EP0276371B1 - Verfahren zur Behandlung von Metalloberflächen - Google Patents

Verfahren zur Behandlung von Metalloberflächen Download PDF

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Publication number
EP0276371B1
EP0276371B1 EP87114670A EP87114670A EP0276371B1 EP 0276371 B1 EP0276371 B1 EP 0276371B1 EP 87114670 A EP87114670 A EP 87114670A EP 87114670 A EP87114670 A EP 87114670A EP 0276371 B1 EP0276371 B1 EP 0276371B1
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EP
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Prior art keywords
acid
parts
weight
group
compound
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Expired - Lifetime
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EP87114670A
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English (en)
French (fr)
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EP0276371A1 (de
Inventor
Toshio Nishikawa
Nobuhiro Ayukawa
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NOF Metal Coatings Asia Pacific Co Ltd
Original Assignee
Nippon Dacro Shamrock Co Ltd
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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
    • C23C22/02—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 non-aqueous solutions
    • C23C22/04—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 non-aqueous solutions containing hexavalent chromium compounds
    • 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
    • C23C22/02—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 non-aqueous solutions
    • C23C22/03—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 non-aqueous solutions containing phosphorus compounds

Definitions

  • This invention relates to a process for treating metal surface, by which corrosion resistance of the metal and adhesion of coating thereto are improved.
  • a phosphating treatment composition consisting of 100 parts by weight of a halogenated hydrocarbon solvent (carbon tetrachloride, chloroform, methylene chloride, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, trichlorotrifluoroethylene, perchloroethylene, trichlorotrifluoroethane, tetrachlorodifluoroethane, dichlorotetrafluoroethane, trifluoromonofluoromethane, etc.
  • a halogenated hydrocarbon solvent carbon tetrachloride, chloroform, methylene chloride, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, trichlorotrifluoroethylene, perchloroethylene, trichlorotrifluoroethane, tetrachlorodifluoroethane, dichlorotetrafluoroethan
  • phosphoric acid compound such as orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid such as triphosphoric acid, a salt thereof, an acidic metal salt of phosphoric acid, an acidic alkyl ester of phosphoric acid, or a mixture thereof
  • alcohol solubilizer having 1-10 carbon atoms such as methanol, ethanol, isopropyl alcohol, n-propanol, n-butanol, sec-butanol, t-butanol, etc.
  • This phosphating composition may contain a small amount of a quinone, an aromatic compound having a nitroso or azo functional group or a zinc compound such as zinc phosphate, zinc fluoride, zinc oxide, a fatty acid salt of zinc, etc. as a stabilizer for halogenated hydrocarbon solvent.
  • the phosphating composition may further contain 0.5-15 parts by weight of aprotic polar organic compound such as N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, acetone, nitromethane, nitrobenzene and tetramethylenesulfone.
  • aprotic polar organic compound such as N,N-dimethylformamide, dimethylsulfoxide, acetonitrile, acetone, nitromethane, nitrobenzene and tetramethylenesulfone.
  • the phosphating composition may still further contain not less than 0.4 part by weight and not more than 5 parts by weight of water (in an amount that maintains a homogeneous phase). Water acts as a reaction promoter.
  • Japanese Patent Publication Nos. 57-49111, 56-31878, etc. Japanese Patent Publication Nos. 57-49111, 56-31878, etc.
  • Japanese Laying-Open Patent Publication No. 61-34184 of the applicant of the present application discloses a metal-surface-treating solution consisting of 100 parts by weight of a chlorofluorinated hydrocarbon organic solvent (typically, trichlorotrifluoroethane, tetrachlorodifluoroethane, tetrachlorodifluoroethane, dichlorotetrafluoroethane, trichloromonofluoromethane, etc.
  • a chlorofluorinated hydrocarbon organic solvent typically, trichlorotrifluoroethane, tetrachlorodifluoroethane, tetrachlorodifluoroethane, dichlorotetrafluoroethane, trichloromonofluoromethane, etc.
  • an organic acid reaction promoter can be dispensed with 0.01-10 part by weight of chromic acid anhydride, 0.001-0.1 part by weight of an organic acid having 1-20 carbon atoms (typically, formic acid, acetic acid, lactic acid, stearic acid, oxalic acid, fumaric acid, naleic acid, malic acid, etc.) and 1-20 parts by weight of an alcohol solubilizer having 3-20 carbon atoms (typically isopropyl alcohol, tert-butanol, tert-amyl alcohol, triphenyl carbinol, etc. or a mixture thereof).
  • an organic acid reaction promoter can be dispensed with.
  • the treated metal surface exhibits excellent adhesion property to coatings (paints).
  • This invention provides a process for treating metal surface comprising subjecting a metal surface to phosphating treatment and subjecting the phosphated surface to chromic acid chemical conversion treatment, said process being characterized in that the phosphating treatment is carried out using a non-aqueous phosphating treatment solution in which a chlorinated or chlorofluorinated hydrocarbon is used as the solvent and the chromic acid chemical conversion treatment is carried out using a non-aqueous chromic acid chemical conversion treatment solution in which a chlorofluorinated hydrocarbon is used as the solvent.
  • the phosphating treatment composition per se is known as stated above.
  • the chromic acid chemical conversion composition per se is also known as stated above.
  • the process of the present invention is applicable to all the metals to which the known phosphating treatment and chromic acid chemical conversion treatment are applicable, that is, iron and steel, zinc, aluminum, tin and alloys thereof.
  • a phosphating treatment solution consisting of 100 parts by weight (hereinafter referred to simply as parts) trichlorotrifluoroethane, 22 parts methanol and 0.6 part orthophosphoric acid and 4 parts N,N-dimethylformamide was kept at the boiling temperature thereof.
  • Test panels 70 x150 x 0.8 mm cold-rolled steel sheets which had been degreased and cleansed beforehand were immersed in the boiling solution for 1 minute, were thereafter washed with the vapor in the vapor zone above the treating solution, and then were dried in the vapor-free space above the vapor zone.
  • a chromic acid chemical conversion treatment solution consisting of 100 parts trichlorotrifluoroethane, 5 parts t-amyl alcohol, and 1 part chromic acid anhydride was kept at the boiling temperature thereof, and the test panels which had been phosphated as described above were immersed in the boiling treating solution for 15 seconds, and then were dried in the vapor-free space.
  • the thus treated panels were coated with an epoxy resin powder paint ("Konac No. 3500” manufactured by Nippon Oil and Fats Company, Ltd.) or an acrylic resin powder paint ("Konac No. 4500” manufactured by Nippon Oil and Fats Company, Ltd.) by the electrostatic painting process, and the thus painted panels were baked at 180°C for 20 minutes.
  • an epoxy resin powder paint ("Konac No. 3500” manufactured by Nippon Oil and Fats Company, Ltd.) or an acrylic resin powder paint ("Konac No. 4500” manufactured by Nippon Oil and Fats Company, Ltd.) by the electrostatic painting process, and the thus painted panels were baked at 180°C for 20 minutes.
  • the adhesion of the paint was tested by scoring some of the painted panels in a grid pattern at intervals of 1 mm reaching the substrate, forming 100 small squares by means of a knife edge, applying a cellophane adhesive tape 20 mm in width (manufactured by Nichiban Co.) onto the scored surface and peeling off the tape quickly at an angle of 45°. The number of the remaining squares of the coating (paint) was counted and the adhesion of the coating film before the corrosion test (named primary adhesion) was evaluated.
  • Example 1 was repeated using the same chromic acid chemical conversion treatment composition which had been continuously used for 12 months.
  • Example 1 The procedure of Example 1 was repeated using a conventional chromic acid chemical conversion treatment composition in which methylene chloride (chlorinated hydrocarbon) was used as the solvent instead of the composition in which the fluorochlorinated hydrocarbon solvent was used.
  • methylene chloride chlorinated hydrocarbon
  • Example 1 The procedure of Example 1 was repeated using the same chromic acid chemical conversion treatment composition as used in Comparative Example 1 (using the chlorinated hydrocarbon) which had been continuously used for one week.
  • Test panels of the same kind as used in Example 1 were phosphated in the same manner as in Example 1. Then the thus phosphated panels were immersed in a fresh chromic acid chemical conversion treatment solution consisting of 100 parts trichlorotrifluoroethane, 5 parts t-amyl alcohol, and 0.05 part chromic acid anhydride, which was kept at the boiling temperature thereof, for 30 seconds, and then dried in the vapor-free space above the solution.
  • a fresh chromic acid chemical conversion treatment solution consisting of 100 parts trichlorotrifluoroethane, 5 parts t-amyl alcohol, and 0.05 part chromic acid anhydride, which was kept at the boiling temperature thereof, for 30 seconds, and then dried in the vapor-free space above the solution.
  • the thus treated panels were coated with the same epoxy and acrylic resin powder paints as used in Example 1 and the primary adhesion and the secondary adhesion were respectively measured.
  • Example 2 The procedure of Example 2 was repeated with the exception that trichloroethane was used as the solvent in the chromic acid chemical conversion treatment solution.
  • a phosphating treatment solution consisting of 100 parts methylene chloride, 36 parts methanol, 0.5 part orthophosphoric acid and 6 parts N,N-dimethyl formamide was kept at the boiling temperature thereof.
  • Test panels of the same kind as used in Example 1 which had been degreased and cleansed beforehand were immersed in this boiling solution for 1 minute, thereafter they were dried in the vapor-free zone in the treating vessel. (Phosphating treatment)
  • a chromic acid chemical conversion treatment solution consisting of 100 parts trichlorotrifluoroethane, 5 parts t-amyl alcohol and 0.5 part chromic acid anhydride was kept at the boiling temperature thereof, and the test panels which had been phosphated as described above were immersed in this boiling solution for 20 seconds, and then were dried in the vapor-free space.
  • Example 3 The procedure of Example 3 was repeated with the exception that trichloroethylene was used as the solvent and 0.007 part zinc fluoride was added to the chromic acid chemical conversion treatment solution as a stabilizer. The results are indicated in Table 3 together with the results of Example 3. There was marked occurrence of blisters at the cross cutting, and the width of the peeled-off zone of the coating caused by the cellophane tape was broader.
  • Example 3 The procedure of Example 3 was repeated with the exception that the panels were coated with a phthalic acid resin paint ("Glastone No. 1000" manufactured by Nippon Oil and Fats Co.) by spraying and were forcedly dried at 80°C for 30 minutes. The results are indicated in Table 4.
  • Comparative Example 3 The procedure of Comparative Example 3 was repeated with the exception that the panels were coated with the phthalic acid resin paint used in Example 4 and was forcedly dried at 80°C for 30 minutes. The results are indicated in Table 4 together with the results of Example 4. The coating around the cross cutting was markedly damaged.
  • Example 3 The procedure of Example 3 was repeated with the exception that the panels were coated with a melamine alkyd resin paint ("Melamine No. 1" manufactured by Nippon Oil and Fats Co.) by spraying and baked at 150°C for 20 minutes, and the panels were tested in the same manner as in Example 3. The results are indicated in Table 5.
  • Example 3 The procedure of Example 3 was repeated with the exception that the panels were coated with the melamine alkyd resin paint used in Example 5 by spraying and baked at 150°C for 20 minutes and the panels were tested in the same manner. The results are indicated in Table 5.
  • a phosphating solution consisting of 100 parts trichlorotrifluoroethane, 22 parts methanol, 0.6 part orthophosphoric acid and 4 parts N,N-dimethylformamide was kept at the boiling temperature thereof.
  • Test panels 70 x 150 x 0.8 mm galvanized steel sheets which had been degreased and cleansed beforehand were immersed in the boiling solution for 1 minute, were thereafter washed with the vapor in the vapor zone above the treating solution and then dried in the vapor-free space. (Phosphating treatment).
  • a chromic acid chemical conversion treatment solution consisting of 100 parts trichlorotrifluoroethane, 5 parts t-amyl alcohol and 1 part chromic acid anhydride was kept at the boiling temperature thereof.
  • the test panels which had been phosphated as described above were immersed in this boiling solution for 15 seconds and dried in the vapor-free space.
  • the thus treated panels were coated with an acrylic resin cationic electrodeposition paint ("Aqua No. 8000” manufactured by Nippon Oil and Fats Co.) by the conventional electrodeposition process, and baked at 170°C for 25 minutes.
  • an acrylic resin cationic electrodeposition paint (“Aqua No. 8000” manufactured by Nippon Oil and Fats Co.) by the conventional electrodeposition process, and baked at 170°C for 25 minutes.
  • Example 6 The procedure of Example 6 was repeated with the exception that methylene chloride was used as the solvent in the chromic acid chemical conversion treatment solution. The test results are indicated in Table 6 together with the results of Example 6.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (6)

  1. Verfahren zur Behandlung einer Metalloberfläche gemäß dem eine Metalloberfläche einer Phosphatierung unterworfen wird und die phosohatierte Oberfläche einer chemischen Umformungsbehandlung mit Chromsäure unterworfen wird, wobei das Verfahren dadurch gekennzeichnet ist, daß die Phosphatierung unter Verwendung einer nicht wässrigen Phosphatierungslösung in der ein chlorierter oder chlorfluorierter Kohlenwasserstoff als Lösungsmittel verwendet wird, durchgeführt wird, und die chemische Umformungsbehandlung mit Chromsäure unter Verwendung einer nicht wässrigen Chromsäurelösung zur chemischen Umformungsbehandlung in der ein chlorfluorierter Kohlenwasserstoff als Lösungsmittel verwendet wird, durchgeführt wird.
  2. Verfahren zur Behandlung einer Metalloberfläche nach Anspruch 1, gemäß dem die nicht wässrige Phosphatierungslösung 100 Gewichtsteile eines chlorierten oder chlorfluorierten Kohlenwasserstoffs, 0,05 bis 5 Gewichtsteile einer Phosphorsäureverbindung, 1 bis 75 Gewichtsteile eines alkoholischen Lösungsvermittlers mit 1 bis 20 Kohlenstoffatomen, 0 bis 2 Gewichtsteile einer stickstoffhaltigen organischen Verbindung als Reaktionsbeschleuniger und 0 bis 15 Gewichtsteile einer aprotischen polaren Verbindung enthält; und die nicht wässrige Chromsäurelösung für die chemische Umformungsbehandlung 100 Gewichtsteile eines chlorfluorierten Kohlenwasserstoffs, 0,01 bis 10 Gewichtsteile Chromsäureanhydrid, 0 bis 0,1 Gewichtsteile einer organischen Säure mit 1 bis 20 Kohlenstoffatomen und 1 bis 20 Gewichtsteile eines alkoholischen Lösungsvermittlers mit 3 bis 20 Kohlenstoffatomen enthält.
  3. Verfahren zur Behandlung einer Metalloberfläche nach Anspruch 1, gemäß dem für die Phosphatierungslösung der chlorierte oder chlorfluorierte Kohlenwasserstoff ausgewählt wird unter Tetrachlorkohlenstoff, Chloroform, Methylenchlorid, 1,1,1-Trichlorethan, Trichlorethylen, Perchlorethylen, Trichlortrifluorethan, Tetrachlordifluorethan, Dichlortetrafluorethan, Trichlormonofluormethan und Gemischen aus einer oder mehrerer dieser Verbindungen; die Phosphorsäureverbindung ausgewählt wird unter Orthophosphorsäure, Pyrophosphorsäure, Polyphosphorsäure, deren Salzen, einem sauren Metallsalz der Phosphorsäure, einem sauren Alkylester der Phosphorsäure, und deren Gemischen; der alkoholische Lösungsvermittler ausgewählt wird unter Methanol, Ethanol, Isopropylalkohol, n-Propanol, n-Butanol, Isobutanol und t-Butanol; die stickstoffhaltige organische Verbindung ausgewählt wird unter Harnstoff, Pyridin, Thioharnstoff, Dimethylisobutylenamin, Ethylendiamintetraacetat und Dinitrotoluol; und die arrotische polare Verbindung ausgewählt wird unter N,N-Dimethylformamid, Dimethylsulfoxid, Acetonitril, Aceton, Nitromethan, Nitrobenzol und Tetramethylensulfon; und gemäß dem für die Chromsäurelösung für die chemische Umformungsbehandlung die chlorfluorierte Verbindung ausgewählt wird unter Trichlortrifluorethan, Tetrachlordifluorethan, Dichlortetrafluorethan und Trichlormonofluormethan; die organische Säure ausgewählt wird unter Ameisensäure, Essigsäure, Milchsäure, Stearinsäure, Oxalsäure, Fumarsäure, Maleinsäure und Apfelsäure; und der alkoholische Lösungsvermittler ausgewählt wird unter Isopropylalkohol, n-Propanol, tert-Butanol, tert-Amylalkohol, Triphenylmethanol und Gemischen aus einer oder mehrerer dieser Verbindungen.
  4. Verfahren zur Behandlung einer Metalloberfläche nach Anspruch 2 oder 3, gemäß dem die Phosphatierungslösung eine kleine Menge eines Stabilisators für das chlorierte Kohlenwasserstofflösungsmittel enthält, der ausgewählt wird unter einem Cuinon, einer aromatischen Verbindung mit einer funktionellen Nitroso- oder Azogruppe und einer Zinkverbindung.
  5. Verfahren zur Behandlung einer Metalloberfläche nach Anspruch 4, gemäß dem für die Phosphatierungslösung die chlorfluorierte Verbindung ausgewählt wird unter Methylenchlorid und Trichlortrifluorethan; die Säureverbindung ausgewählt wird unter Orthophosphorsäure, Pyrophosphorsäure und Polyphosphorsäure; der alkoholische Lösungsvermittler ausgewählt wird unter Methanol, Ethanol, Isopropylalkohol und t-Butanol; die stickstoffhaltige organische Verbindung ausgewählt wird unter Dinitrotoluol, Thioharnstoff und Dimethylisobutylenamin; und gemäß dem für die Chromsäurelösung für die chemische Umformung das chlorfluorierte Kohlenwasserstofflösungsmittel ausgewählt wird unter Trichlortrifluorethan, Tetrachlordifluorethan und Trichlormonofluormethan; die organische Säure ausgewählt wird unter Ameisensäure, Fumarsäure, Oxalsäure, Essigsäure und Milchsäure; der alkoholische Lösungsvermittler ausgewählt wird unter t-Butanol, t-Amylalkohol und Isopropylalkohol.
  6. Verfahren zur Behandlung einer Metalloberfläche nach Anspruch 5, gemäß dem die Phosphatierungslösung aus 100 Gewichtsteilen Methylenchlorid oder Trichlortrifluorethan, 0,1 bis 3,0 Gewichtteilen Orthophosphorsäure oder Pyrophosphorsäure, 10 bis 40 Gewichtsteilen Methanol, Ethanol oder t-Butanol, 0,1 bis 1 Gewichtsteilen Dinitrotoluol oder Thioharnstoff, und 1 bis 10 Gewichtsteilen N,N-Dimethylformamid oder Dimethylsulfoxid besteht; und die Chromsäurelösung für die chemische Umformungsbehandlung 100 Gewichtsteile Trichlorfluorethan oder Tetrachlordifluorethan, 0,07 bis 2 Gewichtsteile Chromsäureanhydrid, 0,01 bis 0,05 Gewichtsteile Ameisensäure, Fumarsäure oder Oxalsäure enthält.
EP87114670A 1987-01-09 1987-10-08 Verfahren zur Behandlung von Metalloberflächen Expired - Lifetime EP0276371B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1824/87 1987-01-09
JP62001824A JPS63171884A (ja) 1987-01-09 1987-01-09 金属表面処理法

Publications (2)

Publication Number Publication Date
EP0276371A1 EP0276371A1 (de) 1988-08-03
EP0276371B1 true EP0276371B1 (de) 1991-03-20

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EP87114670A Expired - Lifetime EP0276371B1 (de) 1987-01-09 1987-10-08 Verfahren zur Behandlung von Metalloberflächen

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EP (1) EP0276371B1 (de)
JP (1) JPS63171884A (de)
DE (1) DE3768801D1 (de)
ZA (1) ZA877722B (de)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2927046A (en) * 1958-11-20 1960-03-01 Parker Rust Proof Co Coated metals and solutions and process for making the same
US3285788A (en) * 1963-06-14 1966-11-15 Du Pont Anhydrous chromic acid solution and process of treating metal therewith
US3437531A (en) * 1962-07-26 1969-04-08 Du Pont Anhydrous chromic acid metal treating solution
US4008101A (en) * 1975-03-20 1977-02-15 Diamond Shamrock Corporation Methylene chloride phosphatizing
US4029523A (en) * 1975-03-20 1977-06-14 Diamond Shamrock Corporation Solvent phosphatizing compositions yielding non water soluble coatings
DE3209829A1 (de) * 1982-03-18 1983-10-06 Huels Chemische Werke Ag Organische phosphatierloesung zur phosphatierung von metalloberflaechen
JPS6134184A (ja) * 1984-07-25 1986-02-18 Nippon Dakuro Shamrock:Kk 金属表面処理液

Also Published As

Publication number Publication date
JPH0551667B2 (de) 1993-08-03
EP0276371A1 (de) 1988-08-03
JPS63171884A (ja) 1988-07-15
ZA877722B (en) 1988-04-20
DE3768801D1 (de) 1991-04-25

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