EP0824565B1 - Zusammensetzung und verfahren zur behandlung von metall - Google Patents

Zusammensetzung und verfahren zur behandlung von metall Download PDF

Info

Publication number
EP0824565B1
EP0824565B1 EP95918314A EP95918314A EP0824565B1 EP 0824565 B1 EP0824565 B1 EP 0824565B1 EP 95918314 A EP95918314 A EP 95918314A EP 95918314 A EP95918314 A EP 95918314A EP 0824565 B1 EP0824565 B1 EP 0824565B1
Authority
EP
European Patent Office
Prior art keywords
water
parts
composition
liquid composition
aqueous liquid
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 - Lifetime
Application number
EP95918314A
Other languages
English (en)
French (fr)
Other versions
EP0824565A1 (de
EP0824565A4 (de
Inventor
David Y. Dollman
Shawn E. Dolan
Lester E. Steinbrecher
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.)
Filing date
Publication date
Priority claimed from US07/862,012 external-priority patent/US5281282A/en
Priority claimed from US08/429,431 external-priority patent/US5534082A/en
Application filed by Henkel Corp filed Critical Henkel Corp
Publication of EP0824565A1 publication Critical patent/EP0824565A1/de
Publication of EP0824565A4 publication Critical patent/EP0824565A4/de
Application granted granted Critical
Publication of EP0824565B1 publication Critical patent/EP0824565B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C22/34—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 fluorides or complex fluorides
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/37—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 fluorides or complex fluorides containing also hexavalent chromium compounds

Definitions

  • This invention relates to processes of treating metal surfaces with aqueous acidic compositions to increase the resistance to corrosion of the treated metal surfaces, either as thus treated or after subsequent overcoating with some conventional organic based protective layer.
  • a major object of the invention is to provide a storage stable, preferably single package, treatment that can be substantially free from hexavalent chromium but can protect metals substantially as well as hexavalent chromium containing treatments of the prior art, or can improve the stability of treatment solutions that do contain hexavalent chromium.
  • This invention also relates to reaction of fluorometallic acids with other metal or metalloid containing materials to produce compositions or intermediates for compositions useful for such treatments.
  • compositions comprising water-soluble or -dispersible polyvinyl alcohol and/or polymers and copolymers of acrylic and/or methacrylic acids are known, for example from European Publications Nos. EP 0,450,437 and EP 0,645,428, British Publication No. GB 2,090,603, United States Publication No. US 3,133,865, and Japanese Publications Nos. JP 62,001,882 and JP 62,010,280 (Patent Abstracts of Japan vol. 011, no. 176 (C-426) and no. 185 (C-428).)
  • percent, "parts of”, and ratio values are by weight;
  • the term "polymer” includes oligomer;
  • the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred;
  • description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed;
  • specification of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole (any counterions thus implicitly specified should preferably be selected from among other constituents explicitly specified in ionic form, to the extent possible; otherwise such counterions may be freely selected, except for avoiding counterions that act adversely to the stated objects of the invention); and the term "mole” and its variations may be applied to elemental, ionic, and any other chemical species defined by number and type of atoms present, as well as
  • the present invention provides a composition and process for coating surfaces of aluminium and alloys thereof, wherein the composition comprises preferably consists essentially of, or more preferably consists of, water and a mixture of:
  • compositions above do not preclude the possibility of unspecified chemical interactions among the components listed, but instead describes the components of a composition according to the invention in the form in which they are generally used as ingredients to prepare such a composition.
  • a chemical interaction most probably to produce oxyfluoro complexes of the metal or metalloid elements or their compounds heated in contact with fluorometallic acids, is believed to occur, but the invention is not limited by any such theory.
  • compositions are suitable for treating metal surfaces to achieve excellent resistance to corrosion, particularly after subsequent conventional coating with an organic binder containing protective coating.
  • the compositions are particularly useful on iron and steel, galvanised iron and steel, zinc and those of its alloys that contain at least 50 atomic percent zinc, and, most preferably, aluminium and its alloys that contain at least 50 atomic percent aluminium.
  • the treating may consist either of coating the metal with a liquid film of the composition and then drying this liquid film in place on the surface of the metal, or simply contacting the metal with the composition for a sufficient time to produce an improvement in the resistance of the surface to corrosion, and subsequently rinsing before drying. Such contact may be achieved by spraying, immersion, and the like as known per se in the art.
  • the invention also provides a process for effectively coating the above-stated metallic surfaces in the absence of an intermediate rinsing step.
  • the process comprises the steps of (i) cleaning the metal surface to be coated, (ii) rinsing the cleaned metal surface with water so as to remove any excess cleaning solution, (iii) contacting the metallic surface with the above-described coating composition, and (iv) drying the coated metallic surface.
  • the major type of coating used in the invention employing a coating composition including necessary components (A'), (B') and (C') as already described above, has been found to be especially useful for treating metallic surfaces that are exposed to alkali metal ions, particularly sodium such as often occurs in detergents and other cleaners, after the treatment with a composition according to this invention has been completed.
  • a coating composition including necessary components (A'), (B') and (C') as already described above, has been found to be especially useful for treating metallic surfaces that are exposed to alkali metal ions, particularly sodium such as often occurs in detergents and other cleaners, after the treatment with a composition according to this invention has been completed.
  • Protective coatings applied to metallic surfaces, particularly aluminium preferably are water insoluble and inhibit corrosion.
  • metallic surfaces bearing a protective coating are often exposed to sodium ions later.
  • the composition contacted with a metallic surface comprises water and: (A') from 0.5 to 50 g/l and (B') from 0.5 to 50, and more preferably from 0.5 to 16g/l of polyvinyl alcohol.
  • the polyvinyl alcohol used in the invention preferably is a low molecular weight polyvinyl alcohol which is 75 - 99+ mole % hydrolysed, and has an average degree of polymerisation ranging from 100-600.
  • water soluble or dispersible polymer having at least one -OH group per polymer molecule may be employed without departing from the spirit of the invention
  • preferred polymers and amounts thereof include the above-stated polyvinyl alcohol; from 0.3 to 16g/l , preferably from 0.3 to 1.2g/l, of polyethylene glycol having a molecular weight of from 90,000 to 900,0000; from 0.5 to 16g/l, and preferably from 0.5 to 10 g/l of dextrin, cyclodextrin, or a modified starch.
  • modified starch is one commonly known in the art. It refers to any of several water-soluble polymers derived from a starch by acetylation, chlorination, acid hydrolysis, or enzymatic action. These reactions yield starch acetates, esters, and ethers in the form of stable and fluid solutions and films. These starch derivatives useful herein are well known.
  • the hydroxyalkyl starch ethers and starch esters can be obtained by known etherification and esterification processes. These starch ethers and esters should have a degree of substitutions (hereinafter often abbreviated "D.S.") of 0.01 to 0.5, and preferably 0.1 to 0.5. As used herein D.S. means the average degree of substitution of starch hydroxyl groups per anhydroglucose unit of the chemical modifying substituent, as for example a hydroxyalkyl or carbonyl group.
  • D.S. means the average degree of substitution of starch hydroxyl groups per anhydroglucose unit of the chemical modifying substituent, as for example a hydroxyalkyl or carbonyl group.
  • Oxidised starch can be obtained by known processes involving oxidation of starch with a suitable oxidising agent, as for example sodium hypochlorite, potassium dichromate, and sodium permanganate.
  • the starch can be oxidised under acid, alkaline or neutral conditions, and the resulting product can contain carboxyl and carbonyl groups.
  • the oxidised starch has a "D.O.” value of 0.01 to 1.0, where "D.O.” refers to the number of carboxyl groups introduced per anhydroglucose unit.
  • Dextrins and cyclodextrins are polysaccharide products of a complex nature resulting from the partial degradation of starch, such as corn starch, potato starch, wheat starch, and the like, with heat, as for example, by roasting with acid or alkaline catalysts.
  • Linear and branched dextrins are classified in three types. The particular type obtained depends on the heating time, temperature, and catalyst employed in the treatment of the starch. These types are classified as white dextrins, yellow or canary dextrins, and British gums, and all such dextrins are suitable herein. White and canary dextrins are preferred in that British gums are brown in colour.
  • White dextrins are preferably pregelatinised (made water soluble during manufacture), if necessary, to render them more readily mixed with other water soluble components. Dextrins and methods for obtaining them are well known. See, for example, Whistler and Paschall op . cit. Vol. I, p. 421 ff and vol. II, p. 253 ff.
  • the starch hydrolysates useful in the compositions of this invention are a relatively new class of starch materials. These starch hydrolysates are made by subjecting a source of starch, such as hereinbefore mentioned, to enzyme or acid treatment or a combination of both. It is important that the starch hydrolysate have a relatively low dextrose equivalent (hereinafter often abbreviated "D.E.”).
  • the starch hydrolysate should have a D.E. of from 2 to 35, and preferably have a D.E. of from 5 to 25. The most preferred materials have a D.E. within the range of 5 to 15. (The term D.E.
  • modified starches include cyclodextrins, which are macrocyclic non-reducing D-glucosyl polymers containing six or more D-glucosyl residues bonded by ⁇ -(1,4) links.
  • cyclodextrins are macrocyclic non-reducing D-glucosyl polymers containing six or more D-glucosyl residues bonded by ⁇ -(1,4) links.
  • the pH of a composition according to this invention that contains components (A'), (B'), and (C') as necessary components preferably is in the range from 1.0 to 5.0, and more preferably from 1.0 to 3.5.
  • the treating composition also includes 0.2 to 19.0, and more preferably from 0.2 to 8.0 g/l, of fluoroacids component (C') admixed therein.
  • Component (C') is preferably selected from the group consisting of H 2 TiF 6 , H 2 ZrF 6 , and H 2 SiF 6 , and more preferably is H 2 TiF 6 and/or H 2 ZrF 6 .
  • Another embodiment of the invention is a process of treating a metal with a composition prepared as described above.
  • the aqueous composition as described above be applied to the metal surface and dried in place thereon.
  • coating the metal with a liquid film may be accomplished by immersing the surface in a container of the liquid composition, spraying the composition on the surface, coating the surface by passing it between upper and lower rollers with the lower roller immersed in a container of the liquid composition, and the like, or by a mixture of methods. Excessive amounts of the liquid composition that might otherwise remain on the surface prior to drying may be removed before drying by any convenient method, such as drainage under the influence of gravity, squeegees, passing between rolls, and the like.
  • the surface to be coated is a continuous flat sheet or coil and precisely controllable coating techniques such as gravure roll coaters are used, a relatively small volume per unit area of a concentrated composition may effectively be used for direct application.
  • the coating equipment used does not readily permit precise coating at low coating add-on liquid volume levels, it is equally effective to use a more dilute acidic aqueous composition to apply a thicker liquid coating that contains the same amount of active ingredients.
  • Drying may be accomplished by any convenient method, of which many are known per se in the art; examples are hot air and infrared radiative drying. Independently, it is preferred that the maximum temperature of the metal reached during drying fall within the range from 30 to 200, more preferably from 30 to 150, still more preferably from 30 to 75,°C. Also independently, it is often preferred that the drying be completed within a time ranging from 0.5 to 300, more preferably from 2 to 50, still more preferably from 2 to 10, seconds (hereinafter abbreviated "sec") after coating is completed.
  • sec seconds
  • the metal to be treated preferably is contacted with a composition prepared as described above at a temperature within the range from 25 to 90, more preferably from 30 to 85, still more preferably from 30 to 60, °C for a time ranging from 1 to 1800, more preferably from 1 to 300, still more preferably from 3 to 30, sec, and the metal surface thus treated is subsequently rinsed with water in one or more stages before being dried.
  • at least one rinse after treatment with a composition according to this invention preferably is with demonised, distilled, or otherwise purified water.
  • the maximum temperature of the metal reached during drying fall within the range from 30 to 200, more preferably from 30 to 150, or still more preferably from 30 to 75, °C and that, independently, drying be completed within a time ranging from 0.5 to 300, more preferably from 2 to 50, still more preferably from 2 to 10, sec after the last contact of the treated metal with a liquid before drying is completed.
  • a process according to the invention as generally described in its essential features above may be, and usually preferably is, continued by coating the dried metal surface produced by the treatment as described above with a siccative coating or other protective coating, relatively thick as compared with the coating formed by the earlier stages of a process according to the invention as described above.
  • Such protective coatings may generally, in connection with this invention, be selected and applied as known per se in the art. Surfaces thus coated have been found to have excellent resistance to subsequent corrosion, as illustrated in the examples below.
  • Particularly preferred types of protective coatings for use in conjunction with this invention include acrylic and polyester based paints, enamels, lacquers, and the like.
  • hexavalent chromium may impart sufficient additional corrosion protection to the treated metal surfaces to justify the increased cost of using and lawfully disposing of it.
  • the metal surface to be treated according to the invention is first cleaned of any contaminants, particularly organic contaminants and foreign metal fines and/or inclusions.
  • cleaning may be accomplished by methods known to those skilled in the art and adapted to the particular type of metal substrate to be treated.
  • the substrate is most preferably cleaned with a conventional hot alkaline cleaner, then rinsed with hot water, squeegeed, and dried.
  • the surface to be treated most preferably is first contacted with either an aqueous alkaline cleaning solution in accordance with that disclosed in U.S. Patent No. 4,762,638, incorporated herein by reference, or an aqueous acidic cleaning solution as disclosed in U.S. Pat. No.
  • aqueous acidic cleaning solution a source of fluoride such as HF may also be employed to even further enhance the cleaning process.
  • a source of fluoride such as HF may also be employed to even further enhance the cleaning process.
  • the aluminum is then subjected to a water rinse, after which a composition in accordance with the present invention may then be coated onto the aluminum in accordance with the processes disclosed herein.
  • Test pieces of Type 3105 aluminum were spray cleaned for 15 seconds at 54.4° C with an aqueous cleaner containing 28 g/L of PARCO® Cleaner 305 (commercially available from the Parker+Amchem Division of Henkel Corp., Madison Heights, Michigan, USA). After cleaning, the panels were rinsed with hot water, squeegeed, and dried before roll coating with an acidic aqueous composition as described for the individual examples and comparison examples below.
  • an aqueous cleaner containing 28 g/L of PARCO® Cleaner 305 (commercially available from the Parker+Amchem Division of Henkel Corp., Madison Heights, Michigan, USA).
  • the applied liquid composition according to the invention was flash dried in an infrared oven that produces approximately 49° C peak metal temperature. Samples thus treated were subsequently coated, according to the recommendations of the suppliers, with various commercial paints as specified further below.
  • T-Bend tests were according to American Society for Testing materials (hereinafter "ASTM") Method D4145-83; Impact tests were according to ASTM Method D2794-84E1; Salt Spray tests were according to ASTM Method B-117-90 Standard; Acetic Acid Salt Spray tests were according to ASTM Method B-287-74 Standard; and Humidity tests were according to ASTM D2247-8 Stahdard.
  • the Boiling water immersion test was performed as follows: A 2T bend and a reverse impact deformation were performed on the treated and painted panel. The panel was then immersed for 10 minutes in boiling water at normal atmospheric pressure, and areas of the panel most affected by the T-bend and reverse impact deformations were examined to determine the percent of the paint film originally on these areas that had not been exfoliated. The rating is reported as a number that is one tenth of the percentage of paint not exfoliated. Thus, the best possible rating is 10, indicating no exfoliation; a rating of 5 indicates 50 % exfoliation; etc.
  • amorphous fumed silicon dioxide 396.2 parts of deionized water 56.6 parts of aqueous 60 % fluotitanic acid (i.e., H 2 TiF 6 ) 325.4 parts of deionized water 216.2 parts of an aqueous solution containing a mixture of 4.1 g/l polyacrylic acid and 4.0 g/l polyvinyl alcohol
  • Example 1 56.4 parts of aqueous 60 % fluotitanic acid 56.4 parts of deionized water 2.1 parts of AerosilTM R-972 (a surface treated dispersed silica) 667.0 parts of deionized water 218.1 parts of the 10 % water soluble polymer solution as used in Example 1
  • Example 1 58.8 parts of aqueous 60 % fluotitanic acid 3.7 parts of amorphous fumed silicon dioxide 10.3 parts of zirconium basic carbonate 647.7 parts of deionized water 279.5 parts of the 10 % solution of water soluble polymer as used in Example 1
  • Example 4 For each of Examples 1 - 6 and 8 - 10, the ingredients were added in the order indicated to a container provided with stirring. (Glass containers are susceptible to chemical attack by the compositions and generally should not be used, even on a laboratory scale; containers of austenitic stainless steels such as Type 316 and containers made of or fully lined with resistant plastics such as polymers of tetrafluoroethene or chlorotrifluoroethene have proved to be satisfactory.)
  • the mixture was heated to a temperature in the range from 38 - 43 ° C and maintained within that range of temperatures for a time of 20 - 30 minutes. Then the mixture was cooled to a temperature below 30° C, and the remaining ingredients were stirred in without additional heating, until a clear solution was obtained after each addition.
  • Example 4 the SiO 2 used was surface modified with a silane, and because of its hydrophobic nature, the mixture containing this form of silica was heated for 1.5 hours at 70° C to achieve transparency. The remaining steps of the process were the same as for Example 1.
  • Example 7 the first three ingredients listed were mixed together arid maintained at 40 ⁇ 5 ° C for 20 - 30 minutes with stirring and then cooled.
  • the CrO 3 was dissolved in about fifteen times its own weight of water, and to this solution was added a slurry of the corn starch in twenty-four times its own weight of water.
  • the mixture was then maintained for 90 minutes with gentle stirring at 88 ⁇ 6 ° C to reduce part of the hexavalent chromium content to trivalent chromium.
  • this mixture was cooled with stirring and then added to the previously prepared heated mixture of fluotitanic acid, silicon dioxide, and water.
  • This composition is used in the manner known in the art for compositions containing hexavalent and trivalent chromium and dispersed silica, but it is much more stable to storage without phase separation.
  • Example 5 65 mg/m 2 e N e N as Ti s N s N Vf 9
  • Example 5 10 10 22 mg/m 2 e N e N as Ti s N s N Vf 9
  • Example 5 10 54 mg/m 2 e N e N s N s N Vf 9
  • Example 6 10 22 mg/m 2 e 0-1 s e N s N Vf 9
  • Example 6 10 54 mg/m 2 e 0-1 s e N s N s N Vf 9
  • Example 8 9.8 10 12 mg/m 2 e N e N s 0-1 s s N N N
  • Example 8 9.6
  • Example 9 10 11 mg/m 2 e N e N s 0-1 s 0-1 s N
  • Example 9 9.8 10 24 mg/m 2 e 0-1 s e N s 0-1 s 0-1 N
  • Example 2 The storage stability of the compositions according to all of the examples above except Example 2 was so good that no phase separation could be observed after at least 1500 hours of storage. For Example 2, some settling of a slight amount of apparent solid phase was observable after 150 hours.
  • test pieces of Type 5352 or 5182 aluminum were spray cleaned for 10 seconds at 54.4° C with an aqueous cleaner containing 24 g/L of PARCO® Cleaner 305 (commercially available from the Parker+Amchem Division of Henkel Corp., Madison Heights, Michigan, USA).
  • the panels were rinsed with hot water; then they were sprayed with the respective treatment solutions according to the invention, which were the same as those already described above with the same Example Number, except that they were further diluted with water to the concentration shown in the tables below, for 5 seconds; and then were rinsed successively with cold tap water and deionized water and dried, prior to painting.
  • DOWFAXTM 2A1 is commercially available from Dow Chemical and is described by the supplier as 45 % active sodium dodecyl diphenyloxide disulfonate.
  • the "Cross Hatch” test after this treatment was made in the same way as described above for steps 2 - 4 after “Ninety Minute Steam Exposure”.
  • the "Reverse Impact” test was made as described in ASTM D2794-84E1 (for 20 inch pounds impact), then proceeding in the same way as described above for steps 3 - 4 after "Ninety Minute Steam Exposure”.
  • the "Feathering” test was performed as follows: Using a utility knife, scribe a slightly curved "V" on the back side of the test panel.
  • Type 5352 aluminum was used, and the process sequence used in part I, except for final drying, was used but was then followed by passing the test pieces, still wet from the deionized water rinse after contact with a composition according to this invention, through power driven squeegee rolls arranged so that the test pieces passed through the squeegee rolls in a horizontal position immediately after being sprayed liberally with the final treatment liquid composition at a temperature of 60° C before being dried.
  • Example 11 the treatment liquid in this final stage was simply deionized water with a conductivity of not more than 4.0 ⁇ Siemens/cm, while in Example 12 the treatment liquid in this final stage was obtained by mixing 35 ml of ParcoleneTM 95AT and 2.0 ml of ParcoleneTM 88B with 7 liters of deionized water and had a pH of 5.18 and a conductivity of 56 ⁇ Siemens/cm.
  • Bottom ParcoleneTM products noted are commercially available from the Parker+Amchem Div.
  • This latter type of final treatment liquid is an example of one containing polymers and/or copolymers of one or more x-(N-R 1 -N-R 2 -aminomethyl)-4-hydroxy-styrenes as already described above.
  • Concentrate II-II used in each of Examples 11 - 13 had the following composition: 1892.7 parts of deionized water 83.7 parts of 60 % aqueous fluotitanic acid 5.3 parts of Cab-O-SilTM M-5 fumed amorphous silicon dioxide 18.3 parts of zirconium basic carbonate. These ingredients were simply mixed together with mechanical agitation in the order shown, with a pause after each addition until the solution became optically clear. Although the partial mixture was not transparent immediately after addition of the silicon dioxide, it became clear after a few minutes of mixing, even without any heating.
  • the working solution for Examples 11 and 12 was prepared by diluting 200 grams of the concentrate II-II, along with sufficient sodium carbonate to result in a pH of 2.92 ⁇ 0.2, to form 6 liters of working composition.
  • the working solution was made in the same way, except that it also contained 5 grams of a concentrated polymer solution made according to the directions of column 11 lines 39 - 49 of U.S.
  • Patent 4,963,596 except as follows: The preparation was carried out on a substantially larger scale; the proportions of ingredients were changed to the following: 241 parts of PropasolTM P, 109 parts of Resin M, 179 parts of N-methylglucamine, 73.5 parts of aqueous 37 % formaldehyde, and 398 parts of deionized water, of which 126 parts were reserved for a final addition not described in the noted patent, with the remainder used to slurry the N-methylglucamine as noted in the patent; and the temperature noted as 60 - 65 ° C in the patent was reduced to 57° C.
  • a first concentrate was made by mixing 750 parts of tap water and 274 parts of AcrysolTM A-1, a commercially available product from Rohm and Haas containing 25.% solids of polymers of acrylic acid with a molecular weight of less than 50,000.
  • a second concentrate was made by mixing, in a container separate from that used for the first concentrate 951.3 parts of tap water and 66.7 g/l of GohsenolTM GLO-5, a commercially available product from Nippon Gohsei which is a low molecular weight polyvinyl alcohol; the latter was added to the tap water with stirring at a slow and controlled flow, after which the temperature was increased to 49 - 54 ° C for 30 minutes with slow stirring until all was dissolved.
  • This composition was then contacted with an aluminum surface by dipping or spraying for a time from 30 to 60 seconds, after which time the surfaces treated were removed from contact with the treating composition, allowed to dry in the ambient atmosphere without rinsing, and then baked in a warm air oven at 88° C for 5 minutes to simulate commercial operating conditions.
  • the surfaces thus prepared were painted with conventional paints.
  • the treating composition is prepared in the same general manner as in Example 14, by making separate concentrates of the hydroxyl group containing polymer and polyacrylic acid components, mixing an appropriate amount of these concentrates with a larger volume of water, adding any additional components used, and finally adjusting to the final desired volume or mass by the addition of more water. These compositions are then applied to aluminum surfaces in the same manner as described for Example 14.
  • the specific active ingredients and concentrations or amounts thereof in the treatment composition for each example are as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (8)

  1. Wässrige, flüssige Zusammensetzung, die neben Wasser im wesentlichen aus den folgenden Komponenten besteht:
    (A') einem wasserlöslichen oder wasserdispergierbaren Polyvinylalkohol, der in einem Konzentrationsbereich von 0,5 bis 50 g/l vorhanden ist;
    (B') einem Stoff oder einer Mischung von mehr als einem der folgenden Stoffe, nämlich Polymere und Copolymere von Acrylsäure und Methacrylsäure und deren Salze, die in einer Gesamtkonzentration von 0,5 bis 50 g/l vorhanden sind;
    (C') einer aus H2TiF6, H2ZrF6, H2HfF6, H3AlF6, H2SiF6, H2GeF6, H2SnF4, HBF4 und Mischungen davon ausgewählte Komponente, die in einer Gesamtkonzentration von 0,01 bis 7 M vorhanden ist;
    und gegebenenfalls einer oder mehrerer der folgenden Komponenten:
    (D') einer Komponente, die ausgewählt ist aus den wasserunlöslichen Oxiden, wasserunlöslichen Hydroxiden, wasserunlöslichen Carbonaten und/oder wasserunlöslichen elementaren Formen von Titan (Ti), Zirconium (Zr), Hafnium (Hf), Bor (B), Aluminium (Al), Silicium (Si), Germanium (Ge) und/oder Zinn (Sn); und
    (E') einer Komponente aus wasserlöslichen Oxiden, wasserlöslichen Carbonaten und/oder wasserlöslichen Hydroxiden von Ti, Zr, Hf, B, Al, Si, Ge und/oder Sn.
  2. Wässrige, flüssige Zusammensetzung nach Anspruch 1, wobei Komponente A1 ein Polyvinylalkohol mit einem Polymerisationsgrad im Bereich von 100 bis 600 ist oder einen solchen umfasst.
  3. Wässrige, flüssige Zusammensetzung nach Anspruch 2, wobei der Polyvinylalkohol in einer Konzentration im Bereich von 0,5 bis 16 g/l vorhanden ist.
  4. Wässrige, flüssige Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei Komponente B' Polyacrylsäure mit einer mittleren Molmasse in der Größenordnung von 50 000 ist oder diese umfasst.
  5. Wässrige, flüssige Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei Komponente C' H2ZrF6 und/oder H2TiF6 ist.
  6. Wässrige, flüssige Zusammensetzung nach einem der vorhergehenden Ansprüche'mit einem pH-Wert im Bereich von 1,0 bis 5,0.
  7. Wässrige, flüssige Zusammensetzung nach einem der vorhergehenden Ansprüche mit einem pH-Wert im Bereich von 1,0 bis 3,5.
  8. Verfahren zur Behandlung von Aluminium und Aluminiumlegierungen, wobei die Aluminiumoberfläche mit einer in einem der vorhergehenden Ansprüche beanspruchten wässrigen, flüssigen Zusammensetzung in Kontakt gebracht wird.
EP95918314A 1992-04-01 1995-05-08 Zusammensetzung und verfahren zur behandlung von metall Expired - Lifetime EP0824565B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/862,012 US5281282A (en) 1992-04-01 1992-04-01 Composition and process for treating metal
US08/429,431 US5534082A (en) 1992-04-01 1995-04-21 Composition and process for treating metal
CA002220419A CA2220419A1 (en) 1992-04-01 1995-05-08 Composition and process for treating metal
PCT/US1995/005225 WO1996035745A1 (en) 1992-04-01 1995-05-08 Composition and process for treating metal

Publications (3)

Publication Number Publication Date
EP0824565A1 EP0824565A1 (de) 1998-02-25
EP0824565A4 EP0824565A4 (de) 1999-01-07
EP0824565B1 true EP0824565B1 (de) 2001-07-25

Family

ID=27427402

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95918314A Expired - Lifetime EP0824565B1 (de) 1992-04-01 1995-05-08 Zusammensetzung und verfahren zur behandlung von metall

Country Status (8)

Country Link
EP (1) EP0824565B1 (de)
JP (1) JPH11505571A (de)
AT (1) ATE203574T1 (de)
AU (1) AU2428795A (de)
CA (1) CA2220419A1 (de)
DE (1) DE69521916T2 (de)
ES (1) ES2158946T3 (de)
WO (1) WO1996035745A1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10010758A1 (de) * 2000-03-04 2001-09-06 Henkel Kgaa Korrosionsschutzverfahren für Metalloberflächen
JP4544450B2 (ja) * 2002-12-24 2010-09-15 日本ペイント株式会社 化成処理剤及び表面処理金属
EP1788051A4 (de) * 2004-08-26 2009-10-21 Kansai Paint Co Ltd Zusammensetzung zur beschichtung von elektroabscheidungen und beschichteter artikel
TWI340770B (en) 2005-12-06 2011-04-21 Nippon Steel Corp Composite coated metal sheet, treatment agent and method of manufacturing composite coated metal sheet
DE102006039633A1 (de) * 2006-08-24 2008-03-13 Henkel Kgaa Chromfreies, thermisch härtbares Korrosionsschutzmittel
US8273190B2 (en) * 2009-05-29 2012-09-25 Bulk Chemicals, Inc. Method for making and using chromium III salts
US8951362B2 (en) 2009-10-08 2015-02-10 Ppg Industries Ohio, Inc. Replenishing compositions and methods of replenishing pretreatment compositions
DE102014213474A1 (de) * 2013-07-10 2015-01-15 Chemetall Gmbh Verfahren zum Beschichten von metallischen Oberflächen von Substraten und nach diesem Verfahren beschichteten Gegenstände
KR20170026594A (ko) * 2014-07-03 2017-03-08 바스프 에스이 종이 및 판지용 수성 표면 코팅제

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3133865A (en) * 1961-05-22 1964-05-19 American Home Prod Waveset composition comprising an aqueous lotion of polyvinyl alcohol and a carboxy vinyl polymer
JPS5126932B1 (de) * 1971-03-12 1976-08-10
US4191596A (en) * 1978-09-06 1980-03-04 Union Carbide Corporation Method and compositions for coating aluminum
NZ199130A (en) * 1980-12-15 1985-07-31 Colgate Palmolive Co Water-soluble film;mixture of polyvinyl alcohol and polyacrylic acid
US4719038A (en) * 1983-12-27 1988-01-12 Nippon Paint Co., Ltd. Corrosion resistant, coated metal laminate, its preparation and coating materials
EP0181377A4 (de) * 1984-05-04 1986-09-15 Amchem Prod Metallbearbeitung.
JPS621882A (ja) * 1985-06-26 1987-01-07 Nippon Light Metal Co Ltd アルミニウム材用耐食親水性皮膜形成材
JPS6210280A (ja) * 1985-07-05 1987-01-19 Nippon Light Metal Co Ltd アルミニウム材用耐食親水性皮膜処理剤
DE4010563A1 (de) * 1990-04-02 1991-10-10 Basf Ag Copolymerisate auf basis von c(pfeil abwaerts)1(pfeil abwaerts)-c(pfeil abwaerts)8(pfeil abwaerts)-alkylacrylaten und/oder -methacrylaten
US5158622A (en) * 1991-02-12 1992-10-27 Betz Laboratories, Inc. Method and composition for treatment of aluminum
US5281282A (en) * 1992-04-01 1994-01-25 Henkel Corporation Composition and process for treating metal
JP2736600B2 (ja) * 1993-09-27 1998-04-02 呉羽化学工業株式会社 ガスバリヤー性フィルム及びその製造方法

Also Published As

Publication number Publication date
WO1996035745A1 (en) 1996-11-14
ATE203574T1 (de) 2001-08-15
DE69521916T2 (de) 2002-04-04
JPH11505571A (ja) 1999-05-21
AU2428795A (en) 1996-11-29
ES2158946T3 (es) 2001-09-16
DE69521916D1 (de) 2001-08-30
CA2220419A1 (en) 1996-11-14
EP0824565A1 (de) 1998-02-25
EP0824565A4 (de) 1999-01-07

Similar Documents

Publication Publication Date Title
US5534082A (en) Composition and process for treating metal
US5769967A (en) Composition and process for treating metal
US5356490A (en) Composition and process for treating metal
US5281282A (en) Composition and process for treating metal
US5897716A (en) Composition and process for treating metal
US3912548A (en) Method for treating metal surfaces with compositions comprising zirconium and a polymer
US4992116A (en) Method and composition for coating aluminum
US5868872A (en) Chromium-free process for the no-rinse treatment of aluminum and its alloys and aqueous bath solutions suitable for this process
US5129967A (en) Composition and method for non-chromate coating of aluminum
AU609327B2 (en) Chromium-free process for pretreating metallic surfaces prior to coating same with organic materials
AU1705800A (en) Visible chromium- and phosphorus-free conversion coating for aluminum and its alloys
DE69521916T2 (de) Zusammensetzung und verfahren zur behandlung von metall
US20040112470A1 (en) High performance non-chrome pretreatment for can-end stock aluminum
US4391652A (en) Surface treatment for aluminum and aluminum alloys
RU2125118C1 (ru) Способ получения композиции и способ обработки ею металла, его вариант
HK1008057B (en) Process for treating metal

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19971204

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT DE ES FR GB IT

RHK1 Main classification (correction)

Ipc: C23C 22/00

A4 Supplementary search report drawn up and despatched
AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT DE ES FR GB IT

17Q First examination report despatched

Effective date: 19990211

RIC1 Information provided on ipc code assigned before grant

Free format text: 7C 23C 22/00 A, 7C 09D 5/02 B, 7C 09D 133/06 B, 7C 23C 22/34 B, 7C 23C 22/37 B, 7C 09D 133/06 J, 7C 09D 129:04 J, 7C 09D 133/06 K, 7C 09D 103:00 K, 7C 09D 133/06 L, 7C 09D 171:02 L

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT DE ES FR GB IT

REF Corresponds to:

Ref document number: 203574

Country of ref document: AT

Date of ref document: 20010815

Kind code of ref document: T

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 69521916

Country of ref document: DE

Date of ref document: 20010830

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2158946

Country of ref document: ES

Kind code of ref document: T3

EN Fr: translation not filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

EN Fr: translation not filed

Free format text: BO 01/51 PAGES: 265, IL Y A LIEU DE SUPPRIMER: LA MENTION DE LA NON REMISE. LA REMISE EST PUBLIEE DANS LE PRESENT BOPI.

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20030422

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20030606

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040510

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20040510

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20060517

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060525

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060531

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060630

Year of fee payment: 12

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070508

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20080131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070508