JPH0133509B2 - - Google Patents
Info
- Publication number
- JPH0133509B2 JPH0133509B2 JP61210159A JP21015986A JPH0133509B2 JP H0133509 B2 JPH0133509 B2 JP H0133509B2 JP 61210159 A JP61210159 A JP 61210159A JP 21015986 A JP21015986 A JP 21015986A JP H0133509 B2 JPH0133509 B2 JP H0133509B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- molybdate
- water
- calcium
- weight
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229920005749 polyurethane resin Polymers 0.000 claims description 24
- -1 amine compound Chemical class 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 3
- NFVZIERLAZUYBQ-UHFFFAOYSA-N [K].[Zn] Chemical compound [K].[Zn] NFVZIERLAZUYBQ-UHFFFAOYSA-N 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- XMYLSWOTJKUSHE-UHFFFAOYSA-N cyanamide;lead Chemical compound [Pb].NC#N XMYLSWOTJKUSHE-UHFFFAOYSA-N 0.000 claims description 3
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 3
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 3
- XLUBVTJUEUUZMR-UHFFFAOYSA-B silicon(4+);tetraphosphate Chemical compound [Si+4].[Si+4].[Si+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XLUBVTJUEUUZMR-UHFFFAOYSA-B 0.000 claims description 3
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 claims description 3
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 claims description 3
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000007769 metal material Substances 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-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
- WLXGQMVCYPUOLM-UHFFFAOYSA-N 1-hydroxyethanesulfonic acid Chemical compound CC(O)S(O)(=O)=O WLXGQMVCYPUOLM-UHFFFAOYSA-N 0.000 description 1
- NDILXMGQMAJWQB-UHFFFAOYSA-N 3,5-dinitrobenzoic acid;piperidine Chemical compound C1CCNCC1.OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 NDILXMGQMAJWQB-UHFFFAOYSA-N 0.000 description 1
- OTTPFCJTQXRWHO-UHFFFAOYSA-N 3-(2,3-dichloroanilino)cyclohex-2-en-1-one Chemical compound ClC1=CC=CC(NC=2CCCC(=O)C=2)=C1Cl OTTPFCJTQXRWHO-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
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- SGMYMNACCZOAMT-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OC(C=C)=O.[Na] Chemical compound C(C1=CC=CC=C1)(=O)OC(C=C)=O.[Na] SGMYMNACCZOAMT-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229910001141 Ductile iron Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 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
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N beta-hydroxyethanesulfonic acid Natural products OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- AFSKMUFTKFPHCZ-UHFFFAOYSA-N calcium;oxolead Chemical compound [Ca].[Pb]=O AFSKMUFTKFPHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 108700004121 sarkosyl Proteins 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 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 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、防錆用塗料組成物に関するものであ
る。
従来からの金属材料用水系防錆塗料としては水
系アクリル樹脂、アルキツド−メラミン樹脂、水
系エポキシ樹脂塗料等が挙げられ、これらを塗装
し、常温あるいは約80〜150℃の比較的低温で乾
燥している。
しかしながら、これらの水系樹脂塗料を塗装し
た金属材料でも耐食性が不充分であり、錆の発
生、密着性の低下に伴うふくれ、又ははがれの発
生等がみられるという問題点があつた。
さらに水系ポリウレタン樹脂は、他の水系アル
キツド樹脂、アクリル樹脂、アルキツド−メラミ
ン樹脂、エポキシ樹脂等と比較して耐薬品性、耐
摩耗性、耐屈曲性等に優れていることはよく知ら
れているが、金属材料に対する防錆用塗料として
は、価格が高いため一般の金属材料用防錆塗料と
して使用されていなかつたのが実状である。
本発明者等は、前記問題点を解決するため鋭意
研究を重ねた結果、本発明を提供するに至つたも
のである。すなわち、
(A) 架橋密度が1000原子量あたり0.02〜1.00個で
ある水系ポリウレタン樹脂に、
(B) 鉛丹、亜酸化鉛、シアナミド鉛、塩基性クロ
ム酸鉛、鉛酸カルシウム、塩基性硫酸鉛、ジン
ククロメート、ストロンチウムクロメート、リ
ン酸亜鉛、リン酸カルシウム、リン酸アンモニ
ウム、リン酸チタン、リン酸ケイ素、縮合リン
酸アルミニウム、モリブデン酸亜鉛、モリブデ
ン酸カルシウム、モリブデン酸亜鉛カルシウ
ム、モリブデン酸亜鉛カリウム、モリブデン酸
アルミニウム、モリブデン酸カルシウム、メタ
ホウ酸バリウム、ホウ酸カルシウム、酸化亜鉛
及び雲母状酸化鉄から成る群から選らばれた少
なくとも1種の防錆顔料及び/又は有機インヒ
ビターを、
全固形分中に0.5〜97重量%となるよう配合し
た防錆用塗料組成物において、
前記水系ポリウレタン樹脂が、平均分子量50〜
10000で2個以上の活性水素原子含有ポリヒドロ
キシ化合物又は前記ポリヒドロキシ化合物と平均
分子量50〜10000で2個以上の活性水素原子含有
多価アミン化合物の併用、有機ポリイソシアネー
ト、並びにNCO基と反応性の活性水素原子及び
塩形成基を有する化合物から合成される塩形成基
を有するポリウレタン樹脂を、塩形成剤を使用す
ることにより、水中に混合乳化させたアニオン性
水系ポリウレタン樹脂であることを特徴とする防
錆用塗料組成物である。
本発明に使用される水系ポリウレタン樹脂とし
ては、前記の如く、平均分子量50〜10000で2個
以上の活性水素原子含有ポリヒドロキシ化合物又
は前記ポリヒドロキシ化合物と平均分子量50〜
10000で2個以上の活性水素原子含有多価アミン
化合物の併用、有機ポリイソシアネート、並びに
NCO基と反応性の活性水素原子及び塩形成基を
有する化合物から合成される塩形成基を有するポ
リウレタン樹脂を、塩形成剤を使用することによ
り、公知の方法で水中に混合乳化させたアニオン
系水系ポリウレタン樹脂等が挙げられる。
かかる前記水系ポリウレタン樹脂において、平
均分子量50〜10000で2個以上の活性水素原子含
有ポリヒドロキシ化合物としては、ジエチレング
リコール、ブタンジオール、ヘキサンジオール、
ビスフエノールA、トリメチロールプロパン、グ
リセリン、ペンタエリスリトール等の多価アルコ
ール、それらのアルキレン誘導体又はそれらのエ
ステル化物;
ポリ(オキシエチレンエーテル)ポリオール、
ポリ(オキシプロピレンエーテル)ポリオール、
ポリ(オキシエチレンプロピレンエーテル)ポリ
オール、ポリエステルポリオール、ポリチオエー
テルポリオール、ポリアセタールポリオール、ポ
リテトラメチレングリコール、ポリブタジエンポ
リオール、ヒマシ油ポリオール等のポリオール化
合物等が、
平均分子量50〜10000で2個以上の活性水素原
子含有多価アミン化合物としては、エチレンジア
ミン、プロピレンジアミン、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
ンタミン等の低分子量多価アミン;エポキシアミ
ンアダクト体又はポリアミド樹脂等の高分子量多
価アミン化合物等がそれぞれ挙げられる。
前記ポリヒドロキシ化合物又は多価アミン化合
物は、平均分子量50〜10000であることが必要で
ある。前記ポリヒドロキシ化合物又は多価アミン
化合物の平均分子量が50〜10000の範囲より外れ
た場合、本発明の目的は達成されない。
次に有機ポリソシアネートとしてはナフチレン
ジイソシアネート、イソホロンジイソシアネー
ト、キシリレンジイソシアネート、ヘキサメチレ
ンジイソシアネート、水素添加ジフエニルメタン
ジイソシアネート、ジフエニルメタンジイソシア
ネート、トリレンジイソシアネート等あらゆる芳
香族、脂肪族、脂環族系のイソシアネート類の単
独もしくは混合物が挙げられる。
次にNCO基と反応性の活性水素原子及び塩形
成基を有する化合物としては、塩形成性のカルボ
ン酸又はスルホン酸基を持つ化合物及び対応する
塩形成剤等が挙げられる。
塩形成性のカルボン酸又はスルホン酸基を持つ
化合物としては、例えばグリコール酸、リンゴ
酸、グリシン、アミノ安息香酸、アラニン、ジメ
チロールプロピオン酸等のヒドロキシ酸、アミノ
カルボン酸、多価ヒドロキシ酸類やタウリン、2
―ヒドロキシエタンスルホン酸等のアミノスルホ
ン酸、ヒドロキシスルホン酸類等が、それに対応
する塩形成剤としては、例えば水酸化ナトリウ
ム、水酸化カルシウム等の1価の金属水酸化物や
アンモニア、トリメチルアミン、トリエチルアミ
ン等の3級アミン化合物等が挙げられる。
本発明に使用される水系ポリウレタン樹脂は架
橋密度が、1000原子量あたり0.02〜1.00個である
ことが必要である。
水系ポリウレタン樹脂の架橋密度が1000原子量
あたり0.02〜1.00個の範囲より外れた場合、本発
明の目的は達成されない。
ここで、本発明に言う架橋密度とは、例えば次
のように計算されるものである。すなわち、分子
量MW1、官能基数F1の活性水素原子含有化合物
W1gと、分子量MW2、官能基数F2の活性水素原
子含有化合物W2gと、
分子量MWo-1、官能基数Fo-1の活性水素原子
含有化合物Wo-1gと、分子量MWn、官能基数
Fnの有機ポリイソシアネートWngと反応せしめ
てえられる水系ポリウレタン樹脂の1000原子量あ
たりの架橋密度は
次式
CD={W1(F1−2)/MW1}+{W2(F2−2)/MW2}+
……{Wn(Fn−2)/MWn}/W1+W2……+Wn×1000
で計算される。
本発明に使用される防錆顔料としては鉛丹、亜
酸化鉛、シアナミド鉛、塩基性クロム酸鉛、鉛酸
カルシウム、塩基性硫酸鉛、ジンククロメート、
ストロンチウムクロメート、リン酸亜鉛、リン酸
カルシウム、リン酸アンモニウム、リン酸チタ
ン、リン酸ケイ素、縮合リン酸アルミニウム、モ
リブデン酸亜鉛、モリブデン酸カルシウム、モリ
ブデン酸亜鉛カルシウム、モリブデン酸亜鉛カリ
ウム、モリブデン酸アルミニウム、モリブデン酸
カルシウム、メタホウ酸バリウム、ホウ酸カルシ
ウム、酸化亜鉛及び雲母状酸化鉄から成る群から
選らばれた少なくとも1種が挙げられる。
本発明に使用される有機インヒビターとして
は、有機リン酸エステル、ホスホン酸塩、アミン
リン酸塩、ホスホニウム化合物、ザルコシン類、
安息香酸塩、オキシカルボン酸類、アミン類、
1,2,3、ベンゾトリアゾール、ケイ皮酸塩、
ポリアクリルアミド、リグニンスルホン酸塩、リ
グニン類、コハク酸ナトリウム、グルコン酸塩、
p―アミノベンツアルデヒド、高級脂肪酸塩、ベ
ンゾイルアクリル酸ナトリウム、n―ラウロイル
ザルコシン、3,5―ジニトロ安息香酸ピペリジ
ン又はこれらの混合物等が挙げられる。
本発明の防錆の対象とされる金属材料として
は、土木材料、建築材料、自動車用材料、電気及
び電子工業品等の鋼板類、パイプ類、金属加工部
品、各種金属材料等、さらに前記用途における
鉄、鋳鉄、ダクタイル鋳鉄、アルミニウム、銅、
亜鉛、ベリリウム、チタニウム、マグネシウム及
びステンレス等の合金類、トタン、ブリキ等の各
種メツキ類又はそれらのリン酸塩、クロム酸塩等
の表面処理品等が挙げられる。
本発明にかかる防錆用塗料組成物は、
前記水系ポリウレタン樹脂に、前記の防錆顔料
及び/又は有機インヒビターを配合したものであ
る。
防錆顔料及び/又は有機インヒビターは、全固
形分中に0.5〜97重量%となるよう配合すること
が必要である。
防錆顔料及び/又は有機インヒビターが97重量
%を超えると、密度の低下と共に塗膜自体の透水
性が非常に大きくなり、防錆顔料のバインダーと
なる水系ポリウレタン樹脂濃度が不足するため、
耐水性劣化が大きく、耐衝撃性も低下し好ましく
ない。
また防錆顔料及び/又は有機インヒビターが
0.5重量%未満の場合、防蝕性が不充分となる。
本発明においては、防錆顔料及び/又は有機イ
ンヒビターを安定分散させるため各種分散剤、塗
料を調合する際の皮張り防止剤、レベリング剤、
消泡剤、造膜助剤、着色顔料、増粘剤、体質顔料
等の各種添加剤を目的にあつた性状にするために
性能を低下させない範囲内で配合することも可能
である。
本発明の防錆用塗料組成物の金属材料への塗布
方法としては、スプレー方法、浸漬処理方法、刷
毛塗り法、ローラーコーター方式等種々の塗装方
法が挙げられる。
本発明に従つて得られる防錆用塗料組成物は金
属材料に塗装した場合、密着性の低下、ふくれの
発生等が起こらず、かつ耐水性、耐塩水性等の耐
食性に優れた金属材料塗装物を提供するもので、
土木、建築、自動車用材料又は電気機器への利用
を可能とするものである。
以下、本発明を実施例によつて具体的に説明す
るが、本発明は、それらの実施例に拘束されるも
のではない。
合成例 1
ポリブチレンアジペート(MW2000,2.0官能)
70重量部、1,6―ヘキサンジオール(MW118,
2.0官能)20重量部、トリメチロールプロパン
(MW134,3.0官能)3重量部、ジメチロールプ
ロピオン酸(MW134,2.0官能)6.5重量部、イ
ソホロンジイソシアネート(MW222,2.0官能)
70重量部からなるイソシアネートプレポリマーを
アセトン中で合成後、これをトリエチルアミンを
含有した水中に混合乳化した。この水系ポリウレ
タン樹脂の架橋密度は0.132である。
合成例 2
ポリブチレンアジペート(MW2000,2.0官能)
70重量部、1,6―ヘキサンジオール(MW118,
2.0官能)20重量部、トリメチロールプロパン
(MW134,3.0官能)10重量部、ジメチロールプ
ロピオン酸(MW134,2.0官能)6.5重量部、イ
ソホロンジイソシアネート(MW222,2.0官能)
95重量部からなるイソシアネートプレポリマーを
アセトン中で合成後、これをトリエチレンテトラ
ミン(MW146,4.0官能)4.6重量部、及びトリ
エチルアミンを含有した水中に混合乳化した。こ
の水系ポリウレタン樹脂の架橋密度は0.66であ
る。
合成例 3
ポリブチレンアジペート(MW2000,2.0官能)
70重量部、1,6―ヘキサンジオール(MW118,
2.0官能)20重量部、トリメチロールプロパン
(MW134,3.0官能)0.2重量部、ジメチロールプ
ロピオン酸(MW134,2.0官能)6.5重量部、イ
ソホロンジイソシアネート(MW222,2.0官能)
65重量部からなるイソシアネートプレポリマーを
アセトン中で合成後、これをトリエチルアミンを
含有した水中に混合乳化した。この水系ポリウレ
タン樹脂の架橋密度は0.009である。
合成例 4
ポリブチレンアジペート(MW2000,2.0官能)
70重量部、1,6―ヘキサンジオール(MW118,
2.0官能)20重量部、トリメチロールプロパン
(MW134,3.0官能)20重量部、ジメチロールプ
ロピオン酸(MW134,2.0官能)6.5重量部、イ
ソホロンジイソシアネート(MW222,2.0官能)
140重量部からなるイソシアネートプレポリマー
をアセトン中で合成後、これをトリエチレンテト
ラミン(MW146,4.0官能)11.2重量部、及びト
リエチルアミンを含有した水中に混合乳化したが
乳化中にゲル化した。この水系ポリウレタン樹脂
の架橋密度は1.13である。
合成例 5
ポリテトラメチレングリコール(MW1000,
2.0官能)70重量部、1,4―ブタンジオール
(MW90,2.0官能)15重量部、トリメチロールプ
ロパン(MW134,3.0官能)7重量部、ヘキサメ
チレンジイソシアネート(MW168,2.0官能)60
重量部からなるイソシアネートプレポリマーをア
セトン中で合成後、タウリン―水酸化ナトリウム
水溶液を混合した後、水中に混合乳化した。この
水系ポリウレタン樹脂の架橋密度は0.344である。
実施例 1
各種水系ポリウレタン樹脂塗料(固形分)50重
量部に、防錆塗料として酸化亜鉛粉末50重量部を
混合してボールミルで24時間分散後、冷間圧延鋼
板に10ミクロンとなるようにスプレー塗布し、80
℃強制乾燥したものを試験片とした。
尚、比較例は、冷間圧延鋼板に10ミクロンとな
るようにスプレー塗布し、80℃強制乾燥したもの
を試験片とした。
それらの結果を第1表に示す。
40℃耐温水性……40℃の温水に48時間浸漬、
塩水噴霧試験……塩水を120時間噴霧、
耐衝撃試験……Dupont 1/4inch,1Kg,50cm
以下の実施例も同じ。
The present invention relates to a rust-preventing coating composition. Conventional water-based anti-corrosion paints for metal materials include water-based acrylic resins, alkyd-melamine resins, water-based epoxy resin paints, etc. These are applied and dried at room temperature or at a relatively low temperature of about 80 to 150 degrees Celsius. There is. However, even metal materials coated with these water-based resin paints have insufficient corrosion resistance, and there are problems in that rust occurs, and blistering or peeling occurs due to decreased adhesion. Furthermore, it is well known that water-based polyurethane resins have superior chemical resistance, abrasion resistance, and bending resistance compared to other water-based alkyd resins, acrylic resins, alkyd-melamine resins, epoxy resins, etc. However, the actual situation is that it has not been used as a general anti-rust paint for metal materials due to its high price. The inventors of the present invention have conducted extensive research to solve the above-mentioned problems, and as a result, have provided the present invention. That is, (A) a water-based polyurethane resin with a crosslink density of 0.02 to 1.00 per 1000 atomic weight, (B) red lead, lead zinc oxide, lead cyanamide, basic lead chromate, calcium leadate, basic lead sulfate, Zinc chromate, strontium chromate, zinc phosphate, calcium phosphate, ammonium phosphate, titanium phosphate, silicon phosphate, condensed aluminum phosphate, zinc molybdate, calcium molybdate, zinc calcium molybdate, zinc potassium molybdate, aluminum molybdate at least one anticorrosion pigment and/or organic inhibitor selected from the group consisting of , calcium molybdate, barium metaborate, calcium borate, zinc oxide and micaceous iron oxide in an amount of 0.5 to 97% by weight in the total solid content. %, the water-based polyurethane resin has an average molecular weight of 50 to 50%.
10,000 and a polyhydroxy compound containing two or more active hydrogen atoms, or a combination of the above polyhydroxy compound and a polyvalent amine compound having an average molecular weight of 50 to 10,000 and containing two or more active hydrogen atoms, reactive with organic polyisocyanates, and NCO groups. An anionic water-based polyurethane resin prepared by mixing and emulsifying a polyurethane resin having a salt-forming group in water using a salt-forming agent, which is synthesized from a compound having an active hydrogen atom and a salt-forming group. This is a rust-preventing paint composition. As mentioned above, the water-based polyurethane resin used in the present invention is a polyhydroxy compound having an average molecular weight of 50 to 10,000 and containing two or more active hydrogen atoms, or a polyhydroxy compound containing the above polyhydroxy compound and an average molecular weight of 50 to 10,000.
10,000 in combination with a polyvalent amine compound containing two or more active hydrogen atoms, organic polyisocyanate, and
An anionic system in which a polyurethane resin having a salt-forming group synthesized from a compound having an active hydrogen atom reactive with an NCO group and a salt-forming group is mixed and emulsified in water by a known method using a salt-forming agent. Examples include water-based polyurethane resins. In the water-based polyurethane resin, examples of the polyhydroxy compound having an average molecular weight of 50 to 10,000 and containing two or more active hydrogen atoms include diethylene glycol, butanediol, hexanediol,
Polyhydric alcohols such as bisphenol A, trimethylolpropane, glycerin, and pentaerythritol, their alkylene derivatives, or their esterified products; poly(oxyethylene ether) polyols,
poly(oxypropylene ether) polyol,
Polyol compounds such as poly(oxyethylene propylene ether) polyol, polyester polyol, polythioether polyol, polyacetal polyol, polytetramethylene glycol, polybutadiene polyol, and castor oil polyol have an average molecular weight of 50 to 10,000 and two or more active hydrogen atoms. Examples of the contained polyvalent amine compounds include low molecular weight polyvalent amines such as ethylene diamine, propylene diamine, diethylene triamine, triethylene tetramine, and tetraethylene pentamine; high molecular weight polyvalent amine compounds such as epoxy amine adducts or polyamide resins, etc. It will be done. The polyhydroxy compound or polyvalent amine compound needs to have an average molecular weight of 50 to 10,000. If the average molecular weight of the polyhydroxy compound or polyvalent amine compound is outside the range of 50 to 10,000, the object of the present invention will not be achieved. Next, examples of organic polysocyanates include naphthylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and all aromatic, aliphatic, and alicyclic polysocyanates. These isocyanates may be used alone or in mixtures. Next, examples of the compound having an active hydrogen atom and a salt-forming group reactive with the NCO group include compounds having a salt-forming carboxylic acid or sulfonic acid group and corresponding salt-forming agents. Examples of compounds having a salt-forming carboxylic acid or sulfonic acid group include hydroxy acids such as glycolic acid, malic acid, glycine, aminobenzoic acid, alanine, dimethylolpropionic acid, aminocarboxylic acids, polyhydric hydroxy acids, and taurine. ,2
- Aminosulfonic acids such as hydroxyethanesulfonic acid, hydroxysulfonic acids, etc.; corresponding salt forming agents include monovalent metal hydroxides such as sodium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine, etc. Examples include tertiary amine compounds. The water-based polyurethane resin used in the present invention must have a crosslink density of 0.02 to 1.00 pieces per 1000 atomic weight. If the crosslink density of the water-based polyurethane resin is outside the range of 0.02 to 1.00 crosslinks per 1000 atomic weight, the object of the present invention will not be achieved. Here, the crosslinking density referred to in the present invention is calculated as follows, for example. That is, an active hydrogen atom-containing compound with a molecular weight MW 1 and a functional group number F 1
W 1 g, an active hydrogen atom-containing compound W 2 g having a molecular weight MW 2 and a functional group number F 2 , an active hydrogen atom-containing compound W o-1 g having a molecular weight MW o-1 and a functional group number F o- 1 , and a molecular weight MWn, number of functional groups
The crosslinking density per 1000 atomic weight of the water-based polyurethane resin obtained by reacting Fn with organic polyisocyanate Wng is as follows: CD = {W 1 (F 1 -2)/MW 1 } + {W 2 (F 2 -2) /MW 2 }+
...It is calculated as {Wn (Fn-2)/MWn}/W 1 +W 2 ...+Wn×1000. The antirust pigments used in the present invention include red lead, lead zinc oxide, lead cyanamide, basic lead chromate, calcium lead oxide, basic lead sulfate, zinc chromate,
Strontium chromate, zinc phosphate, calcium phosphate, ammonium phosphate, titanium phosphate, silicon phosphate, condensed aluminum phosphate, zinc molybdate, calcium molybdate, zinc calcium molybdate, zinc potassium molybdate, aluminum molybdate, molybdate At least one selected from the group consisting of calcium, barium metaborate, calcium borate, zinc oxide, and micaceous iron oxide is mentioned. Organic inhibitors used in the present invention include organic phosphate esters, phosphonates, amine phosphates, phosphonium compounds, sarcosines,
Benzoates, oxycarboxylic acids, amines,
1,2,3, benzotriazole, cinnamate,
Polyacrylamide, lignin sulfonate, lignins, sodium succinate, gluconate,
Examples include p-aminobenzaldehyde, higher fatty acid salts, sodium benzoyl acrylate, n-lauroylsarcosine, piperidine 3,5-dinitrobenzoate, and mixtures thereof. Metal materials to be subjected to rust prevention in the present invention include civil engineering materials, building materials, automobile materials, steel plates such as electrical and electronic industrial products, pipes, metal processed parts, various metal materials, etc., and the above-mentioned uses. iron, cast iron, ductile iron, aluminum, copper,
Examples include alloys such as zinc, beryllium, titanium, magnesium and stainless steel, various platings such as galvanized iron and tinplate, and surface-treated products thereof such as phosphates and chromates. The rust-preventing coating composition according to the present invention is a composition in which the above-mentioned water-based polyurethane resin is blended with the above-mentioned rust-preventing pigment and/or organic inhibitor. The anticorrosion pigment and/or organic inhibitor must be blended in an amount of 0.5 to 97% by weight based on the total solid content. If the content of the anti-rust pigment and/or organic inhibitor exceeds 97% by weight, the water permeability of the coating film itself will decrease as well as the density will decrease, and the concentration of the water-based polyurethane resin, which is the binder for the anti-rust pigment, will be insufficient.
Water resistance deteriorates significantly and impact resistance also decreases, which is not preferable. In addition, anti-rust pigments and/or organic inhibitors
If it is less than 0.5% by weight, corrosion resistance will be insufficient. In the present invention, various dispersants are used to stably disperse rust-preventing pigments and/or organic inhibitors, anti-skinning agents and leveling agents used when formulating paints,
Various additives such as antifoaming agents, film-forming aids, coloring pigments, thickeners, and extender pigments can be added within the range that does not impair performance in order to achieve desired properties. Examples of methods for applying the anticorrosive coating composition of the present invention to metal materials include various coating methods such as a spray method, a dipping treatment method, a brush coating method, and a roller coater method. When the anticorrosion coating composition obtained according to the present invention is applied to a metal material, it does not cause a decrease in adhesion or the occurrence of blistering, and it is a coated metal material that has excellent corrosion resistance such as water resistance and salt water resistance. It provides
It can be used in civil engineering, construction, automobile materials, or electrical equipment. EXAMPLES Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited to these Examples. Synthesis example 1 Polybutylene adipate (MW2000, 2.0 functionality)
70 parts by weight, 1,6-hexanediol (MW118,
2.0 functional) 20 parts by weight, trimethylolpropane (MW134, 3.0 functional) 3 parts by weight, dimethylolpropionic acid (MW134, 2.0 functional) 6.5 parts by weight, isophorone diisocyanate (MW222, 2.0 functional)
After synthesizing an isocyanate prepolymer consisting of 70 parts by weight in acetone, this was mixed and emulsified in water containing triethylamine. The crosslinking density of this water-based polyurethane resin is 0.132. Synthesis example 2 Polybutylene adipate (MW2000, 2.0 functionality)
70 parts by weight, 1,6-hexanediol (MW118,
2.0 functional) 20 parts by weight, trimethylolpropane (MW134, 3.0 functional) 10 parts by weight, dimethylolpropionic acid (MW134, 2.0 functional) 6.5 parts by weight, isophorone diisocyanate (MW222, 2.0 functional)
After synthesizing 95 parts by weight of an isocyanate prepolymer in acetone, this was mixed and emulsified in water containing 4.6 parts by weight of triethylenetetramine (MW146, 4.0 functional) and triethylamine. The crosslinking density of this water-based polyurethane resin is 0.66. Synthesis example 3 Polybutylene adipate (MW2000, 2.0 functionality)
70 parts by weight, 1,6-hexanediol (MW118,
20 parts by weight of trimethylolpropane (MW134, 3.0 functionality), 6.5 parts by weight of dimethylolpropionic acid (MW134, 2.0 functionality), isophorone diisocyanate (MW222, 2.0 functionality)
After synthesizing 65 parts by weight of an isocyanate prepolymer in acetone, this was mixed and emulsified in water containing triethylamine. The crosslinking density of this water-based polyurethane resin is 0.009. Synthesis example 4 Polybutylene adipate (MW2000, 2.0 functionality)
70 parts by weight, 1,6-hexanediol (MW118,
20 parts by weight of trimethylolpropane (MW134, 3.0 functionality), 6.5 parts by weight of dimethylolpropionic acid (MW134, 2.0 functionality), isophorone diisocyanate (MW222, 2.0 functionality)
After synthesizing 140 parts by weight of an isocyanate prepolymer in acetone, this was mixed and emulsified in water containing 11.2 parts by weight of triethylenetetramine (MW146, 4.0 functional) and triethylamine, but gelation occurred during emulsification. The crosslinking density of this water-based polyurethane resin is 1.13. Synthesis example 5 Polytetramethylene glycol (MW1000,
2.0 functional) 70 parts by weight, 1,4-butanediol (MW90, 2.0 functional) 15 parts by weight, trimethylolpropane (MW134, 3.0 functional) 7 parts by weight, hexamethylene diisocyanate (MW168, 2.0 functional) 60
After synthesizing an isocyanate prepolymer consisting of parts by weight in acetone, a taurine-sodium hydroxide aqueous solution was mixed therein, and the mixture was mixed and emulsified in water. The crosslinking density of this water-based polyurethane resin is 0.344. Example 1 50 parts by weight of various water-based polyurethane resin paints (solid content) were mixed with 50 parts by weight of zinc oxide powder as a rust preventive paint, dispersed in a ball mill for 24 hours, and then sprayed onto a cold rolled steel plate to a thickness of 10 microns. Apply and 80
The sample was force-dried at ℃ and used as a test piece. In addition, as a comparative example, a test piece was prepared by spray coating a cold rolled steel plate to a thickness of 10 microns and forced drying at 80°C. The results are shown in Table 1. 40℃ hot water resistance...Immersed in 40℃ hot water for 48 hours, salt spray test...Sprayed with salt water for 120 hours, impact resistance test...Dupont 1/4inch, 1Kg, 50cm The following examples are the same.
【表】
実施例 2
水系ポリウレタン樹脂と防錆顔料又は有機イン
ヒビターをボールミルで24時間分散したものを冷
間圧延鋼板に10ミクロンとなるようにスプレー塗
布し、80℃強制乾燥したものを試験片とした。
尚、比較例は、冷間圧延鋼板に10ミクロンとな
るようにスプレー塗布し、80℃強制乾燥したもの
を試験片とした。
それらの結果を第2表に示す。[Table] Example 2 A water-based polyurethane resin and anti-corrosion pigment or organic inhibitor were dispersed in a ball mill for 24 hours, and then sprayed onto a cold rolled steel plate to a thickness of 10 microns, and force-dried at 80°C to obtain a test piece. did. In addition, as a comparative example, a test piece was prepared by spray coating a cold rolled steel plate to a thickness of 10 microns and forced drying at 80°C. The results are shown in Table 2.
Claims (1)
個である水系ポリウレタン樹脂に、 (B) 鉛丹、亜酸化鉛、シアナミド鉛、塩基性クロ
ム酸鉛、鉛酸カルシウム、塩基性硫酸鉛、ジン
ククロメート、ストロンチウムクロメート、リ
ン酸亜鉛、リン酸カルシウム、リン酸アンモニ
ウム、リン酸チタン、リン酸ケイ素、縮合リン
酸アルミニウム、モリブデン酸亜鉛、モリブデ
ン酸カルシウム、モリブデン酸亜鉛カルシウ
ム、モリブデン酸亜鉛カリウム、モリブデン酸
アルミニウム、モリブデン酸カルシウム、メタ
ホウ酸バリウム、ホウ酸カルシウム、酸化亜鉛
及び雲母状酸化鉄から成る群から選らばれた少
なくとも1種の防錆顔料及び/又は有機インヒ
ビターを、 全固形分中に0.5〜97重量%となるよう配合
した防錆用塗料組成物において、 該水系ポリウレタン樹脂が、平均分子量50〜
10000で2個以上の活性水素原子含有ポリヒド
ロキシ化合物又は前記ポリヒドロキシ化合物と
平均分子量50〜10000で2個以上の活性水素原
子含有多価アミン化合物の併用、有機ポリイソ
シアネート、並びにNCO基と反応性の活性水
素原子及び塩形成基を有する化合物から合成さ
れる塩形成基を有するポリウレタン樹脂を、塩
形成剤を使用することにより、水中に混合乳化
させたアニオン性水系ポリウレタン樹脂である
こと を特徴とする防錆用塗料組成物。[Claims] 1 (A) Crosslink density is 0.02 to 1.00 per 1000 atomic weight
(B) Red lead, lead zinc oxide, lead cyanamide, basic lead chromate, calcium leadate, basic lead sulfate, zinc chromate, strontium chromate, zinc phosphate, calcium phosphate, phosphoric acid Ammonium, titanium phosphate, silicon phosphate, condensed aluminum phosphate, zinc molybdate, calcium molybdate, zinc calcium molybdate, zinc potassium molybdate, aluminum molybdate, calcium molybdate, barium metaborate, calcium borate, oxidized A rust-preventing paint composition containing at least one rust-preventing pigment and/or organic inhibitor selected from the group consisting of zinc and micaceous iron oxide in an amount of 0.5 to 97% by weight in the total solid content, The water-based polyurethane resin has an average molecular weight of 50 to
10,000 and a polyhydroxy compound containing two or more active hydrogen atoms, or a combination of the above polyhydroxy compound and a polyvalent amine compound having an average molecular weight of 50 to 10,000 and containing two or more active hydrogen atoms, reactive with organic polyisocyanates, and NCO groups. An anionic water-based polyurethane resin prepared by mixing and emulsifying a polyurethane resin having a salt-forming group in water using a salt-forming agent, which is synthesized from a compound having an active hydrogen atom and a salt-forming group. Rust-preventing paint composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21015986A JPS6366266A (en) | 1986-09-05 | 1986-09-05 | Rust-proofing paint composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21015986A JPS6366266A (en) | 1986-09-05 | 1986-09-05 | Rust-proofing paint composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6366266A JPS6366266A (en) | 1988-03-24 |
JPH0133509B2 true JPH0133509B2 (en) | 1989-07-13 |
Family
ID=16584739
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21015986A Granted JPS6366266A (en) | 1986-09-05 | 1986-09-05 | Rust-proofing paint composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6366266A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001152087A (en) * | 1999-11-22 | 2001-06-05 | Kawasaki Steel Corp | Surface treated steel plate excellent in processability and weather resistance |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5322870A (en) * | 1992-12-29 | 1994-06-21 | Board Of Regents, Northern Illinois University | Additive package for in situ phosphatizing paint, paint and method |
JP3347394B2 (en) * | 1993-05-19 | 2002-11-20 | 三菱瓦斯化学株式会社 | Oxygen scavenging paint |
CN1329465C (en) * | 2005-07-13 | 2007-08-01 | 北京格丽斯聚合技术发展有限公司 | Thermostable rustproof metallic paint and preparation method thereof |
JP2009215477A (en) * | 2008-03-12 | 2009-09-24 | Fuji Electric Holdings Co Ltd | Protectant, protective structure and protecting method for metal-made electroconductive part |
JP5945201B2 (en) * | 2011-09-30 | 2016-07-05 | 大日本塗料株式会社 | Rust prevention coating method, new installation method and renovation method of parking facilities |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57174357A (en) * | 1981-04-20 | 1982-10-27 | Kikusui Kagaku Kogyo Kk | Paint composition |
JPS6081258A (en) * | 1983-10-11 | 1985-05-09 | Kikusui Kagaku Kogyo Kk | Troweling aqueous coating material composition |
JPS60104166A (en) * | 1983-10-17 | 1985-06-08 | ピーピージー・インダストリーズ・インコーポレイテツド | Water-dispersible polymer containing metal chelating group |
JPS6153371A (en) * | 1984-08-22 | 1986-03-17 | Kikusui Kagaku Kogyo Kk | Paint composition |
-
1986
- 1986-09-05 JP JP21015986A patent/JPS6366266A/en active Granted
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57174357A (en) * | 1981-04-20 | 1982-10-27 | Kikusui Kagaku Kogyo Kk | Paint composition |
JPS6081258A (en) * | 1983-10-11 | 1985-05-09 | Kikusui Kagaku Kogyo Kk | Troweling aqueous coating material composition |
JPS60104166A (en) * | 1983-10-17 | 1985-06-08 | ピーピージー・インダストリーズ・インコーポレイテツド | Water-dispersible polymer containing metal chelating group |
JPS6153371A (en) * | 1984-08-22 | 1986-03-17 | Kikusui Kagaku Kogyo Kk | Paint composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001152087A (en) * | 1999-11-22 | 2001-06-05 | Kawasaki Steel Corp | Surface treated steel plate excellent in processability and weather resistance |
Also Published As
Publication number | Publication date |
---|---|
JPS6366266A (en) | 1988-03-24 |
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