JP6832122B2 - Two-component mixed paint composition - Google Patents
Two-component mixed paint composition Download PDFInfo
- Publication number
- JP6832122B2 JP6832122B2 JP2016205277A JP2016205277A JP6832122B2 JP 6832122 B2 JP6832122 B2 JP 6832122B2 JP 2016205277 A JP2016205277 A JP 2016205277A JP 2016205277 A JP2016205277 A JP 2016205277A JP 6832122 B2 JP6832122 B2 JP 6832122B2
- Authority
- JP
- Japan
- Prior art keywords
- coating composition
- epoxy resin
- component mixed
- polyamine
- coating film
- 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.)
- Active
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- 239000003973 paint Substances 0.000 title description 38
- 239000000203 mixture Substances 0.000 title description 12
- 238000000576 coating method Methods 0.000 claims description 86
- 239000008199 coating composition Substances 0.000 claims description 85
- 239000003822 epoxy resin Substances 0.000 claims description 85
- 229920000647 polyepoxide Polymers 0.000 claims description 85
- 239000011248 coating agent Substances 0.000 claims description 84
- 239000003795 chemical substances by application Substances 0.000 claims description 83
- 229920000768 polyamine Polymers 0.000 claims description 65
- 239000002904 solvent Substances 0.000 claims description 44
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 34
- 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 31
- 125000002723 alicyclic group Chemical group 0.000 claims description 28
- 230000003449 preventive effect Effects 0.000 claims description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 25
- 239000000049 pigment Substances 0.000 claims description 25
- -1 alkyl phenol Chemical compound 0.000 claims description 24
- 229920003986 novolac Polymers 0.000 claims description 21
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000001723 curing Methods 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 23
- 230000005484 gravity Effects 0.000 description 17
- 229910000831 Steel Inorganic materials 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 230000001429 stepping effect Effects 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 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 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
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- 239000004615 ingredient Substances 0.000 description 4
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- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000005956 Cosmos caudatus Nutrition 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 230000003254 anti-foaming effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
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- 229910052618 mica group Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
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- MDKFWXLKRPZVAQ-UHFFFAOYSA-N 1,11-diazacycloicosane Chemical compound C1CCCCNCCCCCCCCCNCCCC1 MDKFWXLKRPZVAQ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 description 1
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- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- IZKZIDXHCDIZKY-UHFFFAOYSA-N heptane-1,1-diamine Chemical compound CCCCCCC(N)N IZKZIDXHCDIZKY-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- UJCISEHKQQMVCI-UHFFFAOYSA-N n,n'-bis(2-aminoethyl)-2,2-bis[(2-aminoethylamino)methyl]propane-1,3-diamine Chemical compound NCCNCC(CNCCN)(CNCCN)CNCCN UJCISEHKQQMVCI-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 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 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Description
本発明は、低温での硬化性及び塗膜性能に優れ、ミネラルスピリット等の弱溶剤に可溶で、かつ、防錆性に優れた、主剤及び硬化剤からなる二液混合形エポキシ樹脂塗料組成物に関する。 INDUSTRIAL APPLICABILITY The present invention is a two-component mixed epoxy resin coating composition composed of a main agent and a curing agent, which are excellent in curability at low temperature and coating film performance, soluble in a weak solvent such as mineral spirit, and excellent in rust prevention. Regarding things.
エポキシ樹脂は、耐食性、耐薬品性、付着性等に優れているため、防錆塗料用樹脂として広く使用されている。従来、塗料用のエポキシ樹脂及びその硬化剤としてのポリアミンは、トルエン、キシレン等の溶剤にて溶解した、あるいは、溶解可能なものであったが、近年は、人体への有害性が少なく、高引火点、高沸点であるミネラルスピリット等の弱溶剤に可溶なエポキシ樹脂及びポリアミンが使用されつつある。 Epoxy resins are widely used as resins for rust preventive paints because they are excellent in corrosion resistance, chemical resistance, adhesion, and the like. Conventionally, epoxy resins for paints and polyamines as their curing agents have been dissolved or soluble in solvents such as toluene and xylene, but in recent years, they are less harmful to the human body and are highly resistant. Epoxy resins and polyamines that are soluble in weak solvents such as flammable points and high boiling point mineral spirits are being used.
しかしながら、外気温の影響を受けやすい橋梁や石油タンク等の鋼構造物は冬場の基材温度が低くなるため、弱溶剤に可溶なエポキシ樹脂及びポリアミンからなるエポキシ樹脂塗料組成物は、乾燥性、硬化性、旧塗膜に対する塗り重ね性及び塗膜性能において未だ十分なものが得られていない。 However, since the base temperature of steel structures such as bridges and oil tanks, which are easily affected by the outside air temperature, is low in winter, the epoxy resin coating composition composed of an epoxy resin and polyamine soluble in a weak solvent is dry. , Curability, recoatability to old paint film, and paint film performance have not yet been obtained.
例えば、（Ａ）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定される標準ポリスチレン換算の重量平均分子量（Ｍｗ）が１５，０００〜４５，０００であるエポキシ樹脂と、（Ｂ）シランカップリング剤と、（Ｃ）防錆顔料と、（Ｄ）アミン系硬化剤とを含んでなることを特徴とする二液混合形塗料組成物が提案されている（例えば、特許文献１を参照）。 For example, (A) an epoxy resin having a standard polystyrene-equivalent weight average molecular weight (Mw) of 15,000 to 45,000 measured by a gel permeation chromatography (GPC) method, and (B) a silane coupling agent. , (C) A two-component mixed coating composition comprising (C) an epoxy pigment and (D) an amine-based curing agent has been proposed (see, for example, Patent Document 1).
更に、主剤成分（Ａ）及び硬化剤成分（Ｂ）を含有してなるエポキシ樹脂組成物において、主剤成分（Ａ）が、液状エポキシ樹脂（ａ１）とシランカップリング剤（ａ２）を含有し、硬化剤成分（Ｂ）が、アミン系硬化剤（ｂ１）を含有し、主剤成分（Ａ）及び／又は前記硬化剤成分（Ｂ）が、液状炭化水素樹脂を含有する二液混合形塗料組成物が提案されている（例えば、特許文献２を参照）。 Further, in the epoxy resin composition containing the main agent component (A) and the curing agent component (B), the main agent component (A) contains the liquid epoxy resin (a1) and the silane coupling agent (a2). A two-component mixed coating composition in which the curing agent component (B) contains an amine-based curing agent (b1), and the main component (A) and / or the curing agent component (B) contains a liquid hydrocarbon resin. Has been proposed (see, for example, Patent Document 2).
特許文献１に記載された技術を用いることにより、優れた防食性能と共に、超低温時であっても優れた付着性を有する塗膜を形成することができる。また、特許文献２に記載された技術を用いることにより、基材との付着性、耐水性、防食性に優れる防食皮膜を形成することができる。 By using the technique described in Patent Document 1, it is possible to form a coating film having excellent anticorrosion performance and excellent adhesiveness even at an ultra-low temperature. Further, by using the technique described in Patent Document 2, it is possible to form an anticorrosion film having excellent adhesion to a base material, water resistance and corrosion resistance.
しかしながら、特許文献１に記載の技術を用いた場合には、鋼構造物に形成された塗膜が、外気温による鋼材の伸び縮みに対応できず、クラックやはがれ等の塗膜不良が生じるという課題がある。また、特許文献２に記載の技術を用いた場合には、十分な低温硬化性が得られないといった課題がある。二液混合形塗料組成物の有機溶剤として弱溶剤を用いない場合にも同様の課題がある。
これらの課題を同時に解決できる二液混合形塗料組成物が求められている。
However, when the technique described in Patent Document 1 is used, the coating film formed on the steel structure cannot cope with the expansion and contraction of the steel material due to the outside air temperature, and the coating film defects such as cracks and peeling occur. There are challenges. Further, when the technique described in Patent Document 2 is used, there is a problem that sufficient low temperature curability cannot be obtained. There is a similar problem when a weak solvent is not used as the organic solvent of the two-component mixed coating composition.
There is a demand for a two-component mixed coating composition that can solve these problems at the same time.
本発明は、低温硬化性及び塗膜性能に優れた二液混合形塗料組成物を提供することを目的とする。 An object of the present invention is to provide a two-component mixed coating composition having excellent low-temperature curability and coating film performance.
本発明は、金属基材の表面を被覆する防錆塗膜を形成するために用いられる、主剤（Ｉ）及び硬化剤（ＩＩ）を含む二液混合形塗料組成物であって、前記主剤（Ｉ）は、エポキシ樹脂（ａ）を含み、前記硬化剤（ＩＩ）は、ポリアミン（ｂ）を含み、前記エポキシ樹脂（ａ）は、ビスフェノールＡ型エポキシ樹脂又はノボラック型エポキシ樹脂の少なくともいずれかで、かつ、重量平均分子量が６，５００〜１０，０００であり、前記ポリアミン（ｂ）は、脂環式ポリアミン（ｂ−１）と、脂環式ポリアミンを含まないポリアミン（ｂ−２）と、アルキルフェノール（ｂ−３）と、を含む二液混合形塗料組成物に関する。 The present invention is a two-component mixed coating composition containing a main agent (I) and a curing agent (II), which is used for forming an epoxy coating film that covers the surface of a metal substrate. I) contains an epoxy resin (a), the curing agent (II) contains a polyamine (b), and the epoxy resin (a) is at least one of a bisphenol A type epoxy resin and a novolak type epoxy resin. Moreover, the weight average molecular weight is 6,500 to 10,000, and the polyamine (b) is an alicyclic polyamine (b-1), an alicyclic polyamine-free polyamine (b-2), and the like. The present invention relates to a two-component mixed coating composition containing an alkylphenol (b-3).
また、主剤（Ｉ）は、更にシランカップリング剤（ｃ）を含み、前記シランカップリング剤（ｃ）は、異なる２種の官能基の一方の官能基として、トリメトキシシリル基又はトリエトキシシリル基を有することが好ましい。 Further, the main agent (I) further contains a silane coupling agent (c), and the silane coupling agent (c) has a trimethoxysilyl group or a triethoxysilyl group as one of the two different functional groups. It is preferable to have a group.
また、弱溶剤を更に含むことが好ましい。 Further, it is preferable to further contain a weak solvent.
また、前記脂環式ポリアミン（ｂ−１）は、前記硬化剤（ＩＩ）の総質量に対して、１０〜２０質量％含まれることが好ましい。 The alicyclic polyamine (b-1) is preferably contained in an amount of 10 to 20% by mass with respect to the total mass of the curing agent (II).
また、前記脂環式ポリアミンを含まないポリアミン（ｂ−２）は、前記硬化剤（ＩＩ）の総質量に対して、０．６〜６．３質量％含まれることが好ましい。 Further, the polyamine (b-2) containing no alicyclic polyamine is preferably contained in an amount of 0.6 to 6.3% by mass with respect to the total mass of the curing agent (II).
また、アルキルフェノール（ｂ−３）は、前記硬化剤（ＩＩ）の総質量に対して、６〜３０質量％含まれることが好ましい。 Further, the alkylphenol (b-3) is preferably contained in an amount of 6 to 30% by mass with respect to the total mass of the curing agent (II).
また、前記主剤（Ｉ）の顔料体積濃度（ＰＶＣ）が３０〜６０％であることが好ましい。 Further, the pigment volume concentration (PVC) of the main agent (I) is preferably 30 to 60%.
本発明によれば、低温硬化性及び塗膜性能に優れた二液混合形塗料組成物を提供することができる。 According to the present invention, it is possible to provide a two-component mixed coating composition having excellent low-temperature curability and coating film performance.
以下、本発明に係る主剤（Ｉ）及び硬化剤（ＩＩ）からなる二液混合形エポキシ樹脂塗料組成物（以下、「二液混合形塗料組成物」と総す）について具体的に説明する。 Hereinafter, a two-component mixed epoxy resin coating composition (hereinafter collectively referred to as “two-component mixed coating composition”) comprising the main agent (I) and the curing agent (II) according to the present invention will be specifically described.
二液混合形塗料組成物は、金属基材の表面を被覆する防錆塗膜を形成するために用いられ、主剤（Ｉ）及び硬化剤（ＩＩ）からなる。主剤（Ｉ）は、エポキシ樹脂（ａ）を含み、硬化剤（ＩＩ）は、ポリアミン（ｂ）を含む。主剤（Ｉ）は、更に顔料やシランカップリング剤（ｃ）を含むことが好ましい。また、溶剤としては、ミネラルスピリット等の弱溶剤が用いられることが好ましい。 The two-component mixed coating composition is used for forming a rust preventive coating film that covers the surface of a metal substrate, and is composed of a main agent (I) and a curing agent (II). The main agent (I) contains an epoxy resin (a), and the curing agent (II) contains a polyamine (b). The main agent (I) preferably further contains a pigment and a silane coupling agent (c). Further, as the solvent, it is preferable to use a weak solvent such as mineral spirit.
本実施形態に係る二液混合形塗料組成物の低温硬化性は、低温乾燥性、防食性、付着性、塗り重ね性、踏み込み性という観点で評価される。また、防錆塗膜の外観は、ちぢみ性、温冷繰り返し性（耐割れ性）という観点で評価される。 The low-temperature curability of the two-component mixed coating composition according to the present embodiment is evaluated from the viewpoints of low-temperature drying property, corrosion resistance, adhesiveness, recoatability, and stepping property. Further, the appearance of the rust-preventive coating film is evaluated from the viewpoint of smallness and heat / cold repeatability (crack resistance).
＜エポキシ樹脂（ａ）＞
本実施形態に係る二液混合形塗料組成物は、エポキシ樹脂（ａ）として、ノボラック型エポキシ樹脂又はビスフェノールＡ型エポキシ樹脂の少なくともいずれか一方を含み、これらの両方が含まれていてもよい。このようなエポキシ樹脂（ａ）を用いることにより、ミネラルスピリット等の弱溶剤に可溶であり、かつ、低温硬化性及び塗膜性能を向上させることができる二液混合形塗料組成物が得られる。また、ブラスト鋼板、ショップ塗装鋼板、有機ジンク塗装鋼板等の基材に対する付着性を改善することもできる。エポキシ樹脂（ａ）は、それぞれ１種のエポキシ樹脂が用いられてもよく、２種以上併用されてもよい。また、エポキシ樹脂（ａ）は、ミネラルスピリット等の弱溶剤に可溶な構造に変性されてもよい。
<Epoxy resin (a)>
The two-component mixed type coating composition according to the present embodiment contains at least one of a novolak type epoxy resin and a bisphenol A type epoxy resin as the epoxy resin (a), and both of them may be contained. By using such an epoxy resin (a), a two-component mixed coating composition that is soluble in a weak solvent such as mineral spirit and can improve low temperature curability and coating film performance can be obtained. .. It is also possible to improve the adhesiveness to a base material such as a blasted steel sheet, a shop-coated steel sheet, and an organic zinc-coated steel sheet. As the epoxy resin (a), one type of epoxy resin may be used, or two or more types may be used in combination. Further, the epoxy resin (a) may be modified to have a structure soluble in a weak solvent such as mineral spirit.
本発明において、エポキシ樹脂（ａ）は、ノボラック型エポキシ樹脂及びビスフェノールＡ型エポキシ樹脂以外の他のエポキシ樹脂を含有していてもよく、このような他のエポキシ樹脂としては、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ゴム変性エポキシ樹脂等が挙げられる。かかる他のエポキシ樹脂は、１種のみが用いられてもよく、２種以上併用されてもよい。 In the present invention, the epoxy resin (a) may contain an epoxy resin other than the novolak type epoxy resin and the bisphenol A type epoxy resin, and such other epoxy resins include the bisphenol F type epoxy resin. , Bisphenol AD type epoxy resin, Bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, rubber-modified epoxy resin and the like. Only one type of such other epoxy resin may be used, or two or more types may be used in combination.
主剤（Ｉ）の総質量に対して、ノボラック型エポキシ樹脂及びビスフェノールＡ型エポキシ樹脂の合計量は、樹脂固形分として１０〜４０質量％とすることが好ましく、２０〜３０質量％とすることがより好ましい。１０質量％未満であると、十分な低温硬化性が得られない傾向があり、４０質量％を超えると塗膜中の顔料の割合が減ることで塗膜の隠ぺい性が低下する傾向がある。
なお、本明細書において、主剤（Ｉ）の総質量とは、エポキシ樹脂（ａ）等の樹脂と、顔料と、シランカップリング剤（ｃ）と、その他の主剤（Ｉ）に対する添加剤（弱溶剤を含む）とを合算した総質量をいう。
The total amount of the novolak type epoxy resin and the bisphenol A type epoxy resin is preferably 10 to 40% by mass and preferably 20 to 30% by mass as the resin solid content with respect to the total mass of the main agent (I). More preferred. If it is less than 10% by mass, sufficient low-temperature curability tends not to be obtained, and if it exceeds 40% by mass, the proportion of the pigment in the coating film tends to decrease, and the hiding property of the coating film tends to decrease.
In the present specification, the total mass of the main agent (I) is an additive (weak) to the resin such as the epoxy resin (a), the pigment, the silane coupling agent (c), and the other main agent (I). The total mass including the solvent).
低温での硬化性及び塗膜性能の観点から、ノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂及び他のエポキシ樹脂の重量平均分子量は、６，５００〜１０，０００であることが好ましく、８５００〜１０，０００であることがより好ましい。
重量平均分子量が１０，０００を超えると、例えば後述する温冷繰り返し試験後に塗膜の割れが発生し好ましくない。また、形成された塗膜が、外気温による鋼材の伸び縮みに対応できず、クラックやはがれ等の塗膜不良が生じることも想定される。
一方で、重量平均分子量が６，５００未満であると、低温状態においてエポキシ樹脂と硬化剤ポリアミンの、混合後の高分子化が促進しないことから、十分な低温硬化性が得られない。重量平均分子量（Ｍｗ）は、例えば、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定される。
From the viewpoint of curability at low temperature and coating film performance, the weight average molecular weight of the novolak type epoxy resin, the bisphenol A type epoxy resin and other epoxy resins is preferably 6,500 to 10,000, preferably 8500 to 10 More preferably, it is 000.
If the weight average molecular weight exceeds 10,000, cracks of the coating film occur after repeated heating and cooling tests, which will be described later, which is not preferable. Further, it is assumed that the formed coating film cannot cope with the expansion and contraction of the steel material due to the outside air temperature, and the coating film defects such as cracks and peeling occur.
On the other hand, if the weight average molecular weight is less than 6,500, the epoxy resin and the curing agent polyamine do not promote polymerization after mixing in a low temperature state, so that sufficient low temperature curability cannot be obtained. The weight average molecular weight (Mw) is measured, for example, by gel permeation chromatography (GPC).
また、ノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂及び他のエポキシ樹脂のエポキシ当量は、１，０００以上であることが好ましく、１，１００〜１，２００であることがより好ましい。エポキシ当量が１，０００未満であると、十分な低温硬化性が得られない。 The epoxy equivalents of the novolak type epoxy resin, the bisphenol A type epoxy resin and other epoxy resins are preferably 1,000 or more, and more preferably 1,100 to 1,200. If the epoxy equivalent is less than 1,000, sufficient low temperature curability cannot be obtained.
本発明において使用できるノボラック型エポキシ樹脂の市販品としては、例えば、商品名で、「ＥＰＩＣＬＯＮ ５９７０−６０」（フェノールノボラック型エポキシ樹脂、エポキシ当量１０００以上、ＤＩＣ社製）等が挙げられる。ビスフェノールＡ型エポキシ樹脂の市販品としては、例えば、商品名で、「ＥＰＩＣＬＯＮ １０４０−７０Ｘ」（ビスフェノールＡ型エポキシ樹脂、エポキシ当量１３００、比重１．０、ＤＩＣ社製）等があげられる。 Examples of commercially available novolak type epoxy resins that can be used in the present invention include, for example, "EPICLON 5970-60" (phenol novolac type epoxy resin, epoxy equivalent 1000 or more, manufactured by DIC) under the trade name. Examples of commercially available products of bisphenol A type epoxy resin include "EPICLON 1040-70X" (bisphenol A type epoxy resin, epoxy equivalent 1300, specific gravity 1.0, manufactured by DIC) and the like under the trade name.
＜ポリアミン（ｂ）＞
ポリアミン（ｂ）は、硬化剤（ＩＩ）の主成分であり、脂環式ポリアミン（ｂ−１）と、脂環式ポリアミンを含まないポリアミン（ｂ−２）と、アルキルフェノール（ｂ−３）と、を含む。上述のポリアミンは（ｂ）はミネラルスピリット等の弱溶剤に可溶な構造に変性されてもよい。
<Polyamine (b)>
The polyamine (b) is the main component of the curing agent (II), and contains an alicyclic polyamine (b-1), an alicyclic polyamine-free polyamine (b-2), and an alkylphenol (b-3). ,including. The above-mentioned polyamine (b) may be modified to a structure soluble in a weak solvent such as mineral spirit.
脂環式ポリアミン（ｂ−１）としては、例えば、１，４−シクロヘキサンジアミン、４，４’−メチレンビスシクロヘキシルアミン、４，４’−イソプロピリデンビスシクロヘキシルアミン、ノルボルナジアミン、ビス（アミノメチル）シクロヘキサン、ジアミノジシクロヘキシルメタン、イソホロンジアミン、メンセンジアミン（ＭＤＡ）等を含む脂環式ポリアミンが挙げられる。 Examples of the alicyclic polyamine (b-1) include 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornadiamine, and bis (aminomethyl). ) An alicyclic polyamine containing cyclohexane, diaminodicyclohexylmethane, isophorone diamine, mensene diamine (MDA) and the like can be mentioned.
低温での硬化性及び塗膜性能の観点から、脂環式ポリアミン（ｂ−１）は、硬化剤（ＩＩ）の総質量に対して、１０〜２０質量％含まれることが好ましく、１３〜１６質量％含まれることがより好ましい。脂環式ポリアミン（ｂ−１）が１８質量％を超える場合には、形成される塗膜に粘着性が残りやすくなり、踏み込み性が悪くなる傾向ある。また、脂環式ポリアミン（ｂ−１）が１０質量％未満である場合には、十分な低温硬化性が得られない。
なお、本明細書において、硬化剤（ＩＩ）の総質量とは、脂環式ポリアミン（ｂ−１）、脂環式ポリアミンを含まないポリアミン（ｂ−２）、アルキルフェノール（ｂ−３）等のポリアミン（ｂ）と、その他の硬化剤（ＩＩ）に対する添加剤（弱溶剤を含む）とを合算した総質量をいう。
From the viewpoint of curability at low temperature and coating film performance, the alicyclic polyamine (b-1) is preferably contained in an amount of 10 to 20% by mass, preferably 13 to 16% by mass, based on the total mass of the curing agent (II). More preferably, it is contained in% by mass. When the alicyclic polyamine (b-1) exceeds 18% by mass, the adhesiveness tends to remain in the formed coating film, and the stepping property tends to be deteriorated. Further, when the alicyclic polyamine (b-1) is less than 10% by mass, sufficient low-temperature curability cannot be obtained.
In the present specification, the total mass of the curing agent (II) refers to alicyclic polyamines (b-1), polyamines containing no alicyclic polyamines (b-2), alkylphenols (b-3), and the like. It refers to the total mass of the polyamine (b) and the additives (including weak solvents) for the other curing agent (II).
脂環式ポリアミンを含まないポリアミン（ｂ−２）としては、脂肪族系アミン、芳香族系アミン、複素環系アミン等から選択されるいずれかのアミン化合物を含むポリアミン等が挙げられる。 Examples of the polyamine (b-2) containing no alicyclic polyamine include polyamines containing any amine compound selected from aliphatic amines, aromatic amines, heterocyclic amines and the like.
脂肪族系アミンとしては、例えば、アルキレンポリアミン、ポリアルキレンポリアミン、その他の脂肪族系アミン等が挙げられる。
アルキレンポリアミンとしては、例えば、Ｈ２Ｎ−Ｒ１−ＮＨ２（式中、Ｒ１は、１個以上の炭素数１〜１０の炭化水素基で置換されていてもよい炭素数１〜１２の二価の炭化水素基である。）で表されるポリアミン化合物が挙げられる。より具体的には、メチレンジアミン、エチレンジアミン、１，２−ジアミノプロパン、１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノペンタン、１，６−ジアミノヘキサン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１０−ジアミノデカン等が挙げられる。
ポリアルキレンポリアミンとしては、例えば、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサメチレンテトラミン等が挙げられる。
その他の脂肪族系アミンとしては、例えば、テトラ（アミノメチル）メタン、テトラキス（２−アミノエチルアミノメチル）メタン、１，３−ビス（２’−アミノエチルアミノ）プロパン、トリエチレン−ビス（トリメチレン）ヘキサミン、ビス（３−アミノエチル）アミン、ビスヘキサメチレントリアミン［Ｈ２Ｎ（ＣＨ２）６ＮＨ（ＣＨ２）６ＮＨ２］等が挙げられる。
Examples of the aliphatic amine include alkylene polyamines, polyalkylene polyamines, and other aliphatic amines.
Examples of the alkylene polyamine include H 2 N-R 1- NH 2 (in the formula, R 1 has 1 to 12 carbon atoms which may be substituted with one or more hydrocarbon groups having 1 to 10 carbon atoms. A polyamine compound represented by a divalent hydrocarbon group) can be mentioned. More specifically, methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7- Examples thereof include diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10-diaminodecane.
Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine and the like.
Examples of other aliphatic amines include tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2'-aminoethylamino) propane, and triethylene-bis (trimethylene). ) Hexamine, bis (3-aminoethyl) amine, bishexamethylenetriamine [H 2 N (CH 2 ) 6 NH (CH 2 ) 6 NH 2 ] and the like.
芳香族系アミンとしては、例えば、ビス（アミノアルキル）ベンゼン、ビス（アミノアルキル）ナフタレン、ベンゼン環に結合した２個以上の１級アミノ基を有する芳香族ポリアミン化合物、及びその他の芳香族系ポリアミン化合物等が挙げられる。芳香族系アミンは特に限定されるものではないが、より具体的には、ビス（シアノエチル）ジエチレントリアミン、ｏ−キシリレンジアミン、ｍ−キシリレンジアミン（ＭＸＤＡ）、ｐ−キシリレンジアミン、フェニレンジアミン、ナフチレンジアミン、ジアミノジフェニルメタン、ジアミノジエチルフェニルメタン、２，２−ビス（４−アミノフェニル）プロパン、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノベンゾフェノン、４，４’−ジアミノジフェニルスルホン、２，２’−ジメチル−４，４’−ジアミノジフェニルメタン、２，４’−ジアミノビフェニル、２，３’−ジメチル−４，４’−ジアミノビフェニル、３，３’−ジメトキシ−４，４’−ジアミノビフェニル、ビス（アミノメチル）ナフタレン、ビス（アミノエチル）ナフタレン等が挙げられる。 Examples of the aromatic amine include bis (aminoalkyl) benzene, bis (aminoalkyl) naphthalene, an aromatic polyamine compound having two or more primary amino groups bonded to a benzene ring, and other aromatic polyamines. Examples include compounds. Aromatic amines are not particularly limited, but more specifically, bis (cyanoethyl) diethylenetriamine, o-xylylene diamine, m-xylylene diamine (MXDA), p-xylylene diamine, phenylenediamine, etc. Naftyrenideamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Examples thereof include diaminobiphenyl, bis (aminomethyl) naphthalene and bis (aminoethyl) naphthalene.
複素環系アミンとしては、例えば、Ｎ−メチルピペラジン［ＣＨ３−Ｎ（ＣＨ２ＣＨ２）２ＮＨ］、モルホリン［ＨＮ（ＣＨ２ＣＨ２）２Ｏ］、１，４−ビス−（８−アミノプロピル）−ピペラジン、ピペラジン−１，４−ジアザシクロヘプタン、１−（２’−アミノエチルピペラジン）、１−［２’−（２’’−アミノエチルアミノ）エチル］ピペラジン、１，１１−ジアザシクロエイコサン、１，１５−ジアザシクロオクタコサン等が挙げられる。 Examples of the heterocyclic amine include N-methylpiperazine [CH 3- N (CH 2 CH 2 ) 2 NH], morpholine [HN (CH 2 CH 2 ) 2 O], 1,4-bis- (8-). Aminopropyl) -piperazine, piperazine-1,4-diazacycloheptane, 1- (2'-aminoethyl piperazine), 1- [2'-(2''-aminoethylamino) ethyl] piperazine, 1,11 -Diazacycloeikosan, 1,15-diazacyclooctacosan and the like can be mentioned.
脂環式ポリアミンを含まないポリアミン（ｂ−２）は、硬化剤（ＩＩ）の総質量に対して、０．６〜６．３質量％含まれることが好ましく、２．９〜３．６質量％含まれることがより好ましい。脂環式ポリアミンを含まないポリアミン（ｂ−２）が６．３質量％を超える場合には、形成される塗膜に粘着性が残りやすくなり、踏み込み性が悪くなる傾向ある。また、脂環式ポリアミンを含まないポリアミン（ｂ−２）が、０．６質量％未満である場合には、十分な低温硬化性が得られない。 The alicyclic polyamine-free polyamine (b-2) is preferably contained in an amount of 0.6 to 6.3% by mass, preferably 2.9 to 3.6% by mass, based on the total mass of the curing agent (II). % Is more preferable. When the polyamine (b-2) containing no alicyclic polyamine exceeds 6.3% by mass, the coating film to be formed tends to remain sticky and the stepping property tends to be deteriorated. Further, when the polyamine (b-2) containing no alicyclic polyamine is less than 0.6% by mass, sufficient low temperature curability cannot be obtained.
アルキルフェノール（ｂ−３）としては、例えば、メチルフェノール（ｏ，ｍ，ｐ−クレゾール）、エチルフェノール、ブチルフェノール、ターシャリブチルフェノール、オクチルフェノール、ノニルフェノール、ドデシルフェノール、ジノニルフェノール等の１価フェノールが挙げられる。
アルキルフェノール（ｂ−３）のアルキル基の炭素数は、１〜１０であることが好ましく、１〜５であることがより好ましい。
Examples of the alkylphenol (b-3) include monovalent phenols such as methylphenol (o, m, p-cresol), ethylphenol, butylphenol, tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, and dinonylphenol.
The alkyl group of the alkylphenol (b-3) preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
アルキルフェノール（ｂ−３）は、硬化剤（ＩＩ）の総質量に対して、６〜３０質量％含まれることが好ましく、１２〜２４質量％含まれることがより好ましい。アルキルフェノール（ｂ−３）が３０質量％を超える場合には、形成される塗膜に粘着性が残りやすくなり、踏み込み性が悪くなる傾向ある。また、アルキルフェノール（ｂ−３）が、６質量％未満である場合には、十分な低温硬化性が得られない。 The alkylphenol (b-3) is preferably contained in an amount of 6 to 30% by mass, more preferably 12 to 24% by mass, based on the total mass of the curing agent (II). When the amount of alkylphenol (b-3) exceeds 30% by mass, the coating film formed tends to have adhesiveness, and the stepping property tends to be deteriorated. Further, when the alkylphenol (b-3) is less than 6% by mass, sufficient low temperature curability cannot be obtained.
＜添加剤＞
本実施形態に係る二液混合形塗料組成物の主剤（Ｉ）には、顔料、シランカップリング剤（ｃ）、その他の添加剤が含有されてもよい。
<Additives>
The main agent (I) of the two-component mixed coating composition according to the present embodiment may contain a pigment, a silane coupling agent (c), and other additives.
顔料としては、体質顔料、着色顔料、防錆顔料のうちの１種のみが用いられてもよく、２種以上を用いてもよい。 As the pigment, only one of the extender pigment, the coloring pigment, and the rust preventive pigment may be used, or two or more kinds may be used.
体質顔料としては、例えば、タルク、クレー、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、ケイ酸、ケイ酸塩、酸化アルミニウム水和物、硫酸カルシウム、石膏、雲母状酸化鉄（ＭＩＯ）、ガラスフレーク、スゾライト・マイカ、クラライト・マイカ等が挙げられる。石膏を用いる場合には、焼石膏（ＣａＳＯ４・１／２Ｈ２Ｏ）を含有させることで、防錆塗膜の耐水性、防食性をより向上させることができる。具体的には、商品名で「ＰＨ−２００」（焼石膏、丸石石膏社製）等を使用することができる。焼石膏を使用する場合、その添加量は、二液混合形塗料組成物の固形分中、２〜３０質量％とすることが好ましい。２質量％未満であると、効果が認められず、３０質量％を超えると、防錆塗膜の表面への析出、白化現象が生じ、防錆塗膜の外観異常をきたす。 Examples of extender pigments include talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, silicic acid, silicate, aluminum oxide hydrate, calcium sulfate, gypsum, mica-like iron oxide (MIO), glass flakes, and suzolite.・ Mica, clarite, mica, etc. can be mentioned. When using the plaster, by the inclusion of calcined gypsum (CaSO 4 · 1 / 2H 2 O), it is possible to further improve water resistance of Bosabinurimaku, corrosion resistance. Specifically, "PH-200" (Yakigypsum, manufactured by Maruishi Gypsum Co., Ltd.) or the like can be used as a trade name. When gypsum is used, the amount added is preferably 2 to 30% by mass in the solid content of the two-component mixed paint composition. If it is less than 2% by mass, no effect is observed, and if it exceeds 30% by mass, precipitation and whitening of the rust-preventive coating film occur, and the appearance of the rust-preventive coating film becomes abnormal.
着色顔料としては、酸化チタン、カーボンブラック、鉛白、黒鉛、硫化亜鉛、酸化亜鉛（亜鉛華）、酸化クロム、黄色ニッケルチタン、黄色クロムチタン、黄色酸化鉄、赤色酸化鉄、黒色酸化鉄、フタロシアニンブルー、フタロシアニングリーン、ウルトラマリンブルー、キナクリドン類、アゾ系赤・黄色顔料等が挙げられる。 Color pigments include titanium oxide, carbon black, white lead, graphite, zinc sulfide, zinc oxide (zinc white), chromium oxide, yellow nickel titanium, yellow chromium titanium, yellow iron oxide, red iron oxide, black iron oxide, and phthalocyanine. Examples include blue, phthalocyanine green, ultramarine blue, quinacridones, and azo red / yellow pigments.
防錆顔料としては、モリブデン酸亜鉛、モリブデン酸アルミニウム、亜鉛末（Ｚｎ）、リン酸亜鉛、アルミ粉（Ａｌ）等が挙げられる。 Examples of the rust preventive pigment include zinc molybdate, aluminum molybdate, zinc powder (Zn), zinc phosphate, aluminum powder (Al) and the like.
シランカップリング剤（ｃ）は、有機ポリマー（硬化樹脂等）に対して反応性及び／又は親和性を示す有機官能基と、無機系材料（二液混合形塗料組成物に含有される顔料等）に対して反応性及び／又は親和性を示す有機官能基とを併せ持つ化合物である。シランカップリング剤（ｃ）を用いることにより、有機ポリマーと無機系材料とが接する界面の接着性等を向上させることが可能となる。 The silane coupling agent (c) contains an organic functional group exhibiting reactivity and / or affinity with an organic polymer (cured resin, etc.) and an inorganic material (pigment contained in a two-component mixed coating composition, etc.). ) Is a compound having an organic functional group exhibiting reactivity and / or affinity with respect to). By using the silane coupling agent (c), it is possible to improve the adhesiveness of the interface between the organic polymer and the inorganic material.
本発明においては、このようなシランカップリング剤（ｃ）として、異なる２種の官能基の一方の官能基として、トリメトキシシリル基又はトリエトキシシリル基を有する化合物が用いられる。トリメトキシシリル基又はトリエトキシシリル基を有する化合物を用いることにより、防錆塗膜の防食性や基材との付着性を向上させることができる。 In the present invention, as such a silane coupling agent (c), a compound having a trimethoxysilyl group or a triethoxysilyl group as one of the two different functional groups is used. By using a compound having a trimethoxysilyl group or a triethoxysilyl group, the corrosion resistance of the rust preventive coating film and the adhesion to the substrate can be improved.
本発明においては、シランカップリング剤（ｃ）として、１種又は２種以上のシランカップリング剤を用いることができる。シランカップリング剤（ｃ）は、主剤（Ｉ）の総質量に対して、０．５〜５質量％の割合で用いられることが好ましい。この割合でシランカップリング剤（ｃ）を用いることにより、二液混合形塗料組成物から形成される防錆塗膜と基材との付着性や防錆塗膜の耐膨れ性をより優れたものとすることができる。 In the present invention, one kind or two or more kinds of silane coupling agents can be used as the silane coupling agent (c). The silane coupling agent (c) is preferably used in a proportion of 0.5 to 5% by mass with respect to the total mass of the main agent (I). By using the silane coupling agent (c) at this ratio, the adhesion between the rust-preventive coating film formed from the two-component mixed coating composition and the base material and the swelling resistance of the rust-preventive coating film are further improved. Can be.
顔料、シランカップリング剤（ｃ）以外のその他の主剤（Ｉ）に対する添加剤としては例えば、併用樹脂、溶剤、タレ止め・沈降防止剤、色分れ防止剤、消泡・ワキ防止剤、レベリング剤、ツヤ消し剤等が挙げられる。 Additives to the main agent (I) other than the pigment and the silane coupling agent (c) include, for example, a combined resin, a solvent, a sagging / sedimentation inhibitor, a color separation inhibitor, an antifoaming / armpit inhibitor, and leveling. Examples include agents and matting agents.
併用樹脂としては、例えば、石油系樹脂（キシレン樹脂等）、アクリル樹脂、ポリエステル樹脂等を用いることができる。これらの併用樹脂を用いることにより、防錆塗膜の物性を改善することができる。 As the combined resin, for example, a petroleum-based resin (xylene resin or the like), an acrylic resin, a polyester resin or the like can be used. By using these combined resins, the physical characteristics of the rust preventive coating film can be improved.
溶剤としては、当該分野において通常用いられるものを用いることができ、例えば、トルエン、キシレン、イソブチルアルコール、メチルエチルケトン、及びこれらの２種以上の混合溶剤等が挙げられる。後述する弱溶剤を用いることもできる。 As the solvent, those usually used in the art can be used, and examples thereof include toluene, xylene, isobutyl alcohol, methyl ethyl ketone, and a mixed solvent of two or more of these. A weak solvent described later can also be used.
タレ止め・沈降防止剤としては、当該分野において通常用いられるものを用いることができ、例えば、商品名で「ディスパロン ６７００」（脂肪族ビスアマイド揺変剤、楠本化成社製）等を好ましく用いることができる。色分れ防止剤としては、例えば、商品名で「ディスパロン ２１００」（シリコン添加脂肪族系多価カルボン酸、楠本化成社製）等を好ましく用いることができる。消泡・ワキ防止剤としては、例えば、商品名で「ディスパロン １９５０」（特殊ビニル系重合物、楠本化成社製）等を好ましく用いることができる。 As the anti-sagging / sedimentation inhibitor, those usually used in the art can be used. For example, "Disparon 6700" (aliphatic bisamide rocking agent, manufactured by Kusumoto Kasei Co., Ltd.) under the trade name is preferably used. it can. As the color separation inhibitor, for example, "Disparon 2100" (silicon-added aliphatic polyvalent carboxylic acid, manufactured by Kusumoto Kasei Co., Ltd.) or the like can be preferably used under the trade name. As the antifoaming / armpit inhibitor, for example, "Disparon 1950" (special vinyl polymer, manufactured by Kusumoto Kasei Co., Ltd.) under the trade name can be preferably used.
＜溶剤＞
本実施形態に係る二液混合形塗料組成物は、溶剤として弱溶剤を含むことが好ましい。詳細には、主剤（Ｉ）又は硬化剤（ＩＩ）の少なくともいずれか一方の溶剤として弱溶剤が用いられることが好ましく、本実施形態においては、主剤（Ｉ）及び硬化剤（ＩＩ）の溶剤として弱溶剤が用いられる。
<Solvent>
The two-component mixed coating composition according to the present embodiment preferably contains a weak solvent as the solvent. Specifically, a weak solvent is preferably used as the solvent for at least one of the main agent (I) and the curing agent (II), and in the present embodiment, as the solvent for the main agent (I) and the curing agent (II). A weak solvent is used.
従来用いられてきた二液混合形塗料組成物においては、主剤（Ｉ）や硬化剤（ＩＩ）の種類によっては十分な低温硬化性を得られない場合がある。本実施形態に係る二液混合形塗料組成物は、弱溶剤を用いない場合でも十分な低温硬化性が得られるが、弱溶剤が二液混合形塗料組成物の溶剤として用いられることで、更に低温硬化性（特に塗り重ね性）を向上させることができる。また、二液混合形塗料組成物の臭気を低減させることもできる。また、防錆塗膜の外観異常（ちぢみ）を防止することもできる。 In the conventionally used two-component mixed coating composition, sufficient low-temperature curability may not be obtained depending on the type of the main agent (I) and the curing agent (II). The two-component mixed coating composition according to the present embodiment can obtain sufficient low-temperature curability even when a weak solvent is not used, but further, when the weak solvent is used as the solvent of the two-component mixed coating composition, It is possible to improve low temperature curability (particularly recoatability). It is also possible to reduce the odor of the two-component mixed coating composition. In addition, it is possible to prevent abnormal appearance of the rust-preventive coating film.
弱溶剤とは、脂肪族炭化水素系溶剤であり、ミネラルスピリットやターペン等に代表されるような高引火点、高沸点、低有害性であるものをいう。より具体的な弱溶剤としては、ミネラルスピリット、ホワイトスピリット、ミネラルターペン、イソパラフィン、ソルベント灯油、芳香族ナフサ、ＶＭ＆Ｐナフサ、ソルベントナフサ等挙げられる。 The weak solvent is an aliphatic hydrocarbon solvent having a high flash point, a high boiling point, and a low toxicity as typified by mineral spirit and turpen. More specific weak solvents include mineral spirit, white spirit, mineral tarpen, isoparaffin, solvent kerosene, aromatic naphtha, VM & P naphtha, solvent naphtha and the like.
弱溶剤の市販品としては、いずれも商品名で「ソルベッソ１００」、「ソルベッソ１５０」、「ソルベッソ２００」（いずれもエッソ石油社製）や、いずれも商品名で「スワゾール３１０」、「スワゾール１０００」、「スワゾール１５００」（いずれもコスモ石油社製）等が挙げられる。この他、単成分溶剤としてはｎ−ブタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、イソノナン、ｎ−デカン、ｎ−ドデカン、シクロペンタン、シクロヘキサン、シクロブタン等の脂肪族炭化水素類等が挙げられる。 As commercial products of weak solvents, the product names are "Solbesso 100", "Solbesso 150", "Solvesso 200" (all manufactured by Esso Oil Co., Ltd.), and the product names are "Swazole 310" and "Swazole 1000". , "Swazole 1500" (both manufactured by Cosmo Oil Co., Ltd.) and the like. In addition, examples of the single component solvent include aliphatic hydrocarbons such as n-butane, n-hexane, n-heptane, n-octane, isononan, n-decane, n-dodecane, cyclopentane, cyclohexane, and cyclobutane. Be done.
主剤（Ｉ）の溶剤としての弱溶剤は、主剤（Ｉ）の総質量に対して、５〜５０質量％含まれることが好ましい。弱溶剤が５〜５０質量％含まれることにより、塗り重ね性を向上させる効果、臭気を低減させる効果、外観異常（ちぢみ）を抑制させる効果を十分に得ることができる。 The weak solvent as the solvent of the main agent (I) is preferably contained in an amount of 5 to 50% by mass with respect to the total mass of the main agent (I). By containing 5 to 50% by mass of the weak solvent, it is possible to sufficiently obtain the effect of improving the recoatability, the effect of reducing the odor, and the effect of suppressing the appearance abnormality (chijimi).
＜ＰＶＣ＞
本実施形態に係る二液混合形塗料組成物は、その主剤（Ｉ）の顔料体積濃度（ＰＶＣ）が３０〜６０％であることが好ましい。ＰＶＣが６０％を超えると塗膜が脆くなり割れの発生や付着性の低下が生じる。ＰＶＣが２０％未満であると塗膜中の顔料の割合が減ることで塗膜の隠ぺい性が低下する傾向がある。
なお、本実施形態で示すＰＶＣ（ｐｉｇｍｅｎｔ ｖｏｌｕｍｅ ｃｏｎｃｅｎｔｒａｔｉｏｎ）とは、主剤（Ｉ）中の全樹脂分と全顔料との合計固形分に占める当該顔料分の体積百分率（％）である。
<PVC>
The two-component mixed coating composition according to the present embodiment preferably has a pigment volume concentration (PVC) of the main agent (I) of 30 to 60%. If the PVC exceeds 60%, the coating film becomes brittle, cracks occur, and the adhesiveness decreases. If the PVC is less than 20%, the proportion of the pigment in the coating film tends to decrease, and the hiding property of the coating film tends to decrease.
The PVC (pigment volume fraction) shown in the present embodiment is the volume percentage (%) of the pigment content in the total solid content of the total resin content and the total pigment in the main agent (I).
本実施形態に係る二液混合形塗料組成物の塗装は、刷毛、ローラー、スプレー等の一般的な方法により行なうことができる。二液混合形塗料組成物を使用する直前に、主剤（Ｉ）と硬化剤（ＩＩ）とを混合することにより得られる塗料を、上記方法を用いて塗布する。かかる主剤（Ｉ）と硬化剤（ＩＩ）とを混合することにより得られる塗料の塗装は、主剤（Ｉ）と硬化剤（ＩＩ）との混合後、可使時間内に行なう。本実施形態に係る二液混合形塗料組成物は、典型的には、３０分〜８時間程度の可使時間を示す。溶剤の量によっては、２〜８時間程度を示す。塗装を行なった後は、エポキシ基−アミノ基間の硬化反応やシランカップリング剤（ｃ）によるカップリング反応等が進行することによって硬化反応が進行するため、低温硬化性が優れた二液混合形塗料組成物を得ることができる。 The coating of the two-component mixed coating composition according to the present embodiment can be performed by a general method such as a brush, a roller, or a spray. Immediately before using the two-component mixed coating composition, the coating material obtained by mixing the main agent (I) and the curing agent (II) is applied by using the above method. The coating material obtained by mixing the main agent (I) and the curing agent (II) is applied within the pot life after the main agent (I) and the curing agent (II) are mixed. The two-component mixed coating composition according to the present embodiment typically exhibits a pot life of about 30 minutes to 8 hours. Depending on the amount of solvent, it takes about 2 to 8 hours. After coating, the curing reaction proceeds as the curing reaction between the epoxy group and the amino group and the coupling reaction with the silane coupling agent (c) proceed, so that the two-component mixture has excellent low-temperature curability. A shape coating composition can be obtained.
被塗物（本実施形態に係る二液混合形塗料組成物が塗装される対象物）としては、防食を必要とするものであれば特に限定されるものではないが、例えば、船舶、車両（例えば、鉄道車両、大型車両）、航空機、橋梁、海上構築物、プラント、タンク（例えば、石油タンク）、パイプ、鋼管、鋳鉄管等、又は鋼製構造物、建築物の鋼性部分等が挙げられる。また、旧塗膜の残る被塗物に対して適用された場合にも、二液混合形塗料組成物は良好な低温硬化性を示す。また、本発明で述べる低温とは冬場の外気温低下に従って上述被塗物の基材温度が低くなる状態を示し、具体的には基材表面の温度が１０℃より低い状態を示す。 The object to be coated (the object to which the two-component mixed coating composition according to the present embodiment is coated) is not particularly limited as long as it requires anticorrosion, but for example, a ship or a vehicle ( For example, railroad vehicles, large vehicles), aircraft, bridges, marine structures, plants, tanks (eg, oil tanks), pipes, steel pipes, cast iron pipes, etc., or steel structures, steel parts of buildings, etc. .. Further, even when applied to an object to be coated in which the old coating film remains, the two-component mixed type coating composition exhibits good low-temperature curability. Further, the low temperature described in the present invention indicates a state in which the base material temperature of the object to be coated becomes lower as the outside air temperature decreases in winter, and specifically, a state in which the temperature of the base material surface is lower than 10 ° C.
被塗物の表面は、予めブラスト処理されたものであってもよく、さび止め塗装、ショップ塗装、有機又は無機ジンクプライマー塗装が施されたものであってもよい。かかる表面に対しても、二液混合形塗料組成物の低温硬化性は優れている。 The surface of the object to be coated may be pre-blasted, or may have been subjected to rust preventive coating, shop coating, or organic or inorganic zinc primer coating. Even on such a surface, the low temperature curability of the two-component mixed coating composition is excellent.
本実施形態に係る二液混合形塗料組成物の塗布により形成される防錆塗膜の膜厚は、被塗物の種類、用途等に応じて適宜のものとすることができるが、通常、乾燥膜厚は１０〜３００μｍ程度である。また、本実施形態に係る二液混合形塗料組成物の塗布により形成される防錆塗膜は、該組成物を複数回にわたって塗布することにより、積層構造とすることも可能である。その際の１回の塗布量及び塗料組成物の粘度は特に制限されるものではなく、通常、それぞれの防錆塗膜の乾燥膜厚が１０〜３００μｍとなるように塗布される。 The film thickness of the rust-preventive coating film formed by applying the two-component mixed coating composition according to the present embodiment can be appropriately adjusted depending on the type and application of the object to be coated, but is usually used. The dry film thickness is about 10 to 300 μm. Further, the rust preventive coating film formed by applying the two-component mixed coating composition according to the present embodiment can be formed into a laminated structure by applying the composition a plurality of times. At that time, the amount of one coating and the viscosity of the coating composition are not particularly limited, and usually, the coating is applied so that the dry film thickness of each rust preventive coating film is 10 to 300 μm.
以上のようにして形成された防錆塗膜（下塗り層）上には、上塗り層として、上塗り塗料や機能性塗料を塗装してもよい。本実施形態に係る二液混合形塗料組成物から形成される防錆塗膜は、このような上塗り塗料や機能性塗料からなる塗膜に対しても、本実施形態における二液混合形塗料組成物は、優れた付着性を示すことができる。 On the rust preventive coating film (undercoat layer) formed as described above, a topcoat paint or a functional paint may be applied as a topcoat layer. The rust-preventive coating film formed from the two-component mixed coating composition according to the present embodiment also has a two-component mixed coating composition according to the present embodiment, even for a coating film composed of such a topcoat paint or a functional paint. The object can exhibit excellent adhesion.
上塗り塗料としては、例えば、油性系塗料、長油性フタル酸樹脂塗料、シリコンアルキッド樹脂塗料、フェノール樹脂塗料、塩化ゴム系樹脂塗料、エポキシ樹脂塗料、変性エポキシ樹脂塗料、タールエポキシ樹脂塗料、塩化ビニル樹脂塗料、ポリウレタン樹脂塗料、フッ素樹脂塗料、シリコン変性樹脂塗料等が挙げられる。
また、機能性塗料としては、汚染物質に対してセルフクリーニング機能を発現する光触媒塗料、海洋生物等の付着を防止する防汚塗料等が挙げられる。これらのなかでも、エポキシ樹脂塗料、ポリウレタン樹脂塗料、フッ素樹脂塗料、アクリル樹脂系防汚塗料、ビニル樹脂系防汚塗料等が好ましく用いられる。本実施形態に係る二液混合形塗料組成物から形成される防錆塗膜は、同系のエポキシ樹脂系塗料に対しても、また、異系の塗料に対しても優れた付着性を示すことができる。
なお、本実施形態に係る二液混合形塗料組成物は、上塗り層の形成のために用いられてもよい。この場合、上塗り層の乾燥膜厚は、通常、１０〜３００μｍ程度とされる。
Examples of the topcoat paint include oil-based paint, long-oil phthalic acid resin paint, silicon alkyd resin paint, phenol resin paint, rubber chloride resin paint, epoxy resin paint, modified epoxy resin paint, tar epoxy resin paint, and vinyl chloride resin. Examples thereof include paints, polyurethane resin paints, fluororesin paints, and silicon-modified resin paints.
In addition, examples of the functional paint include a photocatalytic paint that exhibits a self-cleaning function against pollutants, an antifouling paint that prevents the adhesion of marine organisms and the like. Among these, epoxy resin paints, polyurethane resin paints, fluororesin paints, acrylic resin-based antifouling paints, vinyl resin-based antifouling paints and the like are preferably used. The rust-preventive coating film formed from the two-component mixed coating composition according to the present embodiment exhibits excellent adhesion to similar epoxy resin-based paints and to different paints. Can be done.
The two-component mixed coating composition according to the present embodiment may be used for forming a topcoat layer. In this case, the dry film thickness of the topcoat layer is usually about 10 to 300 μm.
以上説明したように、本実施形態における二液混合形塗料組成物は、金属基材の表面を被覆する防錆塗膜を形成するために用いられる、主剤（Ｉ）及び硬化剤（ＩＩ）を含む二液混合形塗料組成物であって、主剤（Ｉ）は、エポキシ樹脂（ａ）を含み、硬化剤（ＩＩ）は、ポリアミン（ｂ）を含み、エポキシ樹脂（ａ）は、ビスフェノールＡ型エポキシ樹脂又はノボラック型エポキシ樹脂の少なくともいずれかで、かつ、重量平均分子量が６，５００〜１０，０００であり、ポリアミン（ｂ）は、脂環式ポリアミン（ｂ−１）と、脂環式ポリアミンを含まないポリアミン（ｂ−２）と、アルキルフェノール（ｂ−３）と、を含む。これにより、低温硬化性及び塗膜性能が優れた二液混合形塗料組成物を得ることができる。 As described above, the two-component mixed coating composition in the present embodiment contains the main agent (I) and the curing agent (II) used for forming the rust-preventive coating film that covers the surface of the metal substrate. A two-component mixed coating composition containing, the main agent (I) contains an epoxy resin (a), the curing agent (II) contains a polyamine (b), and the epoxy resin (a) is a bisphenol A type. It is at least one of an epoxy resin and a novolak type epoxy resin, and has a weight average molecular weight of 6,500 to 10,000. The polyamines (b) are alicyclic polyamine (b-1) and alicyclic polyamine. Contains polyamines (b-2) and alkylphenols (b-3) that do not contain. As a result, a two-component mixed coating composition having excellent low-temperature curability and coating film performance can be obtained.
また、主剤（Ｉ）は、更にシランカップリング剤（ｃ）を含み、シランカップリング剤（ｃ）は、異なる２種の官能基の一方の官能基として、トリメトキシシリル基又はトリエトキシシリル基を有する。これにより、防錆塗膜の防食性や基材との付着性を向上させることができる。 Further, the main agent (I) further contains a silane coupling agent (c), and the silane coupling agent (c) has a trimethoxysilyl group or a triethoxysilyl group as one of the two different functional groups. Has. This makes it possible to improve the corrosion resistance of the rust preventive coating film and the adhesion to the base material.
また、二液混合形塗料組成物は、弱溶剤を更に含む。弱溶剤が二液混合形塗料組成物の溶剤として用いられることで、より低温硬化性（特に塗り重ね性）を向上させることができる。また、二液混合形塗料組成物の臭気を低減させることもできる。また、防錆塗膜の外観を良好にできる。 In addition, the two-component mixed coating composition further contains a weak solvent. By using a weak solvent as a solvent for the two-component mixed coating composition, low-temperature curability (particularly recoatability) can be further improved. It is also possible to reduce the odor of the two-component mixed coating composition. Moreover, the appearance of the rust preventive coating film can be improved.
また、脂環式ポリアミン（ｂ−１）は、硬化剤（ＩＩ）の総質量に対して、１０〜２０質量％含まれる。また、脂環式ポリアミンを含まないポリアミン（ｂ−２）は、硬化剤（ＩＩ）の総質量に対して、０．６〜６．３質量％含まれる。また、アルキルフェノール（ｂ−３）は、硬化剤（ＩＩ）の総質量に対して、６〜３０質量％含まれる。また主剤（Ｉ）の顔料体積濃度（ＰＶＣ）は３０〜６０％である。これらの条件を満たすことで、低温硬化性及び塗膜性能がより優れた二液混合形塗料組成物を得ることができる。 The alicyclic polyamine (b-1) is contained in an amount of 10 to 20% by mass with respect to the total mass of the curing agent (II). Further, the polyamine (b-2) containing no alicyclic polyamine is contained in an amount of 0.6 to 6.3% by mass with respect to the total mass of the curing agent (II). Further, the alkylphenol (b-3) is contained in an amount of 6 to 30% by mass with respect to the total mass of the curing agent (II). The pigment volume concentration (PVC) of the main agent (I) is 30 to 60%. By satisfying these conditions, a two-component mixed coating composition having more excellent low-temperature curability and coating film performance can be obtained.
以下、実施例及び比較例により本発明を更に具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
＜実施例１〜２２＞
表１に示される配合処方に従い、配合成分を混合し、エポキシ樹脂を含む主剤（Ｉ）及び硬化剤（ＩＩ）をそれぞれ調製し、実施例１〜２２の二液混合形塗料組成物を得た。表１に示される各配合成分の詳細は次のとおりである。表１には、主剤（Ｉ）の顔料体積濃度（ＰＶＣ）を併記する。
<Examples 1 to 22>
According to the formulation shown in Table 1, the ingredients were mixed to prepare the main agent (I) and the curing agent (II) containing the epoxy resin, respectively, to obtain the two-component mixed coating composition of Examples 1 to 22. .. The details of each compounding ingredient shown in Table 1 are as follows. Table 1 also shows the pigment volume concentration (PVC) of the main agent (I).
（１）ノボラック型エポキシ樹脂Ａ：エポキシ樹脂（ａ）
温度計、撹拌装置及び冷却管をつけた水分離装置を備えた２Ｌ反応器に、ヒタノール＃１１３３（日立化成工業社製；ｐ−第三ブチルフェノールノボラック樹脂、ＯＨ当量１５８、平均核体数３）２５０ｇ、ヒタノール＃１５０１（日立化成工業社製；オクチルフェノールノボラック樹脂、ＯＨ当量２１４、平均核体数３）２５０ｇ及びエピクロルヒドリン１４４０ｇを仕込み、撹拌して均一溶液にした後、４８重量％水酸化ナトリウム２６８ｇを６０〜１１０℃で２時間かけて滴下した。この間、系内で生成した水分はエピクロルヒドリンと共沸させて水分離装置で系外へ除去しながらエピクロルヒドリンを系内で還流させた。滴下終了後、１００〜１２０℃で２時間熟成し、理論水量が流出した時点で反応を終了させた。
得られたエポキシ化合物のエピクロルヒドリン溶液にキシレン１５０ｇを加え、大量の水で洗浄し、生成した食塩及び過剰の水酸化ナトリウムを除去した後、３重量％リン酸水溶液で中和した。次いで、減圧下でエピクロルヒドリン及びキシレンを留去し、これにスワゾール３１０（コスモ石油製；高沸点パラフィン系溶剤）を４６０ｇ加え、液状のエポキシ樹脂（ノボラック型エポキシ樹脂Ａ）を得た。この重量平均分子量は８，５００、エポキシ当量は１０１０、固形分は６０重量％、比重は０．９０であった。
（２）ノボラック型エポキシ樹脂Ｂ：エポキシ樹脂（ａ）
エピクロルヒドリンを２０４０ｇに変更した以外は上述の処方に準じてノボラック型エポキシ樹脂Ｂを得た。この重量平均分子量は６，５００、エポキシ当量は１０００、固形分は６０重量％、比重は０．９０であった。
（３）ノボラック型エポキシ樹脂Ｃ：エポキシ樹脂（ａ）
エピクロルヒドリンを１０４０ｇに変更した以外は上述の処方に準じてノボラック型エポキシ樹脂Ｃを得た。この重量平均分子量は９，５００、エポキシ当量は１０２０、固形分は６０重量％、比重は０．９０であった。
（４）ビスフェノールＡ型エポキシ樹脂Ｄ：エポキシ樹脂（ａ）
ビスフェノールＡ型エポキシ樹脂ＤとしてｊＥＲ１００７（三菱化学社製）を用いた。この重量平均分子量は１０，０００、エポキシ当量は１９７５、固形分は１００重量％、比重は１．１９であった。
（５）重炭：ＫＳ−８０００（比重２．５、カルファイン社製）
（６）タルク：タルクＳＳＳ（比重２．７５、日本タルク社製）
（７）酸化チタン：Ｒ−９９６（比重２．６５、ＬＯＭＯＮ社製）
（８）防錆顔料：ＣＬＦ−１０２（比重０．３、広西化工研究院社製）
（９）シランカップリング剤（ｃ）：トリメトキシシリル基含有シランカップリング剤Ａ：ＫＢＭ−４０３（比重１．０７、信越化学社製）
（１０）シランカップリング剤（ｃ）：トリエトキシシリル基含有シランカップリング剤Ｂ：ＫＢＥ−４０３（比重１．００、信越化学社製）
（１１）脂環式ポリアミン（ｂ−１）：ＷＮ−１５５（比重１．２９、ＤＩＣ社製）
（１２）脂環式ポリアミンを含まないポリアミン（ｂ−２）：メタキシレンジアミン（比重１．０５、東京化成社製）
（１３）アルキルフェノール（ｂ−３）：オルト−ターシャリブチルフェノール（比重０．９０８、東京化成社製）
（１４）弱溶剤：ソルベッソ１００（比重０．８８、エッソ石油社製）
（１５）キシレン：キシロール（昭栄ケミカル社製）
(1) Novolac type epoxy resin A: Epoxy resin (a)
Hitanol # 1133 (manufactured by Hitachi Kasei Kogyo Co., Ltd .; p-third butylphenol novolac resin, OH equivalent 158, average number of nuclei 3) in a 2L reactor equipped with a thermometer, a stirrer and a water separator equipped with a cooling tube. 250 g, 250 g of Hitanol # 1501 (manufactured by Hitachi Kasei Kogyo Co., Ltd .; octylphenol novolac resin, OH equivalent 214, average number of nuclei 3) and 1440 g of epichlorohydrin were charged, stirred to make a uniform solution, and then 268 g of 48 wt% sodium hydroxide was added. The mixture was added dropwise at 60 to 110 ° C. over 2 hours. During this period, the water generated in the system was azeotropically boiled with epichlorohydrin and removed to the outside of the system by a water separator, and epichlorohydrin was refluxed in the system. After completion of the dropping, the mixture was aged at 100 to 120 ° C. for 2 hours, and the reaction was terminated when the theoretical amount of water flowed out.
To the epichlorohydrin solution of the obtained epoxy compound, 150 g of xylene was added, washed with a large amount of water to remove the salt produced and excess sodium hydroxide, and then neutralized with a 3 wt% aqueous phosphoric acid solution. Next, epichlorohydrin and xylene were distilled off under reduced pressure, and 460 g of Swazole 310 (manufactured by Cosmo Oil Co., Ltd .; a high boiling point paraffin solvent) was added thereto to obtain a liquid epoxy resin (novolac type epoxy resin A). The weight average molecular weight was 8,500, the epoxy equivalent was 1010, the solid content was 60% by weight, and the specific gravity was 0.90.
(2) Novolac type epoxy resin B: Epoxy resin (a)
A novolak type epoxy resin B was obtained according to the above formulation except that epichlorohydrin was changed to 2040 g. The weight average molecular weight was 6,500, the epoxy equivalent was 1000, the solid content was 60% by weight, and the specific gravity was 0.90.
(3) Novolac type epoxy resin C: Epoxy resin (a)
A novolak type epoxy resin C was obtained according to the above formulation except that epichlorohydrin was changed to 1040 g. The weight average molecular weight was 9,500, the epoxy equivalent was 1020, the solid content was 60% by weight, and the specific gravity was 0.90.
(4) Bisphenol A type epoxy resin D: Epoxy resin (a)
JER1007 (manufactured by Mitsubishi Chemical Corporation) was used as the bisphenol A type epoxy resin D. The weight average molecular weight was 10,000, the epoxy equivalent was 1975, the solid content was 100% by weight, and the specific gravity was 1.19.
(5) Heavy coal: KS-8000 (specific gravity 2.5, manufactured by Calfine)
(6) Talc: Talc SSS (specific gravity 2.75, manufactured by Japan Talc)
(7) Titanium oxide: R-996 (specific gravity 2.65, manufactured by LOMON)
(8) Rust preventive pigment: CLF-102 (specific gravity 0.3, manufactured by Guangxi Chemical Engineering Research Institute)
(9) Silane coupling agent (c): Trimethoxysilyl group-containing silane coupling agent A: KBM-403 (specific gravity 1.07, manufactured by Shin-Etsu Chemical Co., Ltd.)
(10) Silane coupling agent (c): Triethoxysilyl group-containing silane coupling agent B: KBE-403 (specific gravity 1.00, manufactured by Shin-Etsu Chemical Co., Ltd.)
(11) Alicyclic polyamine (b-1): WN-155 (specific gravity 1.29, manufactured by DIC Corporation)
(12) Polyamines containing no alicyclic polyamine (b-2): m-xylylenediamine (specific gravity 1.05, manufactured by Tokyo Kasei Co., Ltd.)
(13) Alkylphenol (b-3): Ortho-tershaributylphenol (specific gravity 0.908, manufactured by Tokyo Kasei Co., Ltd.)
(14) Weak solvent: Solbesso 100 (specific gravity 0.88, manufactured by Esso Petroleum Co., Ltd.)
(15) Xylene: Xylene (manufactured by Shoei Chemical Co., Ltd.)
＜比較例１〜１０＞
表２に示される配合処方に従い、配合成分を混合し、エポキシ樹脂を含む主剤（Ｉ）及び硬化剤（ＩＩ）をそれぞれ調製し、比較例１〜１０の二液混合形塗料組成物を得た。表２に新たに示される各配合成分の詳細は次のとおりである。表２には、表１と同様に主剤（Ｉ）の顔料体積濃度（ＰＶＣ）を併記する。
<Comparative Examples 1 to 10>
According to the formulation shown in Table 2, the ingredients were mixed to prepare the main agent (I) and the curing agent (II) containing the epoxy resin, respectively, to obtain the two-component mixed coating composition of Comparative Examples 1 to 10. .. Details of each compounding ingredient newly shown in Table 2 are as follows. Table 2 also shows the pigment volume concentration (PVC) of the main agent (I) as in Table 1.
（１６）ビスフェノールＡ型エポキシ樹脂Ｅ
ビスフェノールＡ型エポキシ樹脂ＥとしてｊＥＲ１００９（三菱化学社製）を用いた。この重量平均分子量は２０，０００、エポキシ当量は２８５０、固形分１００重量％であった。
（１７）非ノボラック型かつ非ビスフェノールＡ型エポキシ樹脂Ｆ（重量平均分子量４２０、エポキシ当量１４５）：エポライト１００ＭＦ（共栄社化学社製）
（１８）ノボラック型エポキシ樹脂Ｇ
ノボラック型エポキシ樹脂ＦとしてＥＰＩＣＬＯＮ ＮＫ５９−６０ＭＳ（ＤＩＣ社製）を用いた。この重量平均分子量は５，７００、エポキシ当量は１０００以上、固形分６０重量％、比重０．９５であった。
（１９）脂肪族ポリアミン：フジキュアー ＦＸＰ−８０８８（比重０．９６、Ｔ＆Ｋ ＴＯＫＡ社製）
(16) Bisphenol A type epoxy resin E
JER1009 (manufactured by Mitsubishi Chemical Corporation) was used as the bisphenol A type epoxy resin E. The weight average molecular weight was 20,000, the epoxy equivalent was 2850, and the solid content was 100% by weight.
(17) Non-novolac type and non-bisphenol A type epoxy resin F (weight average molecular weight 420, epoxy equivalent 145): Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.)
(18) Novolac type epoxy resin G
EPICLON NK59-60MS (manufactured by DIC Corporation) was used as the novolak type epoxy resin F. The weight average molecular weight was 5,700, the epoxy equivalent was 1000 or more, the solid content was 60% by weight, and the specific gravity was 0.95.
(19) Aliphatic polyamine: Fujicure FXP-8088 (specific gravity 0.96, manufactured by T & K TOKA)
以上の実施例及び比較例の二液混合形塗料組成物の主剤（Ｉ）と硬化剤（ＩＩ）とを混合、調整し、被塗物に塗布し、二液混合形塗料組成物の低温硬化性と、防錆塗膜の外観とを評価した。 The main agent (I) and the curing agent (II) of the two-component mixed coating composition of the above Examples and Comparative Examples are mixed and adjusted, applied to an object to be coated, and low-temperature curing of the two-component mixed coating composition. The properties and the appearance of the rust preventive coating film were evaluated.
［１］低温硬化性
二液混合形塗料組成物の低温硬化性を、以下に示す低温乾燥性、防食性、付着性、塗り重ね性、踏み込み性の試験により評価した。実施例及び比較例の結果を表３及び表４に示す。
[1] Low-temperature curability The low-temperature curability of the two-component mixed coating composition was evaluated by the following tests of low-temperature drying property, corrosion resistance, adhesiveness, recoatability, and stepping property. The results of Examples and Comparative Examples are shown in Tables 3 and 4.
＜低温乾燥性＞
実施例及び比較例に示す二液混合形塗料組成物の低温乾燥性を、特許第３６５２８６４号公報を参考に評価した。詳細には、二液混合形塗料組成物を、脱脂した磨き鋼板（１５０×７０×０．８ｍｍ）にエアスプレーを用いて乾燥膜厚が約６０μｍとなるように塗装し、０℃の条件で１６時間乾燥し防錆塗膜を得た。防錆塗膜を指触し、以下の評価基準で低温乾燥性を評価した。
（評価基準）
４：指で強く押しても塗膜がずれない。
３：指で強く押すと塗膜がずれるが、軽くこすっても跡が残らない。
２：指で軽くこすると跡がつくが、軽く触っても塗料がつかない。
１：指で軽く触ったときに塗料がつく。
<Low temperature drying property>
The low-temperature drying property of the two-component mixed coating composition shown in Examples and Comparative Examples was evaluated with reference to Japanese Patent No. 3652864. Specifically, the two-component mixed coating composition is coated on a degreased polished steel sheet (150 × 70 × 0.8 mm) using an air spray so that the dry film thickness is about 60 μm, and at 0 ° C. It was dried for 16 hours to obtain a rust preventive coating film. The rust-preventive coating film was touched and the low-temperature drying property was evaluated according to the following evaluation criteria.
(Evaluation criteria)
4: The coating film does not shift even if it is pressed strongly with a finger.
3: The coating film shifts when pressed strongly with a finger, but no trace remains even when rubbed lightly.
2: If you rub it lightly with your finger, it will leave a mark, but even if you touch it lightly, the paint will not adhere.
1: The paint sticks when you touch it lightly with your finger.
＜防食性＞
実施例及び比較例に示す二液混合形塗料組成物の防食性を、ＪＩＳ Ｋ ５６００−７−９を参考に評価した。詳細には、調製直後の二液混合形塗料組成物を、グリッドブラスト鋼板（７ｃｍ×１５ｃｍ×３．２ｍｍ）に、エアスプレーを用いて乾燥膜厚が約６０μｍとなるように塗装し、２３℃５０％ＲＨの条件で７日間養生し、防錆塗膜を得た。二液混合形塗料組成物に対して３枚の防錆塗膜を用意し、ＪＩＳ Ｋ ５６００−７−９ サイクル腐食性試験 １２０ｃｙｃ（サイクルＤ）を参考に、以下の評価基準で防食性を評価した。
（評価基準）
４：防錆塗膜３枚中すべてでさび・ふくれ・われを認めない。
３：防錆塗膜３枚中１枚でさび・ふくれ・われを認める。
２：防錆塗膜３枚中２枚でさび・ふくれ・われを認める。
１：すべての防錆塗膜でさび・ふくれ・われを認める。
なお、防錆塗膜の周辺約１０ｍｍ以内及び塗膜に付けた傷の両側それぞれ４ｍｍ以内の塗膜は評価の対象外とし、さび汁による汚れも評価の対象外とした。
<Anti-corrosion property>
The corrosion resistance of the two-component mixed coating composition shown in Examples and Comparative Examples was evaluated with reference to JIS K 5600-7-9. Specifically, the two-component mixed coating composition immediately after preparation is coated on a grid blast steel sheet (7 cm × 15 cm × 3.2 mm) using an air spray so that the dry film thickness is about 60 μm, and the temperature is 23 ° C. It was cured under the condition of 50% RH for 7 days to obtain a rust preventive coating film. Three rust-preventive coating films were prepared for the two-component mixed paint composition, and the corrosion resistance was evaluated according to the following evaluation criteria with reference to JIS K 5600-7-9 cycle corrosion test 120 cycl (cycle D). did.
(Evaluation criteria)
4: No rust, blisters, or cracks are found in all three rust preventive coatings.
3: Rust, blisters, and cracks are observed on one of the three rust preventive coating films.
2: Rust, blisters, and cracks are observed on 2 out of 3 rust preventive coating films.
1: Rust, blisters and cracks are observed on all rust preventive coatings.
The coating film within about 10 mm around the rust-preventive coating film and within 4 mm on each side of the scratches on the coating film was excluded from the evaluation, and stains caused by rust juice were also excluded from the evaluation.
＜付着性＞
実施例及び比較例に示す二液混合形塗料組成物の付着性を、ＪＩＳ Ｋ ５６００−５−６を参考に評価した。詳細には、二液混合形塗料組成物を、６か月間屋外曝露したＺｎめっき鋼板（１５０×７０×３．２ｍｍ）に、エアスプレーを用いて乾燥膜厚が約６０μｍとなるように塗装し、２３℃５０％ＲＨの条件で７日間養生し、更に、５０℃９５％ＲＨの条件で７日間投入し防錆塗膜を得た。ＪＩＳ Ｋ ５６００−５−６の７．の方法を参考に、２ｍｍ間隔で防錆塗膜の各方面にそれぞれ６本の切り込みを入れ、切り込みを入れた面に粘着テープを圧着し、引きはがし、目視で塗面を観察することで防錆塗膜の付着性を評価した。具体的には、ＪＩＳ Ｋ ５６００−５−６の８．３の表１を参考に、以下の評価基準で付着性を評価した。
（評価基準）
４：分類０又は分類１
３：分類２
２：分類３
１：分類４以下
<Adhesiveness>
The adhesiveness of the two-component mixed coating composition shown in Examples and Comparative Examples was evaluated with reference to JIS K 5600-5-6. Specifically, the two-component mixed coating composition was applied to a Zn-plated steel sheet (150 × 70 × 3.2 mm) exposed outdoors for 6 months using an air spray so that the dry film thickness was about 60 μm. , It was cured under the condition of 23 ° C. and 50% RH for 7 days, and further, it was added for 7 days under the condition of 50 ° C. and 95% RH to obtain a rust preventive coating film. JIS K 5600-5-6 7. With reference to the method of, make 6 notches in each direction of the rust preventive coating film at 2 mm intervals, press the adhesive tape on the notched surface, peel it off, and visually observe the coated surface to prevent it. The adhesiveness of the rust coating film was evaluated. Specifically, the adhesiveness was evaluated according to the following evaluation criteria with reference to Table 1 of 8.3 of JIS K 5600-5-6.
(Evaluation criteria)
4: Category 0 or Category 1
3: Classification 2
2: Classification 3
1: Classification 4 or less
＜塗り重ね性＞
実施例及び比較例に示す二液混合形塗料組成物の塗り重ね性を、ＪＩＳ Ｋ ５５５１−７．１０を参考に評価した。詳細には、二液混合形塗料組成物を、ボンデ鋼板（１５０ｍｍ×７０ｍｍ×０．８ｍｍ）にハケを用いて乾燥膜厚が約６０μｍとなるように塗装し、５℃の条件で２４時間乾燥し防錆塗膜を得た。防錆塗膜に対して、上塗り塗料として、ハイポン３０ファイン中塗（商品名、日本ペイント社製）を、塗装器具として刷毛を用いて塗り重ね、刷毛の塗装作業性、下塗り塗膜の再溶解の観点から、以下の評価基準で塗り重ね性を評価した。
（評価基準）
塗装作業性：刷毛作業感が重くないか（ｉ）。
下塗り塗膜の再溶解：上塗り塗料が下塗を再溶解していないか（ｉｉ）、
リフティングが起きていないか（ｉｉｉ）。
４：（ｉ）〜（ｉｉｉ）のうち、いずれも問題ない。
３：（ｉ）〜（ｉｉｉ）のうち、一つの項目で問題がある。
２：（ｉ）〜（ｉｉｉ）のうち、二つの項目で問題がある。
１：（ｉ）〜（ｉｉｉ）のすべての項目で問題がある。
<Recoatability>
The recoatability of the two-component mixed coating composition shown in Examples and Comparative Examples was evaluated with reference to JIS K 5551-7.10. Specifically, the two-component mixed coating composition is coated on a bonded steel sheet (150 mm × 70 mm × 0.8 mm) with a brush so that the dry film thickness is about 60 μm, and dried at 5 ° C. for 24 hours. A rust preventive coating film was obtained. Hypon 30 Fine intermediate coat (trade name, manufactured by Nippon Paint Co., Ltd.) is applied repeatedly to the rust preventive coating film using a brush as a coating tool to improve the painting workability of the brush and redissolve the undercoat coating. From the viewpoint, the recoatability was evaluated according to the following evaluation criteria.
(Evaluation criteria)
Painting workability: Isn't the brush work feeling heavy (i)?
Re-dissolution of the undercoat: Whether the topcoat has re-dissolved the undercoat (ii),
Is lifting occurring (iii)?
4: There is no problem in any of (i) to (iii).
3: There is a problem in one of (i) to (iii).
2: There is a problem in two of (i) to (iii).
1: There is a problem in all items (i) to (iii).
＜踏み込み性＞
実施例及び比較例に示す二液混合形塗料組成物の踏み込み性を、特開２０１０−２４４０８号公報を参考に評価した。詳細には、二液混合形塗料組成物をボンデ鋼板（９００×２２５×０．８ｍｍ）にエアスプレーを用いて乾燥膜厚が約６０μｍとなるように塗装し、０℃の条件で１６時間養生し防錆塗膜を得た。防錆塗膜の塗膜表面を靴で踏み、全体重を３秒間かけた後、以下の評価基準で踏み込み性を評価した。
（評価基準）
４：塗膜に跡がつかない。
３：塗膜に跡はつかないが、粘着性は残っている。
２：粘着性が残っており、かつ、塗膜に跡がつく。
１：踏み込んだ靴の裏に塗料が付着する。
<Stepping on>
The stepping property of the two-component mixed coating composition shown in Examples and Comparative Examples was evaluated with reference to JP-A-2010-24408. Specifically, the two-component mixed coating composition is coated on a bonded steel sheet (900 x 225 x 0.8 mm) using an air spray so that the dry film thickness is about 60 μm, and cured at 0 ° C. for 16 hours. A rust preventive coating film was obtained. After stepping on the surface of the rust-preventive coating film with shoes and applying the total weight for 3 seconds, the stepping property was evaluated according to the following evaluation criteria.
(Evaluation criteria)
4: No trace is left on the coating film.
3: No trace is left on the coating film, but adhesiveness remains.
2: Adhesiveness remains, and a mark is left on the coating film.
1: Paint adheres to the back of the shoes you step on.
［２］防錆塗膜の外観
二液混合形塗料組成物の防錆塗膜の外観を、以下に示すちぢみ性、温冷繰り返し性の試験により評価した。実施例及び比較例の結果を表３及び表４に示す。
[2] Appearance of rust-preventive coating film The appearance of the rust-preventive coating film of the two-component mixed coating composition was evaluated by the following tests of smallness and hot / cold repeatability. The results of Examples and Comparative Examples are shown in Tables 3 and 4.
＜ちぢみ性＞
実施例及び比較例に示す二液混合形塗料組成物のちぢみ性を、評価した。詳細には、アルキド樹脂塗料（速乾ＰＺヘルゴンエコ：商品名、日本ペイント社製）を、溶融亜鉛めっき鋼板（１５０×７０×３．２ｍｍ）に刷毛を用いて乾燥膜厚が約６０μｍとなるように塗装し、２３℃５０％ＲＨの条件で１日乾燥した。ついで、二液混合形塗料組成物を、刷毛を用いて乾燥膜厚が約５０μｍとなるように塗装し防錆塗膜を得たのち、以下の評価基準で防錆塗膜のちぢみ性を評価した。
（評価基準）
４：外観異常なし
３：１０％以下の面積でちぢみが発生
２：５０％以下の面積でちぢみが発生
１：全面でちぢみが発生
<Smallness>
The smallness of the two-component mixed coating composition shown in Examples and Comparative Examples was evaluated. Specifically, alkyd resin paint (quick-drying PZ Helgon Eco: trade name, manufactured by Nippon Paint Co., Ltd.) is applied to a hot-dip galvanized steel sheet (150 x 70 x 3.2 mm) with a brush so that the dry film thickness is about 60 μm. And dried for 1 day under the condition of 23 ° C. and 50% RH. Then, the two-component mixed coating composition is coated with a brush so that the dry film thickness is about 50 μm to obtain a rust-preventive coating film, and then the rust-preventive coating film is evaluated according to the following evaluation criteria. did.
(Evaluation criteria)
4: No abnormalities in appearance 3: Small areas occur in areas of 10% or less 2: Small areas occur in areas of 50% or less 1: Small areas occur on the entire surface
＜温冷繰り返し性＞
実施例及び比較例に示す二液混合形塗料組成物の温冷繰り返し性を、ＪＩＳ−Ｋ−５６００−７−４に従って評価した。詳細には、二液混合形塗料組成物を、ボンデ鋼板（１５０ｍｍ×７０ｍｍ×０．８ｍｍ）に刷毛を用いて乾燥膜厚が約６０μｍとなるように塗装し、２３℃５０％ＲＨにて１６時間養生した。防錆塗膜に対して、上塗り塗料として、ハイポン３０ファイン中塗（商品名、日本ペイント社製）を塗装器具として刷毛を用いて塗り重ね、２３℃５０％ＲＨにて７日間養生した。ついで、２３±２℃にて１８時間、マイナス２０℃にて３時間、５０±３℃にて３時間を１サイクルとして、温冷繰り返し試験を５０サイクル実施した。５０サイクル終了後、以下の評価基準で温冷繰り返し性を評価した。
（評価基準）
４：外観異常なし
３：１０％以下の面積で割れが発生
２：５０％以下の面積で割れが発生
１：全面で割れが発生
<Repeatability of hot and cold>
The hot / cold repeatability of the two-component mixed coating composition shown in Examples and Comparative Examples was evaluated according to JIS-K-5600-7-4. Specifically, the two-component mixed coating composition is coated on a bonded steel sheet (150 mm × 70 mm × 0.8 mm) using a brush so that the dry film thickness is about 60 μm, and at 23 ° C. and 50% RH 16 Cured for hours. Hypon 30 Fine Intermediate Coating (trade name, manufactured by Nippon Paint Co., Ltd.) was repeatedly applied to the rust-preventive coating film using a brush as a coating tool, and cured at 23 ° C. and 50% RH for 7 days. Then, 50 cycles of repeated heating and cooling tests were carried out, with one cycle being 18 hours at 23 ± 2 ° C., 3 hours at −20 ° C., and 3 hours at 50 ± 3 ° C. After the completion of 50 cycles, the hot / cold repeatability was evaluated according to the following evaluation criteria.
(Evaluation criteria)
4: No appearance abnormality 3: Cracks occur in an area of 10% or less 2: Cracks occur in an area of 50% or less 1: Cracks occur on the entire surface
実施例１〜４と比較例２との比較から、実施例１〜４の塗料組成物の方が、比較例２の塗料組成物よりも塗膜形成時の低温乾燥性、塗り重ね性、踏み込み性が良好であることが分かった。この結果から、本発明に示す重量平均分子量８，５００以上のエポキシ樹脂（ａ）を含有させることで、低温硬化性、塗り重ね性、踏み込み性が向上することが確認された。 From the comparison between Examples 1 to 4 and Comparative Example 2, the coating compositions of Examples 1 to 4 have lower temperature drying property, recoatability, and treading property at the time of coating film formation than the coating composition of Comparative Example 2. It turned out to be good. From this result, it was confirmed that the low temperature curability, the recoatability, and the stepping property were improved by containing the epoxy resin (a) having a weight average molecular weight of 8,500 or more shown in the present invention.
実施例１〜４と比較例１との結果から、実施例１〜４の塗料組成物の方が、比較例１の塗料組成物よりも形成される塗膜の温冷繰り返し試験性能が良好であることが分かった。この結果から本発明に示す重量平均分子量１０，０００以下のエポキシ樹脂（ａ）を含有させることで、温冷繰り返し試験性能が向上することが確認された。 From the results of Examples 1 to 4 and Comparative Example 1, the coating compositions of Examples 1 to 4 have better thermal / cooling repeated test performance of the coating film formed than the coating composition of Comparative Example 1. It turned out that there was. From this result, it was confirmed that the hot / cold repeated test performance was improved by containing the epoxy resin (a) having a weight average molecular weight of 10,000 or less shown in the present invention.
実施例１と実施例２２との比較から、実施例１の塗料組成物の方が、実施例２２の塗料組成物よりも塗り重ね後の耐ちぢみ性能が良好であることが分かった。この結果から本発明に示すエポキシ樹脂（ａ）と弱溶剤を含むことで、耐ちぢみ性能が更に向上することが確認された。 From the comparison between Example 1 and Example 22, it was found that the coating composition of Example 1 had better shrinkage resistance after recoating than the coating composition of Example 22. From this result, it was confirmed that the epoxy resin (a) shown in the present invention and the weak solvent were contained to further improve the shrinkage resistance performance.
実施例１と実施例１９との比較から、実施例１の塗料組成物の方が、実施例１９の塗料組成物よりも防食性、付着性が良好であることが分かった。この結果から更にシランカップリング剤（ｃ）を含有させることで、防食性、付着性がより向上することが確認された。 From the comparison between Example 1 and Example 19, it was found that the coating composition of Example 1 had better corrosion resistance and adhesiveness than the coating composition of Example 19. From this result, it was confirmed that the anticorrosion property and the adhesiveness were further improved by further containing the silane coupling agent (c).
実施例１と比較例９との比較から、実施例１の塗料組成物の方が、比較例９の塗料組成物よりも低温乾燥性、塗り重ね性、踏み込み性が良好であることが分かった。この結果からポリアミン（ｂ）として脂環式ポリアミン（ｂ−１）を含有させることで、低温乾燥性、塗り重ね性、踏み込み性が向上することが確認された。 From the comparison between Example 1 and Comparative Example 9, it was found that the coating composition of Example 1 had better low-temperature drying property, recoatability, and stepping property than the coating composition of Comparative Example 9. .. From this result, it was confirmed that the alicyclic polyamine (b-1) contained as the polyamine (b) improved the low-temperature drying property, the recoatability, and the stepping property.
実施例１と比較例５との比較から、実施例１の塗料組成物の方が、比較例５の塗料組成物よりも低温乾燥性、塗り重ね性、踏み込み性が良好であることが分かった。この結果からポリアミン（ｂ）として脂環式ポリアミン（ｂ−１）を含まないポリアミン（ｂ−２）を含有させることで、低温乾燥性、塗り重ね性、踏み込み性が向上することが確認された。 From the comparison between Example 1 and Comparative Example 5, it was found that the coating composition of Example 1 had better low-temperature drying property, recoatability, and stepping property than the coating composition of Comparative Example 5. .. From this result, it was confirmed that the low temperature drying property, the recoatability, and the stepping property are improved by containing the polyamine (b-2) which does not contain the alicyclic polyamine (b-1) as the polyamine (b). ..
実施例１と比較例７との比較から、実施例１の塗料組成物の方が、比較例７の塗料組成物の方が低温乾燥性、塗り重ね性、踏み込み性が良好であることが分かった。この結果から、アルキルフェノール（ｂ−３）を主剤（Ｉ）に対して６質量％以上含有させることで、低温乾燥性、塗り重ね性、踏み込み性が向上することが確認された。
From the comparison between Example 1 and Comparative Example 7, it was found that the coating composition of Example 1 had better low-temperature drying property, recoatability, and stepping property than the coating composition of Comparative Example 7. It was. From this result, it was confirmed that the low-temperature drying property, the recoatability, and the stepping property were improved by containing 6% by mass or more of the alkylphenol (b-3) with respect to the main agent (I).
Claims (4)
前記主剤（Ｉ）は、エポキシ樹脂（ａ）を含み、
前記硬化剤（ＩＩ）は、ポリアミン（ｂ）を含み、
前記エポキシ樹脂（ａ）は、ビスフェノールＡ型エポキシ樹脂又はノボラック型エポキシ樹脂の少なくともいずれかで、かつ、重量平均分子量が６，５００〜１０，０００であり、
前記ポリアミン（ｂ）は、脂環式ポリアミン（ｂ−１）と、脂環式ポリアミンを含まないポリアミン（ｂ−２）と、アルキルフェノール（ｂ−３）と、を含み、
前記脂環式ポリアミン（ｂ−１）は、前記硬化剤（ＩＩ）の総質量に対して、１０〜２０質量％含まれ、
前記脂環式ポリアミンを含まないポリアミン（ｂ−２）は、前記硬化剤（ＩＩ）の総質量に対して、０．６〜６．３質量％含まれ、
前記アルキルフェノール（ｂ−３）は、前記硬化剤（ＩＩ）の総質量に対して、６〜３０質量％含まれる、二液混合形塗料組成物。 A two-component mixed coating composition containing a main agent (I) and a curing agent (II), which is used for forming a rust preventive coating film that covers the surface of a metal substrate.
The main agent (I) contains an epoxy resin (a).
The curing agent (II) contains a polyamine (b) and contains.
The epoxy resin (a) is at least one of a bisphenol A type epoxy resin and a novolak type epoxy resin, and has a weight average molecular weight of 6,500 to 10,000.
Wherein the polyamine (b) is a cycloaliphatic polyamine (b-1), a polyamine containing no alicyclic polyamine (b-2), and alkyl phenol (b-3), only contains,
The alicyclic polyamine (b-1) is contained in an amount of 10 to 20% by mass with respect to the total mass of the curing agent (II).
The alicyclic polyamine-free polyamine (b-2) is contained in an amount of 0.6 to 6.3% by mass based on the total mass of the curing agent (II).
A two-component mixed coating composition containing 6 to 30% by mass of the alkylphenol (b-3) with respect to the total mass of the curing agent (II).
前記シランカップリング剤（ｃ）は、異なる２種の官能基の一方の官能基として、トリメトキシシリル基又はトリエトキシシリル基を有する請求項１に記載の二液混合形塗料組成物。 The main agent (I) further contains a silane coupling agent (c).
The two-component mixed coating composition according to claim 1, wherein the silane coupling agent (c) has a trimethoxysilyl group or a triethoxysilyl group as one of the two different functional groups.
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| US4503174A (en) * | 1983-09-06 | 1985-03-05 | E. I. Du Pont De Nemours And Company | Low temperature curing coating composition |
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