JPS6241628B2 - - Google Patents
Info
- Publication number
- JPS6241628B2 JPS6241628B2 JP57230054A JP23005482A JPS6241628B2 JP S6241628 B2 JPS6241628 B2 JP S6241628B2 JP 57230054 A JP57230054 A JP 57230054A JP 23005482 A JP23005482 A JP 23005482A JP S6241628 B2 JPS6241628 B2 JP S6241628B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- rust
- weight
- resin
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- 239000003973 paint Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- 230000000903 blocking effect Effects 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 12
- 238000004070 electrodeposition Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 230000002265 prevention Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- -1 amino compound Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 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
- 239000002981 blocking agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 210000003660 reticulum Anatomy 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- QUPKCFBHJFNUEW-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCCN1 QUPKCFBHJFNUEW-UHFFFAOYSA-N 0.000 description 1
- SHYARJUKNREDGB-UHFFFAOYSA-N 2-ethyl-5-methyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCC(C)N1 SHYARJUKNREDGB-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- NCVGSSQICKMAIA-UHFFFAOYSA-N 2-heptadecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NCCN1 NCVGSSQICKMAIA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- BTYIFQSAIPDZQW-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole Chemical compound CC(C)C1=NCCN1 BTYIFQSAIPDZQW-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- FQHUDZKKDCTQET-UHFFFAOYSA-N 2-undecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCC1=NCCN1 FQHUDZKKDCTQET-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- JJUVAPMVTXLLFR-UHFFFAOYSA-N 5-methyl-2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1C(C)CN=C1C1=CC=CC=C1 JJUVAPMVTXLLFR-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UWJRJUDLJQOQSP-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1C Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1C UWJRJUDLJQOQSP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XMYLSWOTJKUSHE-UHFFFAOYSA-N cyanamide;lead Chemical compound [Pb].NC#N XMYLSWOTJKUSHE-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DIHAURBCYGTGCV-UHFFFAOYSA-N xi-4,5-Dihydro-2,4(5)-dimethyl-1H-imidazole Chemical compound CC1CN=C(C)N1 DIHAURBCYGTGCV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は防錆塗料、特に自動車の板金部材接合
部位等に防錆処理を施すために塗布する１液形防
錆塗料に関するものである。
近年、寒冷地の道路において大量に散布される
融雪塩による自動車の腐食が問題視され、その対
策が厳しく要求されるようになつてきており、自
動車各部の材料や構造及び組立工程の見直しがな
されている。
従来、自動車のボンネツト、ドア、トランクリ
ツド、フエンダーなどのはぜ折り部は防錆油やプ
レス油が付着した板金部品をスポツト溶接により
接合した後、前処理工程を経て電着による下塗り
塗装が施されていた。しかしながら、この方法で
は車体に組付けられた後、下塗り塗装が施される
ため、はぜ折り部分やその周辺部に電着塗料が浸
透しにくく、いわゆる付き回り性が十分でなく、
電着塗膜による充分な保護がなされない場合も生
ずるため、車の走行中に融雪塩水がはぜ折り部に
浸透、滞留することにより腐食が発生する現象が
見られることもあつた。従つてかかるはぜ折り接
合部に発生する腐食を防止するためにいくつかの
対策が試みられた。例えば融雪塩水の侵入を防ぐ
目的で、はぜ折り部のパネル端部に塩化ビニルペ
ースト系のシーラントを施用する方法が試みられ
ているが、この方法では完全なシールが難しく、
シールが不十分な部分または経年で発生した亀裂
部分から融雪塩類が侵入して錆が発生するため長
期防錆対策とはなり得なかつた。
また高価な防錆処理鋼板を使用し、耐久性の向
上と長期防錆保障を得ようという提案も、例えば
特公昭54―5565号公報でなされているが、電着塗
膜が形成されないために、別個の防錆処理を必要
とする部分がはぜ折り部という極めて僅かな一部
分であるにも拘らず、板金部材全体に防錆処理を
予め施した高価な防錆処理鋼板を使用しなければ
ならず、極めて不経済であるという欠点を有し、
特殊な重要保安部品に重点的に施用されるにとど
まつている。
かかる状況下で、防錆対策を必要とする部位
は、はぜ折り部分およびその近傍であり、且つ前
記したように電着塗料すら浸透し難い部位である
ため、車体に組付ける前、更にはスポツト溶接す
る前に対策材料を塗布する手段しか残されていな
かつた。しかしながら、当該工程において塗布し
得る防錆材料は次に挙げる如き厳しい要求性状、
性能を満足せねばならず好適な対策材料に欠けて
いた。
即ち、(1)帯状にハケ塗りまたは吹き付け可能な
こと、(2)防錆油が塗布されている鋼板に施用して
密着性等の異状をきたさないこと、(3)作業環境保
全の上から高固形分塗料（例えば塗布時固形分が
90％以上）であること、(4)塗布された後、通過す
る脱脂および水洗工程で加圧された状態でノズル
から吹き付けられるアルカリ性の脱脂液および温
水により流出しない程度に常温数時間での初期硬
化性（「耐シヤワー性」という）を有すること、
(5)電着塗装を行う際に塗布された対策材料の周辺
に電着塗装の不十分な場所が生じない程度に導電
性を有すること、(6)スポツト溶接可能なこと、(7)
初期硬化性に加えて170℃前後の高温で焼付けた
際に完全硬化するか、または融出しないこと、(8)
貯蔵安定性に優れていること、更に言うまでもな
く、鋼板との密着性に優れ、且つ電着塗膜以上の
防錆力を有すること等の諸要求を満たす対策材料
が強く求められている。
これらの対策材料として、先に(1)特開昭55―
89367号公報、(2)特開昭55―106270号公報および
(3)特開昭56―72052号公報で防錆材料を提案し
た。これ等の防錆材料は、(1)はエポキシ樹脂成分
（Ａ液）、ポリカルボン酸無水物およびアミノ化合
物から成る硬化剤成分（Ｂ液）、およびＡ液およ
び／またはＢ液に含有される導電性粉末からな
り、(2)および(3)は液状エポキシ樹脂と液状ポリカ
ルボン酸無水物（Ａ液）、液状第一級または第二
級アミノ化合物および硬化促進剤（Ｂ液）、およ
びＡ液および／またはＢ液に含有される導電性粉
末から成る２液形の無溶剤形防錆塗料である。こ
れらの防錆材料は前記の如き各条件を殆んど満足
するものであるが、２液形に伴う作業性の上での
取り扱い難さを有していた。例えば予めＡ液とＢ
液を混合した場合、ポツトライフに制約され、常
時同一条件で塗装することがむずかしく、あるい
は頻繁にＡ液とＢ液の混合を必要とし、更に高価
で特殊なスプレーガンを用いる方法にあつても、
スプレーガン中で１秒以内で混合し塗布するとい
う特殊な内部構造を有するものであるため、Ａ，
B2液が短時間で十分に混合され得なかつた場
合、塗布後の完全な硬化が望めず耐シヤワー性や
防錆性に劣る危惧がある、等の問題点があつた。
また、上記防錆材料にあつては、吹き付けた防
錆材料の縁に緻密に電着塗料を付着することを目
的として導電性粉末、例えば導電性カーボンブラ
ツクおよびグラフアイトが混入されているが、亜
鉛、銅、銀、アルミニウム等の金属粉末は、配合
物の安定性が損われるとして除外している。従つ
て上記提案された防錆材料にあつては、電着塗料
のつき回り性およびスポツト溶接性に優れている
利点は認められるものの長期の防錆力において未
だ不十分であつた。
かかる実情に鑑み本発明者らは前記従来の防錆
材料の問題点を解決すべく鋭意研究を行つた結
果、エポキシ樹脂の硬化剤成分としてブロツクイ
ソシアネート樹脂およびイミダゾール系硬化剤を
組み合せて用いることによつてのみ防錆材料を１
液形と成し得て、２液形に起因する前記諸欠点を
皆無となし、また前記提案した防錆材料にあつて
は、好ましくないとして除外された金属粉末、更
には金属化合物粉末を用いたところ意外にも導電
性および貯蔵安定性が良好で且つ極めて長期の防
錆力を有する防錆材料と成し得ることを知見し、
本発明を達成するに至つた。
即ち本発明はエポキシ当量150〜1000のエポキ
シ樹脂、ブロツクイソシアネート樹脂およびイミ
ダゾール系硬化剤から成る樹脂成分と、該樹脂成
分100重量部当り100〜1000重量部の金属粉末およ
び／または金属化合物粉末と、２〜20重量部の極
性基含有熱可塑性樹脂を含有した高固形分１液形
の防錆塗料に関するものである。
以下本発明につき詳細に説明する。
本発明の防錆塗料を形成する樹脂成分として用
いるエポキシ樹脂は、グリシジル型エポキシ樹脂
および非グリシジル型エポキシ樹脂等如何なるエ
ポキシ樹脂を用いても良く、またグリシジル型エ
ポキシ樹脂においても脂肪族、芳香族および環状
脂肪族を問わず、更に非グリシジル型エポキシ樹
脂にあつても非環状脂肪族エポキシか環状脂肪族
エポキシかは問わない。例えばエピクロルヒドリ
ンとビスフエノールＡ、若しくはビスフエノール
Ｆ等の多価フエノールから得られるエポキシ樹
脂、およびオレフインの過酸によるエポキシ化反
応で得られるエポキシ樹脂を挙げることができ
る。エポキシ樹脂のエポキシ当量としては、150
〜1000が好ましく、エポキシ当量が大き過ぎると
吹付作業性の低下が生じ易く、150未満では耐水
性が低下する。
１液性の防錆塗料となすための本発明による硬
化剤成分について述べると、先ず金属板あるいは
油面状態の金属板に対して良好なる密着性をも顕
現するブロツクイソシアネート樹脂としては、イ
ソシアネート成分と活性水素を含有するブロツク
剤とを反応させて得られるものであつてよい。イ
ソシアネート成分としては、芳香族または脂肪族
のジイソシアネート、例えばヘキサメチレンジイ
ソシアネート、ジフエニルメタンジイソシアネー
ト、オクタメチレンジイソシアネート、トリレン
ジイソシアネート、キシリレンジイソシアネー
ト、フエニルジイソシアネート、テトラメチレン
ジイソシアネート、メチルキシレンジイソシアネ
ート等から選ばれる１種以上が使用できるが、ト
リレンジイソシアネートを使用するのが特に好ま
しい。再生イソシアネートは、イソシアネート含
有量（％）が４〜15％のものを用いることができ
る。
活性水素を含有するブロツク剤としては、フエ
ノール、酸アジド、ラクタム、低級１価アルコー
ル、セロソルブ、カプロラクタム、オキシム類等
が使用できるが、このうちメチルエチルケトキシ
ムを用いたものが好ましい。
次に、他の硬化剤成分としてのイミダゾール系
硬化剤は、〓NHにエポキシ基が付加反応した後
硬化するが、該付加反応は比較的遅いため、１液
性の樹脂配合物をつくるのに好適である。更に可
使時間を長くするために、〓NHの活性水素をシ
アノエチル化したり、アジリジンを付加したもの
も好ましく用いることができる。通常使用するイ
ミダゾール系硬化剤としては、２―メチルイミダ
ゾール、２―エチル―４―メチルイミダゾール、
２―フエニルイミダゾール、２―ウンデシルイミ
ダゾール、２―ヘプタデシルイミダゾール、２―
メチルイミダゾリン、２―エチル―４―メチルイ
ミダゾリン、２―フエニルイミダゾリン、２―ウ
ンデシルイミダゾリン、２―ヘプタデシルイミダ
ゾリン、２―エチルイミダゾール、２―イソプロ
ピルイミダゾール、２，４―ジメチルイミダゾー
ル、２―フエニル―４―メチルイミダゾール、２
―エチルイミダゾリン、２―イソプロピルイミダ
ゾリン、２，４―ジメチルイミダゾリン、２―フ
エニル―４―メチルイミダゾリン等を好ましく用
いることができる。
硬化剤成分である前記ブロツクイソシアネート
樹脂は、エポキシ樹脂100重量部に対して15〜80
重量部用いる。ブロツクイソシアネート樹脂が、
15重量部未満の場合は、塗料の密着性が劣り、塗
膜が硬くなり、一方80重量部を超えると塗料の耐
湿性が劣り好ましくない。
次にイミダゾール系硬化剤については、エポキ
シ樹脂100重量部に対して１〜20重量部用いる。
イミダゾール系硬化剤が、１重量部未満の場合
は、塗膜の硬化不良の危惧があり、一方20重量部
を超えると貯蔵安定性および熱安定性が悪くなり
好ましくない。
以上のエポキシ樹脂、ブロツクイソシアネート
樹脂およびイミダゾール系硬化剤から成る樹脂成
分には、所要に応じて添加剤として沈降防止剤、
分散剤、無機質増粘剤を適宜配合することがで
き、かかる添加剤を配合する場合には、沈降防止
剤、分散剤等は樹脂成分100重量部に対して10重
量部以下の分量で配合するのが好ましく、また無
機質増粘剤は樹脂成分100重量部に対して20重量
部以下の分量で配合するのが好ましい。沈降防止
剤としてはステアリン酸等で表面処理したベント
ナイト、シリカ、炭酸カルシウム等の微粉末顔料
が好ましく、分散剤としては、脂肪族系多価カル
ボン酸、長鎖ポリアミノアマイドと高分子酸ポリ
エステルの塩、長鎖ポリアミノアマイドとリン酸
の塩、ポリエーテルエステル型アニオン系界面活
性剤等を用いるのが好ましく、無機質増粘剤とし
ては、炭酸カルシウム、マイカ、タルク等を用い
ることができるが、特にベントナイト系のものを
好ましく用いる。
次に本発明の防錆塗料は、上記樹脂成分に金属
粉末および／または金属化合物粉末と、極性基含
有熱可塑性樹脂を含有したものであるが、金属粉
末および／または金属化合物粉末に関しては、前
述の既に提案した２液形の防錆材料にあつては、
電着塗料の付き回り性を良くするために導電性を
有する顔料に着目し、その使用を推奨したのに対
し金属粉末は防錆力向上を期待できるが一方では
酸化により導電性が低下するという理由で賞用さ
れていなかつたものである。ところが本発明にお
いては特定の樹脂成分を用いることにより、導電
性を有するが防錆力を期待し得ない導電性顔料に
代えて金属粉末および／または金属化合物を必須
構成成分となし得たものであり、特にこれらの金
属粉末および／または金属化合物粉未の中から適
宜選択組合せることにより、防錆力および導電性
を飛躍的に向上させることを可能にしたものであ
る。例えば防錆効果を顕現させるために、より好
ましいものとして、鉛粉、亜酸化鉛、亜鉛黄、亜
鉛末、ストロンチウムクロメート、シアナミド
鉛、鉛丹、鉛白、塩基性クロム酸塩等を用いるの
が好ましい。また導電性の付与のため、より好ま
しいものとしてFe3P，Fe2P，FeP，FeP2等のリ
ン化鉄類を単独で、又は混合して用いても良く、
特にFe2Pを用いるのが好ましい。
これらのより防錆効果を有する金属粉末およ
び／または金属化合物粉末と、より導電性を顕現
し得る金属化合物を混合して用いるのが好まし
く、混合して用いる場合の混合の混合比は５：５
〜９：１が好ましい。前記金属粉末および／また
は金属化合物粉末全体の配合量は、樹脂成分100
重量部に対して100〜1000重量部用いることを必
須とするもので、100重量部未満の場合には、本
発明の特徴である防錆力と導電性が著しく劣る不
具合を生じ、一方1000重量部を超えると、金属粉
末の沈降が起こり、塗布作業性が悪くなり、加え
て屈曲性および密着性が低下して好ましくない。
また該金属粉末の粒径は１〜50μ程度が作業性良
く好適に用いることができる。
次の極性基含有熱可塑性樹脂に関しては、分子
内に極性基として―COOH，―OH，＝CO，―
CONH2等の基を有するものが好ましく、極性基
を分子内に有していれば熱可塑性樹脂としては、
塩化ビニル樹脂、エチレン酢酸ビニル共重合樹
脂、酢酸ビニル樹脂、ポリビニルアルコール、ア
クリル樹脂、ポリエチレン樹脂等を用いることが
でき、特に酢酸ビニルの配合量がエチレン／酢酸
ビニル＝80/20以上であるエチレン酢酸ビニル共
重合樹脂を用いるのが好ましい。
上記極性基含有熱可塑性樹脂は、前記樹脂成分
100重量部当り２〜20重量部配合することが必要
であり、２重量部末満では経年における耐水性、
耐湿性に劣るようになり、一方20重量部を超える
と、粘度が急上昇し、作業性に支障を来たした
り、焼き付け時に流れ去る等の不具合が生じ好ま
しくない。
本発明の防錆塗料は、以上の成分を含有する１
液形のもので、塗装方法としてはエアレススプレ
ーを用いた帯状にスプレーし、または扁平先端を
有するシーラーガンを用いての塗り付け、或いは
ハケ塗り等何等制限されず、通常粘度を10〜900
ポイズ（25℃）に調製するのが好ましい。粘度調
整用として用いる溶剤は、芳香族系、若しくはエ
ステル系の溶剤でよい。芳香族系溶剤としては、
ベンゼン、トルエン、キシレン、エチルベンゼ
ン、スチレン等を用い、エステル系溶剤として
は、カルボン酸エステル、スルホン酸エステル、
無機酸エステル、グリセリンのエステル等如何な
るものでも差し支えなく、加えて難燃性付与のた
めに粘度調整用溶剤中にトリクロルエタンと他の
溶剤との混合比は、４：６〜８：２とすることで
顕著なる難燃性を得ることができる。
このようにして調整した防錆塗料を用いて実際
に自動車の車体を防錆処理する例を示すと、自動
車のホワイトボデイ組立工程において、板金プレ
ス打ち抜き後の未だ油が付着している板金部材の
所望部位に本発明の防錆塗料を塗布し、その後該
防錆塗料を内面に挾んで所要部分を従来のホワイ
トボデイ組立工程に従つてスポツト溶接すればよ
い。塗布後30分乃至４時間程度の放置時間の後は
通常のライン工程によればよく、前処理工程、
ED下塗の塗装工程を経て焼付乾燥炉にて硬化被
膜を形成することができる。この場合の塗布方法
も、ハケ塗り、スプレー塗装等、帯状塗布が可能
であればよく、何等塗装器具、方法に限定されな
いことは勿論である。
以上のように本発明の防錆塗料は実質的に該防
錆塗料自体に電着塗料に比して著しく優れた防錆
力を有するものであり、加えて耐シヤワー性、初
期硬化性、密着性が極めて優れ、特に自動車のフ
エンダ下部、ドア下部、ボンネツトの先端部およ
びその裏面先端部などの接合部を好適に防錆し
得、加えて１液形であるため、特殊な内部構造を
有するスプレー機器を用いることを要せず、一般
のスプレー機器で塗布できる作業性に優れたもの
であり、また初期硬化性が極めて優れていること
から高度な耐シヤワー性を顕現し得、焼付硬化後
は、未だ類のない優れた防錆力を有するものであ
り、工業的に極めて有用なものである。
以下本発明を実施例および比較例により説明す
る。
実施例１〜３、比較例１〜５
第１表の上欄に示す組成配合（重量部）に基づ
き３本ロールを用いて分散し、表に示す適量の溶
剤により粘度を調整して本発明の防錆塗料および
比較例の防錆塗料を得た。これ等の塗料につき次
に示す試験方法により性能を評価し、得た結果を
第１表に併記する。
防錆力試験
プレス油を塗布した150mm×75mmの鋼板の長辺
方向の下端から約50mmの幅で各試料をハケを用い
て乾燥膜厚が約30μとなる様に塗布し、常温で約
３時間放置した。
次いで60℃の温水によるシヤワーテスト５分
間、60℃のアルカリ脱脂液に浸漬５分間、40℃の
表面調整液に浸漬10分間、50℃の化成処理液に浸
漬５分間の各工程を経て110℃で約10分間水切り
乾燥し、引き続きカチオン電着塗装を施し、185
℃で約30分間焼付を加えて試験片とした。
JIS―Ｚ―2371（塩水噴霧試験方法）に規定さ
れる塩水噴霧試験装置中の所定の位置に試験片を
設置して発錆の有無を48時間毎に観察した。試験
片の周辺部５mmは評価外とし、発錆が確認され始
めるまでに要した時間で評価した。
The present invention relates to a rust-preventing paint, and particularly to a one-component rust-preventing paint that is applied to the joints of sheet metal members of automobiles for rust-preventing treatment. In recent years, corrosion of automobiles due to large amounts of snow-melting salt that is sprayed on roads in cold regions has become a problem, and strict countermeasures have been required, and the materials, structures, and assembly processes of various parts of automobiles have been reviewed. ing. Traditionally, the seams of car bonnets, doors, trunk lids, fenders, etc. are made by spot-welding sheet metal parts coated with anti-corrosion oil or press oil, and then applying a pre-treatment process and an undercoat by electrodeposition. was. However, in this method, the undercoat is applied after the car body is assembled, so it is difficult for the electrodeposition paint to penetrate into the seam folds and surrounding areas, resulting in insufficient coverage.
In some cases, the electrodeposited coating does not provide sufficient protection, and as a result, salt water from melting snow penetrates and stagnates in the creases while the car is running, causing corrosion. Therefore, several measures have been attempted to prevent corrosion occurring at such seam joints. For example, attempts have been made to apply a vinyl chloride paste sealant to the panel edges at the folds in order to prevent saltwater from melting snow from entering, but with this method it is difficult to achieve a complete seal.
Snow melting salts enter through cracks that have formed over time or where the seal is insufficient, causing rust, so this cannot be used as a long-term rust prevention measure. In addition, proposals have been made, for example, in Japanese Patent Publication No. 54-5565, to improve durability and guarantee long-term rust prevention by using expensive anti-corrosion treated steel sheets, but because the electrodeposited coating film is not formed, Although the only part that requires separate anti-corrosion treatment is the seam fold, it is not possible to use an expensive anti-corrosion treated steel plate that has been pre-treated to prevent rust on the entire sheet metal member. However, it has the disadvantage of being extremely uneconomical.
It is only being applied intensively to special and important safety parts. Under such circumstances, the areas that require anti-corrosion measures are the seam folds and their vicinity, and as mentioned above, these are areas where even electrodeposition paint is difficult to penetrate, so it is necessary to take anti-corrosion measures before assembling the car body. The only option left was to apply a countermeasure material before spot welding. However, the anti-rust materials that can be applied in this process have the following strict requirements:
Performance had to be satisfied, and suitable countermeasure materials were lacking. In other words, (1) it can be brushed or sprayed in a band shape, (2) it can be applied to steel plates coated with anti-corrosion oil without causing any abnormality in adhesion, and (3) it is important to preserve the working environment. High solids content paints (e.g. solids content during application
90% or more); (4) After being applied, the alkaline degreasing liquid and hot water that are sprayed from the nozzle under pressure during the degreasing and water washing process pass through the initial stage at room temperature for several hours to the extent that they do not flow out. having hardening properties (referred to as "shower resistance");
(5) Must be conductive to the extent that insufficient electrodeposition will occur around the countermeasure material applied during electrodeposition, (6) Spot weldable, (7)
In addition to initial hardening properties, it must be completely hardened or not melt when baked at a high temperature of around 170℃ (8)
There is a strong demand for a countermeasure material that satisfies various requirements such as excellent storage stability, excellent adhesion to steel plates, and anti-rust properties superior to those of electrodeposited coatings. As materials for these countermeasures, (1) Unexamined Japanese Patent Publication No. 1986-
Publication No. 89367, (2) Japanese Unexamined Patent Publication No. 106270/1989, and
(3) An anti-rust material was proposed in Japanese Patent Application Laid-Open No. 72052/1983. These anti-rust materials are: (1) an epoxy resin component (liquid A), a curing agent component (liquid B) consisting of a polycarboxylic acid anhydride and an amino compound, and a liquid contained in liquid A and/or liquid B. Consisting of conductive powder, (2) and (3) are liquid epoxy resin, liquid polycarboxylic acid anhydride (Liquid A), liquid primary or secondary amino compound and curing accelerator (Liquid B), and A. This is a two-component, solvent-free anticorrosive paint consisting of conductive powder contained in liquid and/or liquid B. Although these rust-preventing materials satisfy most of the above-mentioned conditions, they are difficult to handle due to their two-component nature. For example, in advance, liquid A and B
When mixing liquids, pot life is limited, and it is difficult to always apply under the same conditions, or it is necessary to mix liquids A and B frequently, and even if the method uses an expensive and special spray gun,
A, because it has a special internal structure that allows it to be mixed and applied within one second in a spray gun.
If the B2 liquid could not be sufficiently mixed in a short period of time, there were problems such as complete curing after application and the risk of poor shower resistance and rust prevention. In addition, in the case of the above-mentioned rust-preventing material, conductive powder such as conductive carbon black and graphite is mixed in for the purpose of depositing electrodeposition paint closely on the edges of the sprayed rust-preventing material. Metal powders such as zinc, copper, silver, and aluminum are excluded because they impair the stability of the formulation. Therefore, although the above-mentioned proposed rust-preventing materials have the advantage of being excellent in coverage and spot-weldability of electrodeposition paints, they are still insufficient in terms of long-term rust-preventing power. In view of these circumstances, the inventors of the present invention conducted extensive research to solve the problems of the conventional rust-preventing materials, and as a result, they decided to use a combination of blocking isocyanate resin and imidazole-based hardener as the hardening agent component of epoxy resin. Only use 1 anti-rust material
It can be made into a liquid form, completely eliminating the above-mentioned disadvantages caused by the two-liquid type, and in the case of the rust-preventing material proposed above, it uses metal powders and metal compound powders that have been excluded as undesirable. However, it was discovered that it was possible to make a rust-preventing material that had surprisingly good conductivity and storage stability, and had an extremely long-term rust-preventing ability.
The present invention has now been achieved. That is, the present invention comprises a resin component consisting of an epoxy resin having an epoxy equivalent of 150 to 1000, a blocking isocyanate resin, and an imidazole curing agent, a metal powder and/or metal compound powder in an amount of 100 to 1000 parts by weight per 100 parts by weight of the resin component, The present invention relates to a one-component anticorrosive paint with a high solids content containing 2 to 20 parts by weight of a polar group-containing thermoplastic resin. The present invention will be explained in detail below. The epoxy resin used as the resin component forming the anticorrosion paint of the present invention may be any epoxy resin such as glycidyl-type epoxy resin and non-glycidyl-type epoxy resin. It does not matter whether it is a cycloaliphatic epoxy or whether it is a non-glycidyl epoxy resin or a cycloaliphatic epoxy. Examples include epoxy resins obtained from epichlorohydrin and polyhydric phenols such as bisphenol A or bisphenol F, and epoxy resins obtained by epoxidation reaction of olefin with peracid. The epoxy equivalent of epoxy resin is 150
-1000 is preferable; if the epoxy equivalent is too large, spraying workability tends to decrease, and if it is less than 150, water resistance decreases. Regarding the curing agent components according to the present invention for producing a one-component anticorrosive paint, first of all, as a blocking isocyanate resin that exhibits good adhesion to a metal plate or a metal plate in an oily state, the isocyanate component is and a blocking agent containing active hydrogen. The isocyanate component is selected from aromatic or aliphatic diisocyanates, such as hexamethylene diisocyanate, diphenylmethane diisocyanate, octamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, phenyl diisocyanate, tetramethylene diisocyanate, methylxylene diisocyanate, etc. Although one or more types can be used, it is particularly preferred to use tolylene diisocyanate. As the recycled isocyanate, one having an isocyanate content (%) of 4 to 15% can be used. As blocking agents containing active hydrogen, phenols, acid azides, lactams, lower monohydric alcohols, cellosolves, caprolactams, oximes, etc. can be used, but among these, those using methyl ethyl ketoxime are preferred. Next, the imidazole curing agent as another curing agent component is cured after the addition reaction of the epoxy group to NH, but since this addition reaction is relatively slow, it is difficult to make a one-component resin formulation. suitable. In order to further extend the pot life, it is also preferable to use NH with the active hydrogen thereof cyanoethylated or with aziridine added thereto. Commonly used imidazole curing agents include 2-methylimidazole, 2-ethyl-4-methylimidazole,
2-phenylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-
Methylimidazoline, 2-ethyl-4-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecyl imidazoline, 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl -4-methylimidazole, 2
-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline, etc. can be preferably used. The blocking isocyanate resin, which is a curing agent component, is contained in an amount of 15 to 80 parts by weight per 100 parts by weight of the epoxy resin.
Use parts by weight. Blocking isocyanate resin is
If it is less than 15 parts by weight, the adhesion of the paint will be poor and the coating will become hard, while if it exceeds 80 parts by weight, the moisture resistance of the paint will be poor. Next, the imidazole curing agent is used in an amount of 1 to 20 parts by weight per 100 parts by weight of the epoxy resin.
If the amount of the imidazole curing agent is less than 1 part by weight, there is a risk that the coating film will be insufficiently cured, while if it exceeds 20 parts by weight, storage stability and thermal stability will deteriorate, which is not preferred. The resin component consisting of the above epoxy resin, blocking isocyanate resin and imidazole curing agent may optionally contain an antisettling agent as an additive.
Dispersants and inorganic thickeners can be blended as appropriate, and when such additives are blended, anti-settling agents, dispersants, etc. are blended in an amount of 10 parts by weight or less per 100 parts by weight of the resin component. The inorganic thickener is preferably blended in an amount of 20 parts by weight or less per 100 parts by weight of the resin component. As the antisettling agent, finely powdered pigments such as bentonite, silica, and calcium carbonate whose surface has been treated with stearic acid, etc. are preferable, and as the dispersant, salts of aliphatic polycarboxylic acids, long-chain polyaminoamides, and high-molecular acid polyesters are preferable. , a salt of long-chain polyaminoamide and phosphoric acid, a polyether ester type anionic surfactant, etc. are preferably used, and as the inorganic thickener, calcium carbonate, mica, talc, etc. can be used, but especially bentonite It is preferable to use those of the same type. Next, the anticorrosive paint of the present invention contains a metal powder and/or metal compound powder and a polar group-containing thermoplastic resin in the resin component. Regarding the two-component rust-preventing material already proposed,
In order to improve the coverage of electrodeposition paints, they focused on conductive pigments and recommended their use, whereas metal powders can be expected to improve rust prevention, but on the other hand, conductivity decreases due to oxidation. It was not awarded for some reason. However, in the present invention, by using a specific resin component, a metal powder and/or a metal compound can be used as an essential component instead of a conductive pigment that has conductivity but cannot be expected to have antirust properties. In particular, by appropriately selecting and combining these metal powders and/or metal compound powders, it has become possible to dramatically improve the anticorrosive power and conductivity. For example, it is more preferable to use lead powder, lead zinc oxide, zinc yellow, zinc powder, strontium chromate, lead cyanamide, red lead, white lead, basic chromate, etc. in order to realize the rust prevention effect. preferable. Further, in order to impart conductivity, iron phosphides such as Fe 3 P, Fe 2 P, FeP, FeP 2 may be used alone or in combination, as more preferable ones.
In particular, it is preferable to use Fe 2 P. It is preferable to mix and use these metal powders and/or metal compound powders that have a more rust-preventing effect and metal compounds that can exhibit more conductivity, and when used in combination, the mixing ratio is 5:5.
~9:1 is preferred. The total blending amount of the metal powder and/or metal compound powder is 100% of the resin component.
It is essential to use 100 to 1000 parts by weight, and if it is less than 100 parts by weight, the rust prevention ability and conductivity, which are the characteristics of the present invention, will be significantly inferior. If it exceeds 100%, the metal powder will settle, resulting in poor coating workability, as well as a decrease in flexibility and adhesion, which is undesirable.
Further, the particle size of the metal powder is preferably about 1 to 50 microns, which has good workability. Regarding the following polar group-containing thermoplastic resins, the polar groups in the molecule are -COOH, -OH, =CO, -
A thermoplastic resin having a group such as CONH 2 is preferable, and if it has a polar group in its molecule, it can be used as a thermoplastic resin.
Vinyl chloride resin, ethylene vinyl acetate copolymer resin, vinyl acetate resin, polyvinyl alcohol, acrylic resin, polyethylene resin, etc. can be used, especially ethylene acetic acid in which the blending amount of vinyl acetate is ethylene/vinyl acetate = 80/20 or more. Preferably, a vinyl copolymer resin is used. The polar group-containing thermoplastic resin is the resin component
It is necessary to mix 2 to 20 parts by weight per 100 parts by weight, and at the end of 2 parts by weight, water resistance over time,
Moisture resistance becomes poor, and if it exceeds 20 parts by weight, the viscosity increases rapidly, which may impede workability or cause problems such as running off during baking, which is undesirable. The anticorrosive paint of the present invention contains 1
It is a liquid type, and there are no restrictions on how to apply it, such as spraying it in a strip using an airless sprayer, applying it using a sealer gun with a flat tip, or applying it with a brush.
It is preferable to adjust the temperature to poise (25°C). The solvent used for viscosity adjustment may be an aromatic or ester solvent. As aromatic solvents,
Benzene, toluene, xylene, ethylbenzene, styrene, etc. are used, and as the ester solvent, carboxylic acid ester, sulfonic acid ester,
Any inorganic acid ester, glycerin ester, etc. may be used. In addition, in order to impart flame retardancy, the mixing ratio of trichloroethane and other solvents in the viscosity adjusting solvent should be 4:6 to 8:2. As a result, remarkable flame retardancy can be obtained. To give an example of actually rust-preventing an automobile body using the anti-corrosion paint prepared in this way, in the white body assembly process of an automobile, sheet metal parts that still have oil attached to them after being punched by a sheet metal press are used. The anticorrosive paint of the present invention may be applied to desired areas, and then the anticorrosive paint may be placed on the inner surface and the required portions may be spot welded according to the conventional white body assembly process. After being left for about 30 minutes to 4 hours after application, normal line processes can be carried out, including pre-treatment processes,
After the ED undercoat painting process, a hardened film can be formed in a baking drying oven. The application method in this case may be brush application, spray painting, or the like, as long as band-like application is possible, and it goes without saying that the application method is not limited to any particular application equipment or method. As described above, the rust-preventive paint of the present invention substantially has significantly superior rust-preventive power as compared to electrodeposition paints, and also has excellent shower resistance, initial curing properties, and adhesion. It has excellent corrosion resistance, and is particularly suitable for rust-preventing joints such as the lower part of automobile fenders, the lower part of doors, the tip of the bonnet, and the tip of the back side.In addition, since it is a one-liquid type, it has a special internal structure. It has excellent workability and can be applied with general spray equipment without requiring the use of spray equipment.It also exhibits a high degree of shower resistance due to its extremely excellent initial curing properties, and after baking and hardening. has unprecedented rust prevention properties and is extremely useful industrially. The present invention will be explained below with reference to Examples and Comparative Examples. Examples 1 to 3, Comparative Examples 1 to 5 The composition according to the present invention was dispersed using three rolls based on the composition (parts by weight) shown in the upper column of Table 1, and the viscosity was adjusted with an appropriate amount of solvent shown in the table. A rust-preventive paint and a comparative rust-preventive paint were obtained. The performance of these paints was evaluated using the test method shown below, and the results are also listed in Table 1. Rust prevention power test Each sample was coated with press oil on a width of about 50 mm from the lower end in the long side direction of a 150 mm x 75 mm steel plate, using a brush, so that the dry film thickness was about 30μ, and the thickness was about 30μ at room temperature. I left it for a while. Next, a shower test with warm water at 60°C for 5 minutes, immersion in an alkaline degreasing solution at 60°C for 5 minutes, immersion in a surface conditioning solution at 40°C for 10 minutes, and a 5-minute immersion in a chemical conversion treatment solution at 50°C were performed. Drain and dry for about 10 minutes, then apply cationic electrodeposition coating and apply 185
A test piece was prepared by baking at ℃ for about 30 minutes. The test piece was placed at a predetermined position in a salt spray test device specified in JIS-Z-2371 (salt spray test method), and the presence or absence of rust was observed every 48 hours. A 5 mm peripheral area of the test piece was excluded from evaluation, and evaluation was made based on the time required until rusting began to be observed.
【表】
以上の結果から本発明の１液形の防錆塗料は極
めて作業性に優るのみならず、常温での初期乾燥
性に優れ、脱脂―洗浄―表面処理の各工程におい
て流出したりする問題も生せず、しかも電着塗膜
のつき回り性にも問題なく、油面鋼板に塗布する
という悪条件にも拘らず密着性に優れ、これらの
総合的な相乗効果により著しく優れた防錆力を顕
現し得ることが明らかとなつた。
また、これらの優れた効果および厳しい適用条
件を満たすには、ブロツクイソシアネートとイミ
ダゾール系硬化剤との組合せからなるエポキシ樹
脂に対する特定の硬化剤と、極性基含有熱可塑性
樹脂、金属粉末および／または金属化合物粉末と
を必須成分として含有する本発明の防錆塗料にお
いてのみ可能となつたもので、これらの必須成分
のうちどれが欠けても優れた効果は顕現し得ない
ことが明らかとなつた。[Table] From the above results, the one-component anticorrosion paint of the present invention not only has excellent workability, but also has excellent initial drying properties at room temperature, and does not leak during each step of degreasing, cleaning, and surface treatment. There are no problems, and there are no problems with the coverage of the electrodeposited coating, and it has excellent adhesion despite the adverse conditions of applying it to oily steel plates.The overall synergistic effect of these coatings results in extremely excellent protection. It has become clear that rust power can be manifested. In addition, in order to achieve these excellent effects and meet strict application conditions, a specific curing agent for epoxy resin consisting of a combination of blocking isocyanate and an imidazole-based curing agent, a polar group-containing thermoplastic resin, metal powder and/or metal This is possible only with the anticorrosive paint of the present invention which contains compound powder as an essential component, and it has become clear that excellent effects cannot be realized even if any of these essential components is missing.
Claims (1)
エポキシ樹脂100重量部に対して15〜80重量のブ
ロツクイソシアネート樹脂及び１〜20重量部のイ
ミダゾール系硬化剤から成る樹脂成分と、該樹脂
成分100重量部当り100〜1000重量部の金属粉末お
よび／または金属化合物粉末と、２〜20重量部の
極性基含有熱可塑性樹脂を含有したことを特徴と
する防錆塗料。1. An epoxy resin with an epoxy equivalent of 150 to 1000,
A resin component consisting of 15 to 80 parts by weight of blocking isocyanate resin and 1 to 20 parts by weight of an imidazole curing agent based on 100 parts by weight of the epoxy resin, and 100 to 1000 parts by weight of metal powder and/or per 100 parts by weight of the resin component. Or, a rust-preventing paint characterized by containing metal compound powder and 2 to 20 parts by weight of a polar group-containing thermoplastic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23005482A JPS59124965A (en) | 1982-12-29 | 1982-12-29 | Rust-resisting coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23005482A JPS59124965A (en) | 1982-12-29 | 1982-12-29 | Rust-resisting coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59124965A JPS59124965A (en) | 1984-07-19 |
| JPS6241628B2 true JPS6241628B2 (en) | 1987-09-03 |
Family
ID=16901835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23005482A Granted JPS59124965A (en) | 1982-12-29 | 1982-12-29 | Rust-resisting coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59124965A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2560499B2 (en) * | 1989-12-13 | 1996-12-04 | 日立電線株式会社 | Inner surface coated metal tube |
| JP5579967B2 (en) * | 2008-02-20 | 2014-08-27 | Ｎｋｍコーティングス株式会社 | Epoxy resin coating composition, coating film forming method, and coated article |
| WO2024048627A1 (en) * | 2022-09-01 | 2024-03-07 | タツタ電線株式会社 | Conductive coating, and method for resin molded article having shielding layer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5186528A (en) * | 1975-01-28 | 1976-07-29 | Kansai Paint Co Ltd |
-
1982
- 1982-12-29 JP JP23005482A patent/JPS59124965A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5186528A (en) * | 1975-01-28 | 1976-07-29 | Kansai Paint Co Ltd |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59124965A (en) | 1984-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20050074626A1 (en) | Conductive organic coatings | |
| WO2007013761A1 (en) | Pre-sealed steel sheet with improved anti- corrosion and weldability and preparing method thereof | |
| JP2686205B2 (en) | Rust prevention paint composition | |
| JP3143046B2 (en) | Organic composite coated steel sheet with excellent press formability and perforated corrosion resistance | |
| JPH0753913B2 (en) | Method for manufacturing organic composite plated steel sheet | |
| JPS63297417A (en) | Polymer composition | |
| US4324713A (en) | Two-package solventless rust preventive material | |
| JP4846118B2 (en) | Pigment for corrosion prevention coating composition and corrosion prevention coating composition using the same | |
| JP4534592B2 (en) | Weldable high corrosion-resistant surface-treated steel sheet for automobiles and method for producing the same | |
| JPH0853644A (en) | Water-based coating composition | |
| JPS6241628B2 (en) | ||
| JPH0450349B2 (en) | ||
| JP4457820B2 (en) | High corrosion resistance surface-treated steel sheet and method for producing the same | |
| JP2001146567A (en) | Zinc-rich powder coating composition, its coating method and coated product | |
| JPS6136551B2 (en) | ||
| JP2008284539A (en) | Coating steel material and rustproof coating | |
| JPH0448348B2 (en) | ||
| KR910002569B1 (en) | Highly corrosion-resistant surface-treated steel plate | |
| JP3071376B2 (en) | Organic composite coated steel sheet excellent in press formability and rust resistance | |
| JP6916350B1 (en) | Paint composition and coating | |
| JP7493360B2 (en) | Metal pipe with corrosion-resistant layer | |
| JPS6279282A (en) | Resin composition | |
| JPH11172156A (en) | Oil face coating type rust preventing agent composition and rust prevention | |
| JPH0749550B2 (en) | Primer for polyolefin coated steel with excellent hot water resistance | |
| JPH07145225A (en) | Bonding epoxy resin composition |