KR101854595B1 - Under coating compositions for pre-coated metal color steel sheet and painted steel sheet using the same - Google Patents
Under coating compositions for pre-coated metal color steel sheet and painted steel sheet using the same Download PDFInfo
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- KR101854595B1 KR101854595B1 KR1020150168919A KR20150168919A KR101854595B1 KR 101854595 B1 KR101854595 B1 KR 101854595B1 KR 1020150168919 A KR1020150168919 A KR 1020150168919A KR 20150168919 A KR20150168919 A KR 20150168919A KR 101854595 B1 KR101854595 B1 KR 101854595B1
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- weight
- steel sheet
- pcm
- coating composition
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- 239000008199 coating composition Substances 0.000 title claims abstract description 47
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 34
- 239000010959 steel Substances 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 title description 4
- 239000002184 metal Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000003973 paint Substances 0.000 claims abstract description 34
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000000049 pigment Substances 0.000 claims description 29
- 239000004645 polyester resin Substances 0.000 claims description 23
- 229920001225 polyester resin Polymers 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims 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 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 239000004606 Fillers/Extenders Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004640 Melamine resin Substances 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- -1 8-octanediol Chemical compound 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 5
- BLRJSXFWDNMKQT-UHFFFAOYSA-N 2-n-methoxy-1,3,5-triazine-2,4,6-triamine Chemical compound CONC1=NC(N)=NC(N)=N1 BLRJSXFWDNMKQT-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010494 dissociation reaction Methods 0.000 claims description 3
- 230000005593 dissociations Effects 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003449 preventive effect Effects 0.000 claims description 3
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 claims description 3
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 claims description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002987 primer (paints) Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 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
- 239000003377 acid catalyst Substances 0.000 description 3
- NGDPCAMPVQYGCW-UHFFFAOYSA-N dibenzothiophene 5-oxide Chemical compound C1=CC=C2S(=O)C3=CC=CC=C3C2=C1 NGDPCAMPVQYGCW-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012974 tin catalyst Substances 0.000 description 3
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000003187 abdominal effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000013100 final test Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000000699 topical effect Effects 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 101000644279 Homo sapiens Putative 2-oxo-4-hydroxy-4-carboxy-5-ureidoimidazoline decarboxylase Proteins 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 102100020935 Putative 2-oxo-4-hydroxy-4-carboxy-5-ureidoimidazoline decarboxylase Human genes 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- RLUCXJBHKHIDSP-UHFFFAOYSA-N propane-1,2-diol;propanoic acid Chemical compound CCC(O)=O.CC(O)CO RLUCXJBHKHIDSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Inorganic Chemistry (AREA)
Abstract
본 발명은 PCM 다색 강판의 하도용 도료 조성물 및 이를 이용한 도장 강판에 관한 것으로, 보다 상세하게는 다가알코올과 2가 산의 축합반응에 의해 생성되며, 방향족 모노머를 40 내지 70 중량% 함유하는 열경화성 폴리에스테르 수지를 포함하는 하도용 도료 조성물 및 상기 하도용 도료 조성물이 적어도 일면에 도장된 PCM 다색 강판에 관한 것이다. The present invention relates to a coating composition for undercoating a PCM multicolor steel sheet and a coated steel sheet using the same, and more particularly to a coating composition for a PCM multicolor steel sheet which comprises a thermosetting poly An ester resin, and a PCM multicolored steel sheet coated on at least one surface of the undercoat paint composition.
Description
본 발명은 PCM 다색 강판의 하도용 도료 조성물 및 이를 이용한 도장 강판에 관한 것으로, 보다 상세하게는 향상된 물성을 갖는 다색(Multi-Color) 컬러 강판에 관한 하도용 도료 조성물 및 이를 이용한 도장 강판에 관한 것이다.
The present invention relates to a paint composition for undercoating a PCM multicolor steel sheet and a coated steel sheet using the same, and more particularly to a paint composition for undercoats of a multi-color color steel sheet having improved physical properties and a coated steel sheet using the same .
일반적으로 피씨엠(PCM, Pre-Coated Metal) 강판에 적용되는 도료는 선도장 후가공의 공정을 거치게 되므로 후가공성이 요구된다. 또한, 제품 제조 이후부터는 생활환경 속의 각종 스크레치 요인들에 노출되므로 소지를 보호하고 외관을 유지하기 위해서는 고경도를 가져야 한다.
In general, the paint applied to the PCM (Pre-Coated Metal) steel sheet is subjected to a post-coating process, and thus post-processability is required. In addition, since the product is exposed to various scratch factors in the living environment after the manufacture of the product, it must have high hardness in order to protect the appearance and maintain appearance.
그러나, 일반적으로 경도와 가공성은 서로 상반되는 물성이기 때문에 어느 한쪽의 물성을 향상시키려면 다른 쪽의 물성은 떨어지게 된다. 따라서, 경도와 가공성을 동시에 만족시키는 수지를 합성하여 경화 시스템을 구축하는 것은 매우 어려운 일이다. 경도와 가공성을 모두 만족시키는 도료 조성물을 제조하기 위해서는 바인더 수지로서 분자량이 매우 큰 동시에 유리전이온도가 높은 폴리에스테르 수지가 적합하다.
However, in general, since the hardness and workability are opposite to each other, the physical properties of the other are deteriorated in order to improve the properties of either one. Therefore, it is very difficult to construct a curing system by synthesizing a resin that simultaneously satisfies hardness and workability. In order to prepare a coating composition which satisfies both hardness and workability, a polyester resin having a very high molecular weight and a high glass transition temperature is suitable as the binder resin.
현재, 피씨엠(pre-coated metal, PCM)용 도장 강판의 경우 일반적으로 하도(Primer)와 상도(Top)의 2 코팅(Coating) 2 베이킹(Baking) 시스템, 또는 하도(Primer), 중도(Base) 및 클리어(Clear)의 3 코팅(Coating) 3 베이킹(Baking) 시스템으로 이루어진다.
In the case of coated steel sheets for pre-coated metal (PCM), coating and baking of two primer and top two baking systems or primer, ) And a Clear 3 Coating 3 Baking system.
종래의 피씨엠(pre-coated metal, PCM) 도료는 대부분 하도와 상도 2 코팅(Coating) 2 베이킹(Baking) 시스템으로 이루어지고 있으며, 이는 도막의 가공성과 외관 등 기타 물성의 최적의 조건을 고려한 방법이다. 이것은 지금까지 소비자의 요구에 부응할 수 있는 최적의 물성조건을 나타낼 수 있는 최적의 도장 시스템으로 알려져 있다.
Conventional pre-coated metal (PCM) paints are mostly made of Hadouwa Sangdo 2 Coating 2 Baking system, which is based on the optimum condition of the physical properties such as the workability and appearance of the coating film to be. This is known as an optimal coating system that can represent optimal physical property conditions that can meet consumer's demands.
한편, 미건조된 하도(Primer)용 도료 조성물 상에 상도(Top)용 도료 조성물이 도장되는 웨트온웨트(Wet on Wet) 시스템을 적용하기 위해서 유연성 및 부착성이 우수한 수지를 적용하여 외관 및 물리적 특성 등을 만족시키는 도료 조성물의 개발이 요구되고 있다.
On the other hand, in order to apply a wet on wet system in which a coating composition for a top is coated on a non-dried primer coating composition, a resin having excellent flexibility and adhesion is applied, And the like have been demanded to be developed.
이에 본 발명의 한 측면은 우수한 물성을 가지며 다양한 색상의 다색 강판 상에 사용될 수 있는 PCM 다색 강판의 하도용 도료 조성물을 제공하는 것이다.
Accordingly, one aspect of the present invention is to provide a coating composition for undercoat of PCM multicolor steel sheet having excellent physical properties and being usable on a multicolored steel sheet of various colors.
본 발명의 다른 측면은 상기 본 발명의 하도용 도료 조성물이 도장된 PCM 다색 강판을 제공하는 것이다.
Another aspect of the present invention is to provide a PCM multicolored steel sheet coated with the coating composition for undercoat of the present invention.
본 발명의 일 견지에 의하면, 다가알코올과 2가 산의 축합반응에 의해 생성되며, 방향족 모노머를 40 내지 70 중량% 함유하는 열경화성 폴리에스테르 수지를 포함하는, 하도용 도료 조성물이 제공된다.
According to one aspect of the present invention, there is provided an undercoating composition comprising a thermosetting polyester resin produced by a condensation reaction of a polyhydric alcohol and a dicarboxylic acid and containing 40 to 70% by weight of an aromatic monomer.
본 발명의 다른 견지에 의하면, 상기 본 발명의 하도용 도료 조성물이 적어도 일면에 도장된 PCM 다색 강판이 제공된다.
According to another aspect of the present invention, there is provided a PCM multicolored steel sheet coated on at least one side of the undercoat paint composition of the present invention.
본 발명에 따른 도료 조성물을 다색(Multi-Color) 강판에 사용할 경우 기존의 단색 강판과 동등 이상의 도막 경화도, 내구성, 내약품성, 기계적 물성 등을 만족하면서, 다양한 색상의 소재 상에 구현되어 미적 효과도 획득할 수 있다. 나아가, 본 발명의 도료 조성물은 2 코팅(Coating) 1 베이킹(Baking) 시스템이 가능하도록 하여 오븐(Oven) 사용 횟수 절감에 따른 열 에너지 비용을 개선하여 원가 경쟁력을 향상시키고, 공정(line) 작업성의 개선 효과를 획득할 수 있다.
When the coating composition according to the present invention is applied to a multi-color steel sheet, it is realized on various color materials while satisfying the coating film hardness, durability, chemical resistance and mechanical properties equal to or more than that of a conventional single color steel sheet, Can also be obtained. Further, the coating composition of the present invention enables a two coating (baking) system to improve the cost competitiveness by improving the cost of heat energy due to the reduction of the number of oven usage, An improvement effect can be obtained.
도 1은 비교예 1의 하도 조성물을 이용한 경우(좌)와 본 발명 실시예 3의 하도 조성물을 이용하고, 제조예 2-A를 웨트온웨트(Wet on wet) 방식으로 적용한 경우(우)의 외관을 비교한 사진이다.Fig. 1 is a graph showing the results obtained when the undercoating composition of Comparative Example 1 was used (left) and the undercoating composition of Example 3 of the present invention was used, and when Production Example 2-A was applied by a wet on wet method It is a photograph comparing appearance.
이하, 첨부된 도면을 참조하여 본 발명의 바람직한 실시 형태를 설명한다. 그러나, 본 발명의 실시 형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.
본 발명에 의하면, 분자량이 증가된 수지를 사용하고, 방향족 성분 비율을 극대화하여, 건조성 및 반응성이 개선되며, 색상, 외관, 가공성, 부착성 등을 동시에 만족시키는 PCM 다색 강판의 하도용 도료 조성물이 제공된다.
INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a coating composition for undercoat of PCM polychrome steel sheet which uses a resin having an increased molecular weight and maximizes an aromatic component ratio to improve dryness and reactivity and simultaneously satisfy color, appearance, / RTI >
보다 상세하게, 본 발명의 하도용 도료 조성물은 다가알코올과 2가 산의 축합반응에 의해 생성되며, 방향족 모노머를 40 내지 70 중량% 함유하는 열경화성 폴리에스테르 수지를 포함하는 것이다.
More specifically, the coating composition for undercoating of the present invention comprises a thermosetting polyester resin which is produced by a condensation reaction of a polyhydric alcohol and a dicarboxylic acid and contains an aromatic monomer in an amount of 40 to 70% by weight.
본 발명에서는 열경화성 폴리에스테르 수지의 분자량을 증가시키고 방향족 성분 비율을 극대화하여 2 코팅(Coating) 1 베이킹(Baking) 시스템 적용 시 발생 할 수 있는 건조 및 작업성 문제를 해결할 수 있다. 즉, 웨트(Wet) 상태의 하도 상에 상도 도장을 하는 시스템에 있어서 외관 도막 끊음 현상 및 다색 경계면의 색겹침 등을 개선할 수 있다.
In the present invention, the molecular weight of the thermosetting polyester resin is increased and the aromatic component ratio is maximized, thereby solving the problem of drying and workability that may occur when applying the 2 coating (baking) system. That is, it is possible to improve the phenomenon of breakage of the external coating film and the color overlapping of the multi-color boundary surface in the system for painting the upper surface on the lower surface of the wet state.
본 발명에 사용되는 상기 열경화성 폴리에스테르 수지는 중량평균분자량이 20,000 내지 30,000이고, 수산기 값이 20 내지 50mgKOH/g이고, 산가가 1 내지 5 mgKOH/g이고, 유리전이온도(Tg)가 45 내지 55℃인 것이다.
The thermosetting polyester resin used in the present invention has a weight average molecular weight of 20,000 to 30,000, a hydroxyl value of 20 to 50 mgKOH / g, an acid value of 1 to 5 mgKOH / g, a glass transition temperature (Tg) of 45 to 55 Lt; / RTI >
이때, 상기 열경화성 폴리에스테르 수지의 중량평균 분자량이 20,000 미만인 경우에는 도막의 내구성을 유지하기 어려우며, 30,000를 초과하는 경우에는 작업성이 저하되는 문제가 있다.
When the weight average molecular weight of the thermosetting polyester resin is less than 20,000, it is difficult to maintain the durability of the coating film. When the weight average molecular weight exceeds 30,000, the workability is deteriorated.
상기 방향족 모노머는 BIS타입의 방향족 모노머인 것이 바람직하며, 예를 들어, 폴리옥시에틸렌 비스페놀-A 에테르 및 폴리옥시프로필렌 비스페놀-A 에테르로 이루어진 그룹으로부터 선택될 수 있으나, 이에 제한되는 것은 아니다.
The aromatic monomer is preferably an aromatic monomer of the BIS type and may be selected from the group consisting of, for example, polyoxyethylene bisphenol-A ether and polyoxypropylene bisphenol-A ether, but is not limited thereto.
이때 상기 방향족 모노머의 함량이 열경화성 폴리에스테르 수지의 총 중량 100%를 기준으로 40 중량% 미만인 경우에는 도막의 내구성 및 건조성을 유지하기 어려우며, 70 중량%를 초과하는 경우에는 작업성이 떨어지는 문제가 있다.
If the content of the aromatic monomer is less than 40% by weight based on 100% of the total weight of the thermosetting polyester resin, it is difficult to maintain the durability and dryness of the coating film. If the content of the aromatic monomer exceeds 70% by weight, .
본 발명의 하도용 도료 조성물은 열경화성 폴리에스테르 수지 25 내지 35 중량%의 함량으로 포함하며, 그 함량이 25 중량% 미만인 경우에는 도막의 내구성 및 건조성이 저하되며, 반면 35 중량%를 초과하는 경우에는 도료 조성물 내에 수지 성분이 지나치게 많아져 도막의 건조도가 저하되는 문제가 있다.
The coating composition for undercoating of the present invention is contained in an amount of 25 to 35% by weight of a thermosetting polyester resin. When the content of the thermosetting polyester resin is less than 25% by weight, durability and dryness of the coating film are lowered. On the other hand, There is a problem that the resin component is excessively increased in the coating composition and the drying degree of the coating film is lowered.
상기 다가알코올은 네오펜틸글리콜, 에틸렌글리콜, 1,6-헥산디올, 3-메틸-1,5-펜탄디올, 1,7-헵탄디올, 1,8-옥탄디올, 1,9-노난디올, 2-메틸-1,8-옥탄디올 및 1,10-데칸디올로 이루어지는 그룹으로부터 선택되는 것이 바람직하나, 이에 제한되는 것은 아니다.
The polyhydric alcohol may be at least one selected from the group consisting of neopentyl glycol, ethylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 2-methyl-1,8-octanediol, and 1,10-decanediol, but the present invention is not limited thereto.
상기 2가 산은 이소프탈산, 테레프탈산, 아디핀산, 피멜산, 수베린산, 아젤라인산, 세바식산, 프탈산, 이소프탈산 및 테레프탈산으로 이루어지는 그룹으로부터 선택되는 것이 바람직하나, 이에 제한되는 것은 아니다.
The divalent acid is preferably selected from the group consisting of isophthalic acid, terephthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid and terephthalic acid.
나아가, 본 발명의 하도용 도료 조성물은 가교제, 경화 촉매, 유기 용제, 방청 안료, 레벨링제, 체질안료, 분산 첨가제 및 에폭시 수지로 이루어진 그룹으로부터 선택된 적어도 하나의 성분을 추가로 포함할 수 있다.
Further, the coating composition for undergarment of the present invention may further comprise at least one component selected from the group consisting of a crosslinking agent, a curing catalyst, an organic solvent , a rust preventive pigment, a leveling agent, an extender pigment, a dispersant additive and an epoxy resin.
보다 상세하게, 본 발명의 상기 하도용 도료 조성물은 열경화성 폴리에스테르 수지 25 내지 35 중량%, 가교제 3 내지 13 중량%, 경화 촉매 0.5 내지 2.5 중량%, 유기 용제 30 내지 45 중량%, 방청 안료 5 내지 10 중량%, 레벨링제 0.5 내지 3.5중량%, 체질안료 2 내지 4 중량%, 분산 첨가제 0.1 내지 0.2 중량% 및 에폭시 수지 1 내지 3중량%를 포함하는 것이 바람직하다.
More specifically, the coating composition for undercoat of the present invention comprises 25 to 35% by weight of a thermosetting polyester resin, 3 to 13% by weight of a crosslinking agent, 0.5 to 2.5% by weight of a curing catalyst, 30 to 45% by weight of an organic solvent, , A leveling agent in an amount of 0.5 to 3.5% by weight, an extender pigment in an amount of 2 to 4% by weight, a dispersion additive in an amount of 0.1 to 0.2% by weight and an epoxy resin in an amount of 1 to 3% by weight.
본 발명의 하도용 도료 조성물에서 수지 성분과 도막을 형성하기 위한 가교제로서 멜라민 수지와 이소시아네이트 수지를 동시에 적용한다. 본 발명의 상기 가교제는 메톡시 멜라민 수지와 블록킹된(Blocked) 이소시아네이트 수지를 사용할 수 있으며, 바람직하게는 상기 멜라민 수지와 이소시아네이트 수지를 1:0.2~0.4의 중량비로 혼합한 혼합물인 것이다.
A melamine resin and an isocyanate resin are simultaneously applied as a crosslinking agent for forming a coating film with a resin component in the coating composition for undercoat of the present invention. The cross-linking agent of the present invention may be a blocked isocyanate resin with a methoxy melamine resin, preferably a mixture of the melamine resin and an isocyanate resin in a weight ratio of 1: 0.2 to 0.4.
상기 가교제로써 멜라민 수지를 단독을 적용하면 도막 강도는 우수하나, 도막의 가공성 및 부착성이 상대적으로 취약한 단점이 있고, 반면 이소시아네이트 수지를 단독으로 적용하면 가공성 및 부착성은 우수하나 상대적으로 도막 경도가 저하되는 단점이 있다. 따라서, 본 발명은 산촉매 적용 시 경화 반응 속도가 빠르고 경화 반응성이 우수한 메톡시 멜라민 수지와 블록킹된(Blocked) 이소시아네이트 수지를 혼합하여 사용한다.
When the melamine resin is used alone as the crosslinking agent, the strength of the coating film is excellent, but the processability and adhesion of the coating film are relatively weak. On the other hand, when the isocyanate resin is used alone, the processability and adhesion are excellent, . Accordingly, the present invention uses a methoxymelamine resin having a fast curing reaction rate and excellent curing reactivity when mixed with an acid catalyst, and a blocked isocyanate resin.
이때, 블록킹된(Blocked) 이소시아네이트 수지가 메톡시 멜라민 수지 1 중량부 당 0.2 중량부 미만일 경우 도막의 가공성 및 내식성이 저하되는 단점이 있고, 0.4 중량부를 초과할 경우 도막의 표면 경화가 저하되는 단점이 있다.
If the amount of the blocked isocyanate resin is less than 0.2 part by weight based on 1 part by weight of the methoxy melamine resin, there is a disadvantage in that the processability and corrosion resistance of the coating film are deteriorated. If the amount exceeds 0.4 parts by weight, have.
상기 가교제는 전체 하도용 도료 조성물의 중량을 기준으로 3 내지 13 중량%로 포함되며, 3 중량% 미만인 경우 경화도 문제가 있으며, 13 중량%를 초과하는 경우 가공성 문제가 있다.
The crosslinking agent is contained in an amount of 3 to 13% by weight based on the weight of the entire coating composition for lower use, and when it is less than 3% by weight, there is a problem of hardening, and when it is more than 13% by weight,
상기 경화 촉매는 Tin 촉매, 또는 p-톨루엔 술폰산(p-TSA), 디노닐나프탈렌 술폰산(DNNSA), 디나프탈렌 디술폰산(DNNDSA) 및 플루오로 술폰산으로 이루어진 그룹으로부터 선택된 술폰산을 아민 또는 에폭시로 중화시킨 것으로 해리 온도가 120 내지 150℃인 해리형 경화제인 것이 바람직하다. 상기 Tin 촉매는 디부틸틴디라우레이트(DBTDL) 등일 수 있으며, 우레탄 가교 결합을 위해 사용되므로 바람직하다.
The curing catalyst is a catalyst obtained by neutralizing a sulfonic acid selected from the group consisting of a Tin catalyst or p-toluenesulfonic acid (p-TSA), dinonylnaphthalenesulfonic acid (DNNSA), dinaphthalene disulfonic acid (DNNDSA), and fluorosulfonic acid with an amine or epoxy And a dissociation type curing agent having a dissociation temperature of 120 to 150 ° C. The Tin catalyst may be dibutyl tin dilaurate (DBTDL) or the like and is preferably used for urethane crosslinking.
상기 경화 촉매는 전체 하도용 도료 조성물의 중량을 기준으로 0.5 내지 2.5 중량%로 포함되며, 0.5 중량% 미만인 경우 경화도에 문제가 있으며, 2.5 중량%를 초과하는 경우 가공성에 문제가 있다.
The curing catalyst is contained in an amount of 0.5 to 2.5% by weight based on the weight of the entire coating composition for undercoating. When the amount is less than 0.5% by weight, there is a problem in the degree of curing. When the amount is more than 2.5% by weight,
본 발명의 도료 조성물은 취급, 피복 작업 시의 특성 등을 고려하여 유기 용제를 함유한다. 상기 유기 용제는 방향족 탄화수소계, 글리콜 에스테르계, 케톤계, 글리콜 에테르계 및 알코올계 용제로 이루어진 그룹으로부터 선택되는 적어도 1종의 용제인 것이 바람직하다.
The coating composition of the present invention contains an organic solvent in consideration of characteristics during handling and coating. The organic solvent is preferably at least one solvent selected from the group consisting of aromatic hydrocarbon solvents, glycol ester solvents, ketone solvents, glycol ether solvents and alcohol solvents.
예를 들어, 상기 방향족 탄화수소계 용제로는 SK사의 코코졸 #100, 코코졸 #150이 있으며, 글리콜 에스테르계 용제로는 유니온 카바이드사의 에틸 아세테이트, n-부틸 아세테이트, 셀로솔브 아세테이트, 프로필렌 글리콜 모노메틸 아세테이트, 3-메톡시 부틸 아세테이트 등이 있다. 글리콜 에테르계 용제로는 유니온 카바이드 사의 메틸 셀로솔브, 에틸 셀로솔브, 에틸렌 글리콜 부틸 에테르, 디에틸렌 글리콜 메틸 에테르, 디에틸렌 글리콜 에틸에테르, 디에틸렌 글리콜부틸 에테르 등이 있으며, 알코올계 용제로는 에탄올, 이소프로판올, n-부탄올, 아밀알콜, 사이클로 헥산올 등을 예로들 수 있다.
Examples of the aromatic hydrocarbon-based solvent include cocosol # 100 and cocosol # 150 manufactured by SK Company. Examples of the glycol ester solvent include ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl Acetate, 3-methoxybutyl acetate, and the like. Examples of the glycol ether type solvent include methyl cellosolve, ethyl cellosolve, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether and the like of Union Carbide Co., Isopropanol, n-butanol, amyl alcohol, cyclohexanol and the like.
상기 용제는 전체 하도용 도료 조성물의 중량을 기준으로 30 내지 45 중량%로 포함되며, 30 중량% 미만인 경우 작업성에 문제가 있으며, 45 중량%를 초과하는 경우 도막 형성에 문제가 있다.
The solvent is contained in an amount of 30 to 45% by weight based on the total weight of the coating composition. When the amount is less than 30% by weight, there is a problem in workability. When the amount is more than 45% by weight,
특히, 가전용 하도용 도료 조성물로 사용되는 경우에는 에스테르계 와 케톤계의 용제를 주로 사용하여 도료의 저장성 및 작업성(픽업성)을 향상시키며 환경친화적인 특성을 살리는 것이 바람직하다.
Particularly, when it is used as a coating composition for household electric appliances, it is preferable to mainly use an ester-based and a ketone-based solvent to improve the storage stability and workability (pickup property) of the paint and to make environmentally friendly properties.
상기 방청 안료는 크롬산스트로튬, 비정형 실리콘디옥사이드와 칼슘의 복합체, 마그네슘옥사이드 및 인산아연으로 이루어지는 그룹으로부터 선택되는 것이 바람직하며, 가전용 제품은 무독성 방청 안료등을 적용하여 내식성을 부여하는 것이 바람직하다.
The rust-preventive pigment is preferably selected from the group consisting of strontium chromate, a complex of amorphous silicon dioxide and calcium, magnesium oxide and zinc phosphate, and it is preferable that the household appliance is provided with corrosion resistance by applying non-toxic rust preventive pigment or the like.
예를 들어, 건재용 하도 도료에 적용되는 크롬산스트로튬 방청 안료는 SOCIETE NOUVELLE DES COULEURS ZINCIQUES 사의 원료를 사용할 수 있으며, 가전용 하도 도료에 적용되는 무독성 방청 안료는 GRACE 사의 비정형 실리콘디옥사이드와 칼슘의 복합체를 동시에 적용하여 내식성을 개선할 수 있다.
For example, raw materials of SOCIETE NOUVELLE DES COULEURS ZINCIQUES can be used for the chromate-free rust-preventive pigment applied to the undercoat paint for construction materials, and the non-toxic rust-preventive pigment applied to the undercoat paint for home electric appliances is a composite of atypical silicon dioxide and calcium At the same time, corrosion resistance can be improved.
일반적으로 하도용 도료 조성물의 경우 방청 안료의 함량이 많아 질수록 단면부의 내식성은 향상되나, 방청 안료를 과량 사용하는 경우에는 습윤 환경에서 장기간 방치 시 도막의 블리스터(BLISTER)가 발생할 확률이 높고, 도료 저장성이 저하되므로 방청 안료 함량은 전체 하도용 도료 조성물의 중량을 기준으로 5 내지 10중량%인 것이 바람직하다.
Generally, the corrosion resistance of the cross section is improved as the content of the anticorrosive pigment is increased in the case of the undercoat paint composition. However, when the anticorrosive pigment is used in an excessive amount, the probability of occurrence of the blister (BLISTER) It is preferable that the content of the anticorrosive pigment is 5 to 10% by weight based on the weight of the total paint composition.
본 발명에서 도막의 평활성을 유지하고 도장 작업 시 소포성 및/또는 레벨링성의 향상을 위하여 아크릴계, 비닐계 또는 실리콘계 레벨링제 및/또는 소포제를 각각 0.5 내지 3.5중량% 함량으로 포함하는 것이 바람직하다.
In order to maintain the smoothness of the coating film and improve the defoaming property and / or the leveling property during the coating operation, it is preferable that the coating composition contains 0.5 to 3.5% by weight of acrylic, vinyl or silicone leveling agent and / or antifoaming agent.
이러한 레벨링제 및 소포제는 DSM 케미칼사의 URAD DD27, BYK사의 BYK310, BYK322, BYK356, BYK410 및 CFC케미탈사의 CFC270, CFC90 등을 사용할 수 있으나, 이에 제한되는 것은 아니며, 상기 레벨링제는 소포제 역할도 할 수 있는 성분을 이용할 수 있다.
Examples of the leveling agent and antifoaming agent include but are not limited to URAD DD27 of DSM Chemical, BYK310, BYK322, BYK356 and BYK410 of BYK, and CFC270 and CFC90 of CFC Chemtahl. Can be used.
또한, 본 발명의 도료 조성물은 안료를 함유하지 않는 투명 도료 조성물로도 사용될 수 있으나, 필요한 경우 안료를 포함할 수 있으며, 상기 안료는 이산화타이타늄, RED 산화철 및 YELLOW 산화철로 이루어지는 그룹으로부터 선택될 수 있고, 상기 안료는 전체 하도용 도료 조성물의 중량을 기준으로 2 내지 4 중량%로 포함되는 것이 바람직하다.
The coating composition of the present invention may also be used as a clear coating composition containing no pigment, but may include a pigment if necessary, and the pigment may be selected from the group consisting of titanium dioxide, RED iron oxide and YELLOW iron oxide , And the pigment is preferably contained in an amount of 2 to 4% by weight based on the weight of the whole undercoating paint composition.
소지에 대한 부착성 및 내식성 등을 보다 향상시키기 위하여 활석, 점토, 실리카, 운모, 알루미나 등과 같은 체질 안료 등을 추가로 포함할 수 있다.
Clay, silica, mica, alumina and the like in order to further improve the adhesion to the substrate and the corrosion resistance, And the like.
분산 첨가제의 경우 액상의 수지에 고체의 안료를 균일하게 분산시키기 위해 사용될 수 있은 것으로, 안료의 분산이 불충분한 경우에는 안료 재응집, 침전, 흐름성 등의 물성 저하를 발생할 수 있으므로, 필요한 경우 분산성의 향상을 위해 첨가할 수 있다. 이때 분산 첨가제의 함량은 전체 하도용 도료 조성물의 중량을 기준으로 0.1 내지 0.2중량% 인 것이 바람직하다.
The dispersion additive can be used to uniformly disperse the solid pigment in the liquid resin. When the dispersion of the pigment is insufficient, the physical properties such as pigment aggregation, sedimentation and flow property may be deteriorated. May be added for improvement of properties. The content of the dispersing additive is preferably 0.1 to 0.2% by weight based on the total weight of the coating composition for undergarment.
나아가, 하도용 도료 조성물에 에폭시 수지가 첨가되는 경우 소지와의 부착력을 향상시켜 가공성, 내식성, 내습성 및 약품성을 향상시킬 수 있으며, 이때 상기 에폭시 수지로는 비스페롤-A, 하이드로제네이티드 비스페놀-A 및 페녹시 타입으로 이루어진 그룹으로부터 선택된 적어도 하나의 에폭시 수지가 적용될 수 있다. 에폭시 수지 함량은 전체 하도용 도료 조성물의 중량을 기준으로 1 내지 3중량% 인 것이 바람직하다.
Further, when an epoxy resin is added to the undercoat paint composition, the adhesion to the substrate can be improved to improve workability, corrosion resistance, moisture resistance and chemical resistance. Examples of the epoxy resins include bisphenol A, hydrogenated bisphenol At least one epoxy resin selected from the group consisting of -A and phenoxy type can be applied. The epoxy resin content is preferably 1 to 3% by weight based on the weight of the entire coating composition.
본 발명의 다른 견지에 의하면, 상술한 바와 같은 본 발명의 하도용 도료 조성물이 적어도 일면에 도장된 PCM 다색 강판이 제공된다.
According to another aspect of the present invention, there is provided a PCM multicolored steel sheet coated on at least one side of the undercoat paint composition of the present invention as described above.
나아가, 본 발명의 하도용 도료 조성물이 도장된 후 적용되는 상도용 도료 조성물은 외관 및 다색 경계면 조절을 위하여 선형 모노머를 주축으로 하고 중량평균 분자량 12,000 내지 14,000, 수산가 30 내지 40 mgKOH/g, 산가 1 내지 5 mgKOH/g, 유리전이온도 15 내지 25℃인 열경화성 폴리에스테르 수지를 포함하는 것이 바람직하다. 이때 상기 상도용 도료 조성물은 상기 열경화성 폴리에스테르 수지를 전체 상도용 도료 조성물의 중량을 기준으로 30 내지 45 중량%로 포함하는 것이 바람직하다.
Further, the coating composition for phase-inversion applied after coating the primer coating composition of the present invention has a weight average molecular weight of 12,000 to 14,000, a hydroxyl value of 30 to 40 mg KOH / g, an acid value of 1 To 5 mgKOH / g, and a glass transition temperature of from 15 to 25 ° C. At this time, it is preferable that the topical coating composition contains the thermosetting polyester resin in an amount of 30 to 45% by weight based on the weight of the total top coating composition.
이와 같이 본 발명의 하도용 도료 조성물과 함께 적용되는 상기 상도용 도료 조성물의 경우 상기 열경화성 폴리에스테르 수지 이외의 조성은 본 발명의 하도용 조성물과 공통될 수 있다. 다만, 상도용 도료 조성물의 교제는 멜라민 수지 단독으로 적용하여 도막 경도 및 스크래치성을 향상시키는 것이 바람직하다.
As such, in the case of the paint composition for topical application to be applied together with the paint composition for undercoat of the present invention, the composition other than the thermosetting polyester resin may be common to the undercoat composition of the present invention. However, it is preferable to use melamine resin alone to improve the hardness and scratch resistance of the coating film composition.
이하, 구체적인 실시예를 통해 본 발명을 보다 구체적으로 설명한다. 하기 실시예는 본 발명의 이해를 돕기 위한 예시에 불과하며, 본 발명의 범위가 이에 한정되는 것은 아니다.
Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
실시예Example
1. 열경화성 폴리에스테르 수지의 제조1. Preparation of thermosetting polyester resin
하도용 도료 조성물에 사용되는 열경화성 폴리에스테르 수지를 제조하기 위하여, 다가알코올과 2가 산을 혼합하고, 여기에 BIS 타입의 방향족 모노머인 (2,2-비스(4-하이드록시페닐)프로판 디알릴에테르)를 첨가하여 축합반응하였다.
In order to prepare a thermosetting polyester resin to be used for a coating composition for undercoating, a polyhydric alcohol and a dicarboxylic acid are mixed, and a BIS type aromatic monomer (2,2-bis (4-hydroxyphenyl) Ether) was added to perform condensation reaction.
이때 사용된 각 성분의 함량은 하기 표 1에 나타난 바와 같다. 원료 투입 전 수지 탱크 내에 질소를 투입한 후 방향족 모노머(BA320T), 다가알코올(네오펜틸글리콜 및 에틸렌글리콜), 2가 산(이소프탈산) 및 첨가제(DBTO)를 혼합하여 235 내지 240℃ 온도에서 15 시간 동안 1차 반응시킨 후, 210 내지 215℃의 온도에서 3시간 동안 2가 산(테레프탈산)과 희석용제를 추가 투입 2차 반응 및 점도 조정 등을 진행한다.The content of each component used herein is shown in Table 1 below same. (BA320T), a polyhydric alcohol (neopentyl glycol and ethylene glycol), a dicarboxylic acid (isophthalic acid) and an additive (DBTO) were mixed in a resin tank before the introduction of the raw material, (Terephthalic acid) and a diluting solvent are further added at a temperature of 210 to 215 ° C for 3 hours, followed by a second-order reaction and viscosity adjustment.
BA320T
DBTO : 디부틸틴옥사이드
점도: 50% 용액(25℃ 가드너), 희석 용제 50%를 적용하여 가드너 점도계로 상대 평가BA320T: 2,2-bis (4-hydroxyphenyl) propane diallyl ether
DBTO: Dibutyltin oxide
Viscosity: 50% solution (25 캜 Gardner), 50% dilution solvent, relative evaluation with Gardner viscometer
즉, 비교예 1과 같이 종래의 하도용 도료 조성물에 사용되는 열경화성 폴리에스테르 수지의 경우 고형분이 약 60 중량%, 점도는 V-Y, 분자량은 14000-16000, 수산기 값은 10-60, Tg는 20-40℃이나, 본 발명의 도용 도료 조성물에 사용되는 열경화성 폴리에스테르 수지의 경우 고형분이 약 50 중량%, 점도는 Z-Z3, 분자량은 20000-30000, 수산기 값은 20-50, Tg는 45-55℃으로, 그 물성이 구분된다.
That is, as in Comparative Example 1, the thermosetting polyester resin used in the conventional undercoat paint composition had a solid content of about 60% by weight, a viscosity of VY, a molecular weight of 14000-16000, a hydroxyl value of 10-60, 40 占 폚. In the case of the thermosetting polyester resin used in the coating composition for paint of the present invention, the solid content is about 50% by weight, the viscosity is Z-Z3, the molecular weight is 20,000-30000, the hydroxyl value is 20-50, Lt; RTI ID = 0.0 > C, < / RTI >
2. 2.
PCMPCM
다색 강판의 Multicolored
하도(Primer)용For Primer
도료 조성물의 제조 Preparation of Coating Composition
상기 1.에서 제조된 열경화성 폴리에스테르 수지와 분산 첨가제, 체질안료 및 방청안료를 70℃ 이하 온도에서 분산(Mill) 과정으로 혼합하고 이후 35℃ 이하의 온도에서 에폭시 수지, 가교제 투입 후 천천히 교반(Stir) 시킨다. 이후 레벨링제와 경화 촉매를 투입 및 교반하며, 마지막으로 유기용제를 적용하여 하도용 조성을 제조하였다. 이때 사용된 각 성분의 함량은 하기 표 2에 나타난 바와 같다.
The thermosetting polyester resin, the dispersant, the extender pigment, and the anticorrosive pigment prepared in the above 1. are mixed at a temperature of 70 ° C or lower by a milling process, and then the epoxy resin and the crosslinking agent are added at a temperature of 35 ° C or lower, ). Then, a leveling agent and a curing catalyst were added and stirred, and finally, an organic solvent was applied to prepare a composition for undercoating. The content of each component used is shown in Table 2 below.
3. 3.
하도용Underwater
도료 조성물이 The coating composition
도장된Painted
PCMPCM
다색 강판의 물성 확인 실험 Experiment to confirm the physical properties of multicolored steel sheet
시험 시편을 제조하기 위하여 0.45T의 GI강판을 메틸에틸케톤으로 탈지하고, 상기표 2의 실시예 1 내지 4의 하도용 도료 조성물을 건조 도막 두께 약 5㎛가 되도록 바코팅하였다. 그 뒤 물성을 확인하고 하기 표 3에 나타내었다.
To prepare the test specimens, 0.45 T GI steel sheets were degreased with methyl ethyl ketone, and the coating compositions for undercoats of Examples 1 to 4 in Table 2 were bar coated to a dry film thickness of about 5 탆. The physical properties were then checked and are shown in Table 3 below.
그 후, 상기 실시예 3의 하도 조성물을 이용하여 도장하고, 이에 하기 표 4의 제조예 1 내지 제조예 4의 상도용 도료 조성물을 추가로 도장하였다. 상기 상도용 도료 조성물을 건조 도막 두께 약 15~20um가 되도록 어플리케이터로 도장한 후 280℃의 분위기 온도에서 40초간 소부하여 최종 물성 시험 시편을 작성하였다.
Thereafter, the undercoating composition of Example 3 was applied, and further the paint composition for phase-inversion of Production Examples 1 to 4 in Table 4 was further coated. The topcoat paint composition was coated with an applicator to a dry film thickness of about 15 to 20 μm, and then baked at an atmospheric temperature of 280 ° C. for 40 seconds to prepare a final physical property test specimen.
이때, 실시예 3의 하도 조성물 및 하기 제조예 2-A를 도장한 경우의 외관은 도 1 우측에 나타낸 사진과 같다.
At this time, the undercoating composition of Example 3 and the appearance of the following Production Example 2-A are shown in the photographs shown on the right side of FIG.
항목
Item
성분
ingredient
안료
Pigment
Extender pigment
유기 용제
Organic solvent
(단위: g)
(Unit: g)
그 뒤, 최종 물성 시험 시편의 물성을 확인하고 하기 표 5에 나타내었다.
After that, physical properties of the final test specimens were confirmed and shown in Table 5 below.
반면, 상기 비교예 1의 하도 조성물을 이용하여 도장하고, 상기 표 4의 제조예 2-A의 상도용 도료 조성물을 추가로 도장하여 동일한 과정에 의해 최종 물성 시험 시편을 작성한 경우의 물성을 확인하고 하기 표 6에 나타내었다.
On the other hand, by using the undercoating composition of Comparative Example 1, the coating composition for phase-inversion of Production Example 2-A in Table 4 was further coated, and the physical properties of the final test specimen were confirmed by the same procedure Are shown in Table 6 below.
상기 물성의 보다 명확한 비교를 위해, 상기 표 4의 제조예 2-A의 상도용 도료 조성물 적용 시 하도용 조성물로 실시예 2와 비교예 1의 하도 조성물을 이용한 경우를 비교하여 나타내었다.
For comparison of the physical properties, the compositions for undercoat compositions of Example 2-A and Comparative Example 1 were compared for comparison.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be obvious to those of ordinary skill in the art.
Claims (15)
다가알코올과 2가 산의 축합반응에 의해 생성되며, 방향족 모노머를 40 내지 70 중량% 함유하며, 유리전이온도(Tg)가 45 내지 55℃인, 열경화성 폴리에스테르 수지를 포함하는 하도용 도료 조성물로 도장된 하도용 도료 조성물층; 및
중량평균 분자량 12,000 내지 14,000, 수산가 30 내지 40 mgKOH/g, 산가 1 내지 5 mgKOH/g, 유리전이온도 15 내지 25℃인 열경화성 폴리에스테르 수지를 상도용 도료 조성물의 중량을 기준으로 30 내지 45 중량%로 포함하는 상도용 도료 조성물에 의해 미건조 상태의 상기 하도용 도료 조성물층 상에 도장되는 상도용 도료 조성물층
을 포함하는, 도장된 PCM 다색 강판.
On at least one side of the steel sheet,
A coating composition for undercoating comprising a thermosetting polyester resin which is produced by a condensation reaction of a polyhydric alcohol and a dicarboxylic acid, contains 40 to 70% by weight of an aromatic monomer, and has a glass transition temperature (Tg) of 45 to 55 ° C A painted undercoat paint composition layer; And
A thermosetting polyester resin having a weight average molecular weight of 12,000 to 14,000, a hydroxyl value of 30 to 40 mg KOH / g, an acid value of 1 to 5 mg KOH / g, and a glass transition temperature of 15 to 25 ° C in an amount of 30 to 45% By weight based on the total weight of the coating composition for phase-in-use
, Wherein the coated PCM multicolored steel sheet comprises:
The coated thermosetting resin composition according to claim 1, wherein the thermosetting polyester resin of the undercoat paint composition has a weight average molecular weight of 20,000 to 30,000, a hydroxyl value of 20 to 50 mgKOH / g and an acid value of 1 to 5 mgKOH / Multicolor steel plate.
The coating composition according to claim 1, wherein the polyhydric alcohol is at least one selected from the group consisting of neopentyl glycol, ethylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-decanediol.
2. The coating composition according to claim 1, wherein the divalent acid of the undercoat paint composition is selected from the group consisting of isophthalic acid, terephthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid and terephthalic acid. Coated PCM multicolored steel.
The coating composition according to claim 1, wherein the undercoating composition further comprises at least one component selected from the group consisting of a crosslinking agent, a curing catalyst, an organic solvent, a rust preventive pigment, a leveling agent, an extender pigment, PCM multicolored steel sheet.
The coating composition according to claim 5, wherein the coating composition for undercoat comprises 25 to 35% by weight of a thermosetting polyester resin, 3 to 13% by weight of a crosslinking agent, 0.5 to 2.5% by weight of a curing catalyst, 30 to 45% by weight of an organic solvent, Wherein the leveling agent comprises 0.5 to 3.5% by weight of an extender pigment, 2 to 4% by weight of an extender pigment, 0.1 to 0.2% by weight of a dispersing additive and 1 to 3% by weight of an epoxy resin.
The painted PCM multicolor steel sheet according to claim 5, wherein the cross-linking agent of the undercoat paint composition is a mixture of methoxy melamine resin and blocked isocyanate resin in a weight ratio of 1: 0.2 to 0.4.
7. The curing catalyst of claim 6, wherein the curing catalyst is selected from the group consisting of dibutyl tin dilaurate (DBTDL), p-toluene sulfonic acid (p-TSA), dinonyl naphthalene sulfonic acid (DNNSA), dinaphthalene disulfonic acid (DNNDSA) Wherein at least one sulfonic acid selected from the group consisting of fluorosulfonic acid and fluorosulfonic acid is neutralized with an amine or epoxy and the dissociation temperature is 120 to 150 ° C.
6. The coating composition according to claim 5, wherein the organic solvent of the undercoat paint composition is at least one solvent selected from the group consisting of aromatic hydrocarbon, glycol ester, ketone, glycol ether and alcohol solvents, Multicolor steel plate.
6. The painted PCM multicolor steel sheet according to claim 5, wherein the rustproof pigment of the undercoat paint composition is at least one selected from the group consisting of strontium chromate, a complex of amorphous silicon dioxide and calcium, magnesium oxide and zinc phosphate.
The painted PCM multicolored steel sheet according to claim 5, wherein the leveling agent of the undergarment paint composition is at least one leveling agent selected from the group consisting of acrylic, vinyl and silicon leveling agents.
The painted PCM multicolored steel sheet according to claim 5, wherein the extender pigment of the undergarment paint composition is at least one selected from the group consisting of aluminum silicate and silica.
The painted PCM multicolored steel sheet according to claim 5, wherein the dispersant additive of the undergarment paint composition is a polycarboxylic acid copolymer.
The painted PCM multicolor steel sheet according to claim 5, wherein the epoxy resin of the undercoat paint composition is at least one selected from the group consisting of bisphenol-A, hydrogenated bisphenol-A and phenoxy.
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| KR102177866B1 (en) * | 2018-08-22 | 2020-11-12 | 현대제철 주식회사 | Manufacturing method for color steel sheet and color steel sheet thereof |
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