EP0624182A1 - Selbsttaetig abscheidbare ueberzugszusammensetzung - Google Patents

Selbsttaetig abscheidbare ueberzugszusammensetzung

Info

Publication number: EP0624182A1
Authority: EP; European Patent Office
Prior art keywords: liter; grams; ion; fluoride ion; coating composition
Prior art date: 1992-01-31
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 Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Withdrawn

Application number

EP93903012A

Other languages

English (en)

French (fr)

Inventor

Takumi Honda

Kazuhisa Naito

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Henkel Corp

Original Assignee

Henkel Corp

Priority date (The priority date 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 date listed.)

1992-01-31

Filing date

1993-01-15

Publication date

1994-11-17

1993-01-15 Application filed by Henkel Corp filed Critical Henkel Corp

1994-11-17 Publication of EP0624182A1 publication Critical patent/EP0624182A1/de

Status Withdrawn legal-status Critical Current

Links

239000008199 coating composition Substances 0.000 title claims abstract description 52
229920005989 resin Polymers 0.000 claims abstract description 42
239000011347 resin Substances 0.000 claims abstract description 42
229910052751 metal Inorganic materials 0.000 claims abstract description 36
239000002184 metal Substances 0.000 claims abstract description 36
PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 16
-1 fluoride ions Chemical class 0.000 claims abstract description 15
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
239000010941 cobalt Substances 0.000 claims abstract description 7
229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
229910052742 iron Inorganic materials 0.000 claims abstract description 7
WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 7
229910052759 nickel Inorganic materials 0.000 claims abstract description 7
239000011701 zinc Substances 0.000 claims abstract description 7
229910052725 zinc Inorganic materials 0.000 claims abstract description 7
KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 34
229910021645 metal ion Inorganic materials 0.000 claims description 20
239000000203 mixture Substances 0.000 claims description 17
238000000576 coating method Methods 0.000 claims description 13
MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 13
239000011248 coating agent Substances 0.000 claims description 11
PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 9
239000011737 fluorine Substances 0.000 claims description 9
229910052731 fluorine Inorganic materials 0.000 claims description 9
SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
239000002253 acid Substances 0.000 claims description 4
TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 3
GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 3
GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
239000005977 Ethylene Substances 0.000 claims description 3
239000001263 FEMA 3042 Substances 0.000 claims description 3
WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
239000004327 boric acid Substances 0.000 claims description 3
CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
239000003822 epoxy resin Substances 0.000 claims description 3
SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
239000000178 monomer Substances 0.000 claims description 3
RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
235000002949 phytic acid Nutrition 0.000 claims description 3
239000000467 phytic acid Substances 0.000 claims description 3
229940068041 phytic acid Drugs 0.000 claims description 3
229920000647 polyepoxide Polymers 0.000 claims description 3
229920001225 polyester resin Polymers 0.000 claims description 3
239000004645 polyester resin Substances 0.000 claims description 3
235000015523 tannic acid Nutrition 0.000 claims description 3
LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
229940033123 tannic acid Drugs 0.000 claims description 3
229920002258 tannic acid Polymers 0.000 claims description 3
229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
229960002645 boric acid Drugs 0.000 claims description 2
235000010338 boric acid Nutrition 0.000 claims description 2
229960004838 phosphoric acid Drugs 0.000 claims description 2
235000011007 phosphoric acid Nutrition 0.000 claims description 2
229940095095 2-hydroxyethyl acrylate Drugs 0.000 claims 2
VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 2
238000005260 corrosion Methods 0.000 abstract description 17
230000007797 corrosion Effects 0.000 abstract description 17
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 10
229910052804 chromium Inorganic materials 0.000 abstract description 10
239000011651 chromium Substances 0.000 abstract description 10
150000002500 ions Chemical class 0.000 abstract description 8
150000001845 chromium compounds Chemical class 0.000 abstract description 4
230000001747 exhibiting effect Effects 0.000 abstract 1
238000012360 testing method Methods 0.000 description 18
238000007654 immersion Methods 0.000 description 11
229910000831 Steel Inorganic materials 0.000 description 6
239000010959 steel Substances 0.000 description 6
238000004519 manufacturing process Methods 0.000 description 5
239000010960 cold rolled steel Substances 0.000 description 4
238000000151 deposition Methods 0.000 description 4
230000008021 deposition Effects 0.000 description 4
150000002739 metals Chemical class 0.000 description 4
230000002378 acidificating effect Effects 0.000 description 3
150000007513 acids Chemical class 0.000 description 3
230000001464 adherent effect Effects 0.000 description 3
239000002390 adhesive tape Substances 0.000 description 3
239000000758 substrate Substances 0.000 description 3
KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
230000015572 biosynthetic process Effects 0.000 description 2
238000001035 drying Methods 0.000 description 2
230000000694 effects Effects 0.000 description 2
239000011777 magnesium Substances 0.000 description 2
229910052749 magnesium Inorganic materials 0.000 description 2
229910017604 nitric acid Inorganic materials 0.000 description 2
239000007787 solid Substances 0.000 description 2
NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
239000004971 Cross linker Substances 0.000 description 1
JZDMNWBZPLJKBT-UHFFFAOYSA-N F.[Zr] Chemical compound F.[Zr] JZDMNWBZPLJKBT-UHFFFAOYSA-N 0.000 description 1
VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
229910019142 PO4 Inorganic materials 0.000 description 1
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
RPJKYODNJDVOOO-UHFFFAOYSA-N [B].F Chemical compound [B].F RPJKYODNJDVOOO-UHFFFAOYSA-N 0.000 description 1
239000003513 alkali Substances 0.000 description 1
125000000129 anionic group Chemical group 0.000 description 1
239000010953 base metal Substances 0.000 description 1
239000011575 calcium Substances 0.000 description 1
229910052791 calcium Inorganic materials 0.000 description 1
BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
150000004649 carbonic acid derivatives Chemical class 0.000 description 1
125000002091 cationic group Chemical group 0.000 description 1
150000001805 chlorine compounds Chemical class 0.000 description 1
230000008602 contraction Effects 0.000 description 1
238000005520 cutting process Methods 0.000 description 1
239000008367 deionised water Substances 0.000 description 1
238000005137 deposition process Methods 0.000 description 1
AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
238000004070 electrodeposition Methods 0.000 description 1
239000000839 emulsion Substances 0.000 description 1
230000002708 enhancing effect Effects 0.000 description 1
230000007613 environmental effect Effects 0.000 description 1
238000005530 etching Methods 0.000 description 1
238000011156 evaluation Methods 0.000 description 1
229910001447 ferric ion Inorganic materials 0.000 description 1
125000000524 functional group Chemical group 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
238000010438 heat treatment Methods 0.000 description 1
150000004679 hydroxides Chemical class 0.000 description 1
238000009863 impact test Methods 0.000 description 1
150000002506 iron compounds Chemical class 0.000 description 1
229910052744 lithium Inorganic materials 0.000 description 1
239000000463 material Substances 0.000 description 1
238000000034 method Methods 0.000 description 1
150000007522 mineralic acids Chemical class 0.000 description 1
VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
150000002823 nitrates Chemical class 0.000 description 1
229940074355 nitric acid Drugs 0.000 description 1
150000007524 organic acids Chemical class 0.000 description 1
235000005985 organic acids Nutrition 0.000 description 1
239000007800 oxidant agent Substances 0.000 description 1
230000001590 oxidative effect Effects 0.000 description 1
239000002245 particle Substances 0.000 description 1
235000021317 phosphate Nutrition 0.000 description 1
150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
239000000049 pigment Substances 0.000 description 1
239000002952 polymeric resin Substances 0.000 description 1
229910052700 potassium Inorganic materials 0.000 description 1
239000011591 potassium Substances 0.000 description 1
159000000001 potassium salts Chemical class 0.000 description 1
230000001105 regulatory effect Effects 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
MNTPMEHIQKUBIC-UHFFFAOYSA-N silicon;hydrofluoride Chemical compound F.[Si] MNTPMEHIQKUBIC-UHFFFAOYSA-N 0.000 description 1
229910052708 sodium Inorganic materials 0.000 description 1
239000011734 sodium Substances 0.000 description 1
235000015393 sodium molybdate Nutrition 0.000 description 1
239000011684 sodium molybdate Substances 0.000 description 1
TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
239000007921 spray Substances 0.000 description 1
239000000126 substance Substances 0.000 description 1
150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
229920003002 synthetic resin Polymers 0.000 description 1
238000010998 test method Methods 0.000 description 1
BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 1
CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/088—Autophoretic paints

Definitions

the invention relates to an aqueous autodeposition coating composition in the form of an acidic coating 5 composition (pH approximately 1.6 to 5) that contains a water-dispersible or water-soluble organic film-forming resin; fluoride ions or fluoride ions and " complex fluoride ions; one or more ions selected from ions of the following metals: zinc, cobalt, manganese, nickel, iron, and
the aqueous autodeposition coating composition is capable of forming a highly corrosion-resistant, strongly adherent resin film on metal surfaces when brought into contact with the surface of a metal, for example, a ferriferous metal,
Autodeposition coating compositions are acidic coating compositions that contain an organic film-forming resin and form a resin film on a metal surface when brought into contact with the metal surface. Autodeposition coating compositions are disclosed in, for example,
a characteristic feature of the known coating compositions is their ability to lay down a resin film upon immersion of a clean metal surface in the particular coating composition. Moreover, the coating film's thickness and weight increase with immersion time. In the case of these compositions, the chemical activity of the coating composition overlying the metal surface (metal ion eluted from the metal surface by etching induces association of the resin particles with resulting deposition on the metal surface) results in the efficient deposition of a resin film on the metal surface without the application, as in electrodeposition, of an external electrical source.
a metal ion-containing coating composition is disclosed in Japanese Patent Publication Number Sho 52-35692. This publication discloses the use of a composition that contains a ferric ion-supplying iron compound to coat ferriferous metal.
a coating composition that contains various metal ions (not including the ferric ion) is disclosed in Japanese Patent Publication Number Sho 53-44949 for the coating of various- types of metal substrates.
the demands made on coating performance have recently become more severe, particularly with regard to adherence and corrosion resistance.
a rinse treatment with a chromium-containing solution or aqueous alkali solution, etc. may be implemented prior to film curing (prior to baking/drying) in order thereby to provide the ultimately produced film with better corrosion resistance and better adherence.
the presence of a chromium compound is particularly effective for enhancing film performance and particularly the corrosion resistance provided by the film.
the present invention provides an essentially chromium compound-free film which has much better adherence and corrosion resistance than the films formed by prior-art coating compositions, but which is produced without a rinse treatment (for example, with a chromium-containing solution) prior to film curing.
the aqueous autodeposition coating composition of the invention has a pH of about 1.6 to about 5 and contains (i) water-dispersible or water-soluble organic film-forming resin; (ii) at least one of fluoride ions or fluoride ions and complex fluoride ions; (i ⁇ ) additional metal ions of at least one metal selected from the group consisting of zinc, cobalt, manganese, nickel, iron, and aluminum; and (iv) at least one of tungstate ion and olybdate ion.
a highly adherent, strongly corrosion-resistant resin film is formed on the metal surface when the aqueous auto ⁇ deposition coating composition of the present invention is brought into contact with a metal surface, for example, the surface of ferriferous, zinciferous, aluminiferous, or magnesium-based metal.
composition of the invention provides films with a better adherence and corrosion resistance than the films afforded by prior autodeposition coating compositions due to an acidic coating composition (pH about 1.6 to about 5) that contains organic film-forming resin; fluoride ion or fluoride ion and complex fluoride ion; one or more additional metal ions selected from the group consisting of zinc, cobalt, manganese, nickel, iron, and aluminum; and also tungstate ion and/or molybdate ion.
the present invention provides a highly adherent, highly corrosion-resistant film without having to carry out a post-treatment (precure rinse treatment, for example, with a chromium-containing solution) that have heretofore been implemented for the purpose of improving the adherence and corrosion resistance of the films produced by autodepositing coating compositions.
a post-treatment precure rinse treatment, for example, with a chromium-containing solution
DETAILED DESCRIPTION OF THE INVENTION Resin of the type disclosed in Japanese Patent Application Sho 61-168673 is an example of resin highly suitable for use as the organic film-forming resin in the present invention.
the organic film-forming resin useful in the practice of the present invention is exemplified by the following: urethane resins, epoxy resins, polyester resins, and polymer resins composed of one or more monomers selected from methyl acrylate, ethyl acrylate, n-butyl acrylate,
the organic film-forming resin useful in the practice of the invention may be anionic, cationic, nonionic, or amphoteric and is not specifically restricted in this regard.
the content of resin solids in the coating composition preferably falls within the range of 5 to 550 g/L and more preferably falls within the range of 50 to 100 g/L.
Sources for the fluoride ion and complex fluoride ion useful in the practice of the invention are, for example, zirconium hydrogen fluoride, titanium hydrogen fluoride, silicon hydrogen fluoride, boron hydrogen fluoride, hydrofluoric acid, and the ammonium, lithium, sodium, and potassium salts of the preceding acids.
the content of fluoride or fluoride ion and complex fluoride ion in the coating composition preferably falls within the range of 0.1 to 5 g/L as fluorine and more preferably falls within the range of 0.5 to 3 g/L as fluorine.
the pH of the coating composition of the invention should be maintained within the range of about 1.6 to about 5. Formation of the resin film becomes problematic when the pH is substantially outside this range.
the pH of the coating composition may be regulated using one or more acids selected from inorganic acids such as the acids listed above as sources of fluoride and complex fluoride ion and their salts, as well as nitric acid, phosphoric acid, and boric acid; and organic acids selected from phytic acid and tannic acid.
inorganic acids such as the acids listed above as sources of fluoride and complex fluoride ion and their salts, as well as nitric acid, phosphoric acid, and boric acid
organic acids selected from phytic acid and tannic acid.
nitric acid, phosphoric acid, boric acid, phytic acid, or tannic acid has the effect of improving film adherence to the substrate.
the zinc, cobalt, manganese, nickel, iron, and aluminum metal ions useful in the practice of the invention can be supplied using the carbonates, nitrates, phosphates, sulfates, hydroxides, oxides, and chlorides of the corresponding metals.
the metal ion is taken into the resin film during film formation (deposition process) , and it functions as a crosslinker for the resin during the heating carried out during film drying and curing.
the metal ion bonds with the functional groups in the resin to bring about a substantial increase in the molecular weight of the resin and thereby improve the corrosion resistance of the film formed on the metal.
the additional metal ions are present in solution in the composition in the range of from about 0.1 to about 20 gram/liter preferably from about 0.2 to about 10 grams/liter and more preferably from about 0.3 to about 6 grams/liter.
a critical feature of the present invention is the additional presence of at least one of tungstate ion and molybdate ion in a coating composition that contains organic film-forming resin; fluoride and/or complex fluoride ion; and one or more ions selected from the ions of the following metals: zinc, cobalt, manganese, nickel, iron, and aluminum.
the tungstate ion and/or molybdate ion present in the aqueous autodeposition coating composition of the invention forms a complex with a portion of the aforementioned metal ions.
the metal (ion) in the complex appears to substitute for metal ion eluted from the surface of the metal . workpiece, which results in efficient deposition onto the surface of the metal workpiece and ultimately coverage of the metal surface together with the organic film-forming resin.
the chromium (ion) taken into the resin film is largely present relatively near the surface of the resin film.
the metal ion taken into the resin film is largely present not only within the resin film, but also in particular in the vicinity of the metal surface of the substrate to a much greater degree than for prior-art coating compositions. This results in the production of a film having excellent adherence and corrosion resistance.
the tungstate ion used in the present invention can be supplied in the form of tungstic acid, sodium tungstate, calcium tungstate, potassium tungstate, and the like.
the molybdate ion used in the present invention can be supplied in the form of molybdic acid, sodium molybdate, calcium molybdate, potassium molybdate, and the like.
the content of tungstate ion and molybdate ion - in the coating composition should be 0.1 to 5 g/L and is preferably 0.3 to 2 g/L.
the coating composition of the present invention may also contain an oxidant as an optional material.
the coating composition of the present invention can contain pigment to impart color to the film. Examples of the present invention and comparison examples are presented below. Composition Production Examples A through 0
Aqueous coating compositions were prepared using an acrylic emulsion (41.5% solids, Rhoplex WL-91 from the Rohm _ Haas Company) and the other components as reported in Table l (brought to a total of 1 L with de-ionized water) .
Examples 1 through 16 The aqueous coating compositions prepared in
composition Production Examples A through P were used in these examples.
the aqueous coating composition baths were held at approximately 20 ⁇ C to 22"C.
the aqueous coating composition prepared in Composition Production Example Q was used in the comparison examples.
the aqueous coating composition baths were held at approximately 20 ⁇ C to 22 ⁇ C.
the aqueous coating composition prepared in Composition Production Example Q was used in this comparison example.
the aqueous coating composition bath was held at approximately 20°C to 22*C.
the sample was immersed in an aqueous chromium- containing solution (Palene 60, trademark of Nihon Parkerizing Company, Limited) for 60 seconds at room temperature and then dried in an oven for 20 minutes at 180 ⁇ C.
the sample was subsequently submitted to the various tests, and the results of the performance testing of the test sheet are reported in Table 2. Test Methods and Evaluation Standards
a grid of one hundred 1 mm x 1 mm squares was cut in the test sheet and peeled with adhesive tape, and the number of remaining film squares was counted. This test was conducted both before and after immersion in water at 40"C for 240 hours. The pre-immersion results are reported in row a and the post-immersion results are reported in row b.
the test sheet was prepared by cutting a cross in the coating to reach the base metal, and the test sheet was then subjected to salt-spray testing in accordance with JIS Z-2371 (500 hours for the cold-rolled steel sheet, galvannealed hot-dipped zinc-plated steel sheet, and electrogalvanized steel sheet and 1,000 hours for the aluminum sheet). The test sheet was subsequently subjected to tape peeling, and the peel width from the cross cut (one side, mm) was measured.
the aqueous autodeposition coating composition of the present invention is environmentally advantageous because it does not contain chromium.
coatings with a much better adherence and corrosion resistance than the coatings obtained from prior-art coating compositions are formed by contacting metal surfaces with the aqueous autodeposition coating composition of the present invention. Furthermore, this is achieved without having to carry out a rinse treatment, for example, with a chromium-containing solution, prior to film curing.

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Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Engineering & Computer Science (AREA)
Materials Engineering (AREA)
General Chemical & Material Sciences (AREA)
Wood Science & Technology (AREA)
Life Sciences & Earth Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
Mechanical Engineering (AREA)
Metallurgy (AREA)
Paints Or Removers (AREA)
Chemical Treatment Of Metals (AREA)
Application Of Or Painting With Fluid Materials (AREA)

EP93903012A 1992-01-31 1993-01-15 Selbsttaetig abscheidbare ueberzugszusammensetzung Withdrawn EP0624182A1 (de)

Applications Claiming Priority (3)

Application Number	Priority Date	Filing Date	Title
JP40571/92		1992-01-31
JP4040571A JPH05214266A (ja)	1992-01-31	1992-01-31	自己析出型水性コーティング組成物
PCT/US1993/000137 WO1993015154A1 (en)	1992-01-31	1993-01-15	Autodeposition coating composition

Publications (1)

Publication Number	Publication Date
EP0624182A1 true EP0624182A1 (de)	1994-11-17

Family

ID=12584167

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP93903012A Withdrawn EP0624182A1 (de)	1992-01-31	1993-01-15	Selbsttaetig abscheidbare ueberzugszusammensetzung

Country Status (8)

Country	Link
EP (1)	EP0624182A1 (de)
JP (1)	JPH05214266A (de)
AU (1)	AU3438393A (de)
BR (1)	BR9305766A (de)
CA (1)	CA2128095A1 (de)
MX (1)	MX9300330A (de)
WO (1)	WO1993015154A1 (de)
ZA (1)	ZA93532B (de)

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NL1000118C2 (nl) *	1995-04-11	1996-10-14	Adw Chem Prod Bv	Chroomvrij bekledingspreparaat voor het behandelen van metaaloppervlakken en werkwijze onder toepassing daarvan.
EP4310223A1 (de)	2022-07-18	2024-01-24	Henkel AG & Co. KGaA	Alkalische reaktionsspülung für dekorative chemiophoresis

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DE19755421A1 (de)	1997-12-13	1999-06-17	Henkel Kgaa	Gummi-Metall-Verbund
US6383307B1 (en)	1998-01-27	2002-05-07	Lord Corporation	Aqueous metal treatment composition
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US20030172998A1 (en) *	2002-03-14	2003-09-18	Gerald Wojcik	Composition and process for the treatment of metal surfaces
JP5249819B2 (ja) *	2009-03-02	2013-07-31	日本パーカライジング株式会社	電着塗料組成物および電着塗装方法
WO2011061784A1 (ja) *	2009-11-17	2011-05-26	日本パーカライジング株式会社	鉄系および／または亜鉛系金属材料への自己析出被膜処理用表面処理液、および表面処理方法
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JP6043689B2 (ja) *	2013-07-31	2016-12-14	日本パーカライジング株式会社	多種金属材料用自己析出型被覆組成物とその製造方法及び有機樹脂被膜を有する金属材料とその製造方法
KR20190043155A (ko)	2016-08-24	2019-04-25	피피지 인더스트리즈 오하이오 인코포레이티드	금속 기판을 처리하기 위한 알칼리성 조성물
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1993
- 1993-01-15 EP EP93903012A patent/EP0624182A1/de not_active Withdrawn
- 1993-01-15 WO PCT/US1993/000137 patent/WO1993015154A1/en not_active Ceased
- 1993-01-15 CA CA002128095A patent/CA2128095A1/en not_active Abandoned
- 1993-01-15 AU AU34383/93A patent/AU3438393A/en not_active Abandoned
- 1993-01-15 BR BR9305766A patent/BR9305766A/pt not_active Application Discontinuation
- 1993-01-22 MX MX9300330A patent/MX9300330A/es unknown
- 1993-01-25 ZA ZA93532A patent/ZA93532B/xx unknown

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EP4310223A1 (de)	2022-07-18	2024-01-24	Henkel AG & Co. KGaA	Alkalische reaktionsspülung für dekorative chemiophoresis
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Also Published As

Publication number	Publication date
BR9305766A (pt)	1997-01-28
CA2128095A1 (en)	1993-08-05
WO1993015154A1 (en)	1993-08-05
JPH05214266A (ja)	1993-08-24
ZA93532B (en)	1993-08-26
AU3438393A (en)	1993-09-01
MX9300330A (es)	1993-12-31

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