 2 to 200 parts by mass (solid content 80 parts by mass), Cymel 303 (Note 4) 20 parts by mass (solid content 20 parts by mass), Petrolite E-2020 (Note 6) 5 parts by mass, Sunsoft No. O- 30B (Note 8) 3 parts by mass (
実施例3〜6
表1に示す配合とする以外は、実施例1と同様に行って固形分30質量%の各キャップ用塗料組成物を得た。
Examples 3-6
A cap coating composition having a solid content of 30% by mass was obtained in the same manner as in Example 1 except that the formulation shown in Table 1 was used.
参考例1〜6
表2に示す配合とする以外は、実施例1と同様に行って固形分30%の各キャップ用塗料組成物を得た。
Reference Examples 1-6
Except for the formulation shown in Table 2, the same procedure as in Example 1 was performed to obtain each cap coating composition having a solid content of 30%.
試験塗装板の作成
実施例及び参考例で得た塗料を厚さ0.24mmの#3105アルミニウム板に、乾燥膜厚が4μmとなるように塗装し、風速3m/秒の熱風で素材到達最高温度(PMT)が180℃となる条件で10分間焼き付けて各試験塗板を得た。得られた各試験塗板については、下記の試験方法に基づいて試験を行った。試験結果を表3、表4に示す。
Preparation of test coating plate The paint obtained in the example and reference example was applied to a # 3105 aluminum plate with a thickness of 0.24 mm so that the dry film thickness would be 4 μm, and the maximum material temperature reached with hot air at a wind speed of 3 m / sec. Each test coated plate was obtained by baking for 10 minutes under the condition that (PMT) was 180 ° C. About each obtained test coating plate, the test was done based on the following test method. The test results are shown in Tables 3 and 4.
(注10)塗膜外観:試験塗板の塗膜外観を肉眼で観察した。
○:塗面にハジキ、凹み、曇りなどの塗面異常の認められない
△:塗面にハジキ、凹み、曇りなどの塗面異常のいずれかが認められる
×:塗面にハジキ、凹み、曇りなどの塗面異常が著しい。
(Note 10) Appearance of coating film: The coating film appearance of the test coating plate was observed with the naked eye.
○: No abnormal paint surface such as repellency, dents, or cloudiness on the paint surface
Δ: Any paint surface abnormality such as repellency, dent or cloudiness is observed on the paint surface. ×: Paint surface abnormality such as repellency, dent or cloudiness is marked on the paint surface.
(注11)密着性:JIS K−5400 8.5.2(1990)碁盤目テープ法に準じて、試験板の塗膜表面にカッターナイフで素地に到達するように、直行する縦横11本づつの並行な直線を1.5mm間隔で引いて、1.5mm×1.5mmのマス目を100個作成した。その表面にセロハン粘着テープを密着させ、テープを急激に剥離した際のマス目の剥がれ程度を観察し、下記基準で評価した。
○:塗膜の剥離が全く認められない。
△:塗膜が僅かに剥離するが、マス目は90個以上残存。
×:塗膜がかなり剥離し、マス目の残存数は90個未満。
(Note 11) Adhesion: In accordance with JIS K-5400 8.5.2 (1990) cross-cut tape method, the vertical and horizontal 11 straight lines are used to reach the substrate with a cutter knife on the coating film surface of the test plate. These parallel straight lines were drawn at intervals of 1.5 mm to create 100 squares of 1.5 mm × 1.5 mm. A cellophane pressure-sensitive adhesive tape was closely adhered to the surface, and the degree of peeling of the cells when the tape was abruptly peeled was observed and evaluated according to the following criteria.
○: No peeling of the coating film is observed.
(Triangle | delta): Although a coating film peels slightly, 90 or more squares remain | survive.
X: The coating film peeled off considerably, and the number of cells remaining was less than 90.
(注12)加工性:試験塗板をエリクセン社製の深絞り試験器で、33mm口径のポンチを用い、ブランク径60mmで外面側に塗膜がくるようにしてカップを作った。上記カップを100℃の沸騰水中に1時間浸漬を行った後、加工側面部について密着性試験を行った。評価基準は下記の通りである。
○:塗膜の剥離が全く認められない。
△:塗膜の剥離が僅かに認められる。
×:著しい塗膜の剥離が認められる。
(Note 12) Workability: A cup was prepared by using a punch with a diameter of 33 mm and a blank diameter of 60 mm so that the coating film was on the outer surface side with a deep drawing tester manufactured by Eriksen. After the cup was immersed in boiling water at 100 ° C. for 1 hour, an adhesion test was performed on the processed side surface portion. The evaluation criteria are as follows.
○: No peeling of the coating film is observed.
Δ: Slight peeling of coating film is observed.
X: Remarkable peeling of the coating film is observed.
(注13)動摩擦係数:キャップ開栓性に係る代用特性である。塗装板をイーガン スリップ テスター モデル NO.225-3(スウイング アルバート インスツルメント カンパニー製)[Egan Slip Tester Model No.225-3 (Thwing Albert Instrument Co.製)]を用いて、引っ張り速度10cm/分の条件にて動摩擦係数を測定した。
◎:動摩擦係数が0.025以下
○:動摩擦係数が0.025を越えて、かつ0.04未満
△:動摩擦係数が0.04を越えて、かつ0.06未満
×:動摩擦係数が0.06以上。
(Note 13) Coefficient of dynamic friction: A substitute characteristic related to cap opening performance. Using an Egan Slip Tester Model No.225-3 (manufactured by Swing Albert Instrument Company) [Egan Slip Tester Model No.225-3 (manufactured by Thwing Albert Instrument Co.)], a tensile speed of 10 cm / min. The dynamic friction coefficient was measured under the conditions.
A: Dynamic friction coefficient is 0.025 or less. O: Dynamic friction coefficient exceeds 0.025 and less than 0.04. Δ: Dynamic friction coefficient exceeds 0.04 and less than 0.06. X: Dynamic friction coefficient is 0.00. 06 or higher.
(注14)ライナー付着性:キャップのライナー付着に係る代用特性である。塗装板にポリエチレンライナー材(幅2cm)をのせ、ヒーターで120℃で10秒間加熱する。このときライナーの上には荷重300gの外力をかけた状態である。冷却後、オートグラフによって180°ピールでの引っ張り強度を測定する。
◎:引っ張り強度が60N以上
○:引っ張り強度が30N以上でかつ60N未満
△:引っ張り強度が5N以上でかつ30N未満
×:引っ張り強度が5N未満
(Note 14) Liner adhesion: A substitute characteristic related to the liner adhesion of the cap. A polyethylene liner (
◎: Tensile strength is 60N or more ○: Tensile strength is 30N or more and less than 60N △: Tensile strength is 5N or more and less than 30N ×: Tensile strength is less than 5N
金属製素材との密着性、加工性、耐食性、キャップ開栓性及びライナー付着性に優れた塗膜を形成するキャップを得ることができる。 It is possible to obtain a cap that forms a coating film excellent in adhesion to metal materials, processability, corrosion resistance, cap opening property, and liner adhesion.
1.金属製キャップ
2.瓶断面
3.金属基材
4.ライナー用塗料組成物
5.ライナー
6.塗装板
7.ヒーター
8.外力を加える
1.
Claims (12)
前記キャップ用塗料組成物が、水酸基含有ポリエステル樹脂(A)及びメラミン樹脂(B)を、それぞれ、70〜95質量部及び5〜30質量部の比率で含有すること、
前記キャップ用塗料組成物が、酸化ポリオレフィン(C)及び脂肪酸エステル(D)を、水酸基含有ポリエステル樹脂(A)及びメラミン樹脂(B)の固形分合計100質量部に対して、それぞれ、1〜15質量部及び0.5〜10質量部含有すること、及び
前記キャップ用塗料組成物が、酸化ポリオレフィン(C)を、水酸基含有ポリエステル樹脂(A)の一部及びメラミン樹脂(B)の一部と加熱しながら混合することにより混合物を生成すると共に、前記混合物を、残余の水酸基含有ポリエステル樹脂(A)、残余のメラミン樹脂(B)、及び脂肪酸エステル(D)と混合することにより生成されたこと、
を特徴とする、前記キャップ用塗料組成物。 A cap coating composition comprising a hydroxyl group-containing polyester resin (A), a melamine resin (B), an oxidized polyolefin (C), and a fatty acid ester (D),
The cap coating composition contains a hydroxyl group-containing polyester resin (A) and a melamine resin (B) in a ratio of 70 to 95 parts by mass and 5 to 30 parts by mass, respectively.
Each of the cap coating compositions contains oxidized polyolefin (C) and fatty acid ester (D) in an amount of 1 to 15 parts per 100 parts by mass in total of the solid content of the hydroxyl group-containing polyester resin (A) and melamine resin (B). Containing 10 parts by weight and 0.5-10 parts by weight, and
The coating composition for a cap produces a mixture by mixing the oxidized polyolefin (C) with a part of the hydroxyl group-containing polyester resin (A) and a part of the melamine resin (B), and the mixture The residual hydroxyl group-containing polyester resin (A), residual melamine resin (B), and fatty acid ester (D),
The cap coating composition characterized by the above-mentioned.
酸化ポリオレフィン(C)を、水酸基含有ポリエステル樹脂(A)の一部及びメラミン樹脂(B)の一部と、加熱しながら混合し、混合物を生成するステップ、そして
前記混合物を、残余の水酸基含有ポリエステル樹脂(A)、残余のメラミン樹脂(B)、及び脂肪酸エステル(D)と混合するステップ、
を含む、前記方法。 A method for producing a coating composition for a cap comprising a hydroxyl group-containing polyester resin (A), a melamine resin (B), an oxidized polyolefin (C), and a fatty acid ester (D),
A step of mixing the oxidized polyolefin (C) with a part of the hydroxyl group-containing polyester resin (A) and a part of the melamine resin (B) while heating to form a mixture, and the mixture with the remaining hydroxyl group-containing polyester Mixing with resin (A), residual melamine resin (B), and fatty acid ester (D);
Said method.
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