WO2006029823A2 - Procede de traitement de surfaces metalliques au moyen de formulations a base d'acide methanesulfonique a faible teneur en eau - Google Patents

Procede de traitement de surfaces metalliques au moyen de formulations a base d'acide methanesulfonique a faible teneur en eau Download PDF

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Publication number
WO2006029823A2
WO2006029823A2 PCT/EP2005/009838 EP2005009838W WO2006029823A2 WO 2006029823 A2 WO2006029823 A2 WO 2006029823A2 EP 2005009838 W EP2005009838 W EP 2005009838W WO 2006029823 A2 WO2006029823 A2 WO 2006029823A2
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Prior art keywords
methanesulfonic acid
amount
formulation
water
weight
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PCT/EP2005/009838
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German (de)
English (en)
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WO2006029823A3 (fr
Inventor
Helmut Witteler
Bernd Laubusch
Thomas Heidenfelder
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Basf Aktiengesellschaft
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Publication of WO2006029823A2 publication Critical patent/WO2006029823A2/fr
Publication of WO2006029823A3 publication Critical patent/WO2006029823A3/fr

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    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium
    • 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
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/18—Polishing of light metals
    • C25F3/20—Polishing of light metals of aluminium

Definitions

  • the present invention relates to a process for treating metallic surfaces, in which methanesulfonic acid formulations are used which comprise less than 28% by weight of water and optionally amines and / or further constituents.
  • Numerous methods for the treatment of metal surfaces are carried out using various inorganic or organic acids. These methods serve, for example, to achieve a certain appearance of the metal surface (eg when shining, "brightening"), to improve the corrosion resistance by smoothing the metal surface (pickling, "pickling"), changing the acidity of Metal surfaces which are covered with hydroxide-containing layers (pickling) or for the chemical or electrochemical deposition of metals on Metalli ⁇ 's surfaces.
  • the methods are described in the technical terms mentioned in Ulimann's Encyclopedia of Industrial Chemistry and other textbooks.
  • the said method has in common that dilute aqueous solutions of acids are applied.
  • Methanesulfonic acid is commercially available as a 70% aqueous solution.
  • product brochures the use in electroplating baths or for electropolishing is suggested as an application example (Technical Information Lutropur® MSA, BASF Aktiengesellschaft, September 2004 Edition).
  • WO 02/4713 discloses the electrolytic coating of metals with zinc.
  • WO 02/4716 and WO 02/4717 disclose the surface treatment of aluminum or aluminum alloys.
  • predominantly water-comprising electrolytes which as a rule comprise 3 to 30% by weight of methanesulfonic acid and other auxiliaries, are used.
  • water-poor formulations with less than 28% by weight of water is not disclosed.
  • Concentrated methanesulfonic acid having a methanesulfonic acid content of at least 99.5% is commercially available.
  • the product brochure only proposes their use as a precursor for the synthesis of pharmaceutical active ingredients and agrochemicals and as a catalyst in esterification, polymerization and alkylation reactions (Technical Information Lutropur® MSA 100, BASF Aktiengesellschaft, November edition 2002).
  • liquid methanesulfonates which can be prepared by quaternization reactions or by silver salt precipitation (for example Golding et al (Green Chemistry 4, 223-229 (2002)), whose use is for the treatment of metallic surfaces not described.
  • the object of the invention was to provide methods for the treatment of metallic surfaces in which the desired effects occur, such as, for example, a very high gloss, but without the surface of the metal being excessively attacked. Accordingly, a process has been found for the treatment of metallic surfaces in which the metal surface is brought into contact with a formulation containing methanesulfonic acid, wherein the formulation contains 20 to 100% by weight of methanesulfonic acid and 0 to 28% by weight of water and / or 0 to 80 .% by weight any artwork least an amine, and optionally 0-30% by weight of one or more auxiliaries holds ent, and wherein the amounts of the apply formulations tion are each based on the amount of all components and the melting point of the formulation less than 100 0th C is.
  • a formulation which contains from 20 to 100% by weight of methanesulfonic acid is used for the treatment of the metallic surfaces.
  • it can therefore also be pure, concentrated methanesulfonic acid.
  • the formulation preferably contains further constituents, namely water and / or amines and optionally adjuvants.
  • the invention is a low-water formulation which contains not more than a maximum of 28% by weight of water, based on the amount of all components of the formulation.
  • the amount of water is preferably 0 to 25% by weight, more preferably 0 to 10% by weight of water, more preferably 0.5 to 8% by weight and most preferably 1 to 5% by weight of water.
  • the selection of the amines which can be used for the process according to the invention is not restricted in principle.
  • the person skilled in the art makes a selection of the amines with the proviso that the melting point of the formulation is less than 100 ° C.
  • aromatic, heterocyclic, aliphatic, cycloaliphatic or araliphatic amines may be monoamines or di- or polyamines.
  • the amines may also comprise further functional groups, provided that the properties of the formulation were not negatively affected thereby.
  • An example of another functional group is an OH group.
  • Suitable amines include in particular (3-aminopropyl) amino-2-ethanol, 1- (1-naphthyl) ethylamine, 1- (3-aminopropyl) imidazole, 1- (4-methoxyphenyl) -2- (ethyl) amino) -propane, 1- (4-methoxyphenyl) ethylamine, 1- (4-methylphenyl) ethylamine, 1,1-dimethylpropin-2-ylamine, 1,1'-iminobis-2-propanol, 1, 2-diaminoquinone, 1,2-ethanediamine, 1,2-propylenediamine techn., 1,3,5-tris- (3-dimethylaminopropyl) -sym-hexahydrotriazine, 1,3-dimethylaminouracil, 1,3-phenylene-bis- diaminotriazine, 1,3-propanediamine, 1,4-diamino
  • mixtures of two or more amines can be used.
  • Preferred amines for carrying out the process according to the invention are heterocyclic, aliphatic or aromatic amines, such as, for example, mono-n-alkylamines having up to 20 carbon atoms, cyclohexylamine, secondary cyclohexylmethylamines and amines which on the nitrogen in addition to the radicals -H and / or -Methyl in addition
  • 2-Ethylhexylreste and / or 2-Propylheptylreste carry. Further preferably, it is at least one amine selected from the group of imidazole, morpholine or piperidine, as well as derivatives of said amines which are alkylated on at least one nitrogen atom but not quaternized. Examples of such derivatives include 1-methylimidazole, 1-ethylimidazole, 4-methylmorpholine or 3-aminopropyl-N-imidazole.
  • tertiary amines of the general formula NR 1 R 2 R 3 wherein the radicals R 1 , R 2 and R 3 are each independently linear, branched or cyclic hydrocarbon radicals having 1 to 24 C atoms, which also may have further substituents, or in which non-adjacent C atoms are replaced by O atoms and / or -NH groups.
  • the radicals R 1 , R 2 and R 3 are preferably, independently of one another, linear, branched or cyclic alkyl radicals having 1 to 24 C atoms.
  • the alkyl radicals preferably have 3 to 20 C atoms, particularly preferably 6 to 18 C atoms and very particularly preferably 8 to 14 C atoms.
  • Examples of such tertiary amines include tributylamine, tertiary cyclohexylmethylamines, trioctylamine, tridecylamine or tridodecylamine.
  • the radicals R 1, R 2 and R 3 independently of each other linear, branched, or cyclic hydroxyalkyl groups having 1 to 18 carbon atoms.
  • a maximum of 1 OH group can be present per 1 C atom, preferably the remainder has at most 1 hydroxyl group per 2 C atoms. As a rule, however, no more than 8-OH groups are present, and more preferably the remainder has only one hydroxy group.
  • the hydroxyalkyl radical preferably has 1 to 12 C atoms, particularly preferably 2 to 6 C atoms. Examples of such tertiary amines include triethanolamine, N, N-dimethylethanolamine and N-methyldiethanolamine.
  • alkyl or hydroxyalkyl radicals can also be linked together to form a ring.
  • radicals R 1, R 2 and R 3 radicals, mines by alkoxylation, particularly ethoxylation and / or propoxylation from A to buy, wherein the terminal OH group may also be etherified.
  • the alkoxy radicals may be radicals of the general formula R 5 - [O-CHR 4 -CHR 4 ] n -, where n is a natural number of 1 to 50, preferably 2 to 30 and particularly preferably 3 to 20, where R 4 or R 4 independently of one another are H and / or methyl and R 5 is H or a linear, branched or cyclic alkyl radical having 1 to 24 C atoms.
  • One of the radicals R 4 or R 4 ' is preferably H, while the other is H or methyl, that is, ethoxylates and / or propoxylates are preferred.
  • R 1 , R 2 and R 3 can also be combined with one another.
  • amines are present, their amount is generally from 1 to 80% by weight, based on the amount of all components of the formulation. Preferably, the amount is 5 to 80 wt.%, Particularly preferably 10 to 75 wt.% And most preferably 20 to 70 wt.%.
  • the formulation may further optionally contain adjuvants.
  • auxiliaries and / or additives for the respective process for the treatment of metallic surfaces.
  • auxiliaries include surface-active substances, electroplating additives, corrosion inhibitors, oxidizing agents, reducing agents, dispersants or organic solvents which are substantially miscible with the formulation.
  • the excipients may also be transition metal oxoanions, fluorometalates or lanthanoid compounds. Particularly suitable are orometallates of Ti (IV) 1 Zr (IV), Hf (IV) and / or of Si (IV), cerium compounds and tungstates and molybdate.
  • Additives are furthermore metal ions, for example in the form of metal salts, such as, for example, aluminum, aluminate, titanyl, titanate, copper, iron, zinc, tin, magnesium, nickel, cobalt, manganese , Chromium, silver, lead, which are to be deposited chemically or electrochemically on the surface.
  • metal salts such as, for example, aluminum, aluminate, titanyl, titanate, copper, iron, zinc, tin, magnesium, nickel, cobalt, manganese , Chromium, silver, lead, which are to be deposited chemically or electrochemically on the surface.
  • the amount of the auxiliaries is selected by the person skilled in the art, depending on the process, and is usually 0 to 30% by weight, preferably 1 to 30% by weight and preferably 5 to 25% by weight.
  • the melting point of the formulation is less than 100 0 C.
  • the melting point of the formulation is less than 50 0 C, more preferably 4O 0 C and most preferably less than 20 ° C.
  • the formulations may contain all four components in common, but are preferred formulations containing either methanesulfonic acid, water and optional auxiliaries or methanesulfonic acid, amines and optional auxiliaries.
  • the aggressiveness of the mixture with respect to metallic surfaces can be adjusted continuously. While the addition of water increases its aggressiveness towards metallic surfaces, for example measurable in the form of greater metal removal, the aggressiveness can be dampened by the addition of amines.
  • the addition of amines to 100% methanesulfonic acid has the additional advantage that its high hygroscopy can be significantly reduced.
  • the viscosity of the formulation increases with increasing amine content, especially when using hydroxyalkylamines. The viscosity of the formulation can thus be adjusted to the desired value without the aid of auxiliaries, such as thickeners.
  • Formulations of methanesulfonic acid, water and optionally auxiliaries preferably contain from 65 to 99% by weight of methanesulfonic acid, from 1 to 28% by weight of water, and from 0 to 30% by weight of auxiliaries. Such mixtures preferably contain 90 to 98.95% by weight of methanesulfonic acid, 1 to 5% by weight of water and 0.05 to 5% by weight of auxiliaries.
  • Formulations of methanesulfonic acid, one or more amines and optional auxiliaries preferably contain from 20 to 99% by weight of methanesulfonic acid, from 1 to 80% by weight of amines and from 0 to 30% by weight of auxiliaries. Particularly preferably included such mixtures 30 to 79.95% by weight of methanesulfonic acid, 20 to 70% by weight of amines and 0.05 to 5% by weight of auxiliaries.
  • Formulations of all four components preferably contain from 20 to 98% by weight of methanesulfonic acid, from 1 to 10% by weight of water, from 1 to 79% by weight of one or more amines and from 0 to 30% by weight of auxiliaries. Such mixtures preferably contain from 30 to 78.95% by weight of methanesulfonic acid, from 1 to 5% by weight of water, from 20 to 70% by weight of one or more amines and from 0.05 to 5% by weight of auxiliaries.
  • processes for the treatment of metallic surfaces are to be understood as meaning all processes in which the properties of the metallic surface are changed with the aid of a liquid treatment agent, e.g. with regard to the chemical composition, the appearance, the corrosion resistance or the smoothness of the metallic surface.
  • a liquid treatment agent e.g. with regard to the chemical composition, the appearance, the corrosion resistance or the smoothness of the metallic surface.
  • processes include the cleaning, stripping, pickling, glazing, polishing, electro polishing, anodizing or passivating of metals or the chemical or electrochemical deposition of metal coatings on metals.
  • the metallic surface can be any metallic surface.
  • it can be the surface of aluminum, copper, steel, zinc, tin, magnesium, nickel, silver, lead, silicon or alloys of the said metals. They may also be substrates coated with these metals, for example metals coated with metals.
  • the surface is the surface of aluminum or aluminum alloys or zinc or zinc alloys. It may also be multilayer metallic materials, for example, galvanized or aluminized steel.
  • the formulation is brought into contact with the metallic surface, for example by spraying, dipping or rolling. After a dip process, you can drain the workpiece to remove excess formulation; In the case of sheet metal, metal foils or the like, however, excess formulation can also be squeezed off, doctored off or blown off, for example.
  • the treatment with the preparation can take place at room temperature or at higher temperatures. After the treatment, the surface can also be rinsed off.
  • the treatment of the metal surface with the formulation can be carried out batchwise or preferably continuously.
  • a continuous process is particularly suitable for treating band metals.
  • the metal strip is driven through a warmer or spray device with the formulation and, optionally, a trough or spray device for the crosslinker and optionally through further pre- or post-treatment stations.
  • the duration of treatment will be determined by the skilled person according to the desired properties of the layer, the composition used for the treatment and the technical conditions. It can be significantly less than a second or several minutes. In the continuous process, it has proven particularly useful to bring the surface into contact with the preparation for a period of from 1 to 60 s.
  • the method according to the invention may be, for example, the pickling or the pickling degreasing of metallic surfaces.
  • the pickling of metallic surfaces serves to clean the metal surface, to remove corrosion and scale residues as well as adhering oxide layers and to prepare them for further process steps.
  • Anhydrous methanesulfonic acid or formulations with up to 5% by weight of water can preferably be used for this purpose.
  • auxiliaries can be added.
  • the pickling with the inventive formulation of at temperatures of 20 to 5O 0 C, for example about 40 0 C performed the was ⁇ should be without higher temperatures thereby excluded.
  • metals of all kinds can be stained by means of the formulations used according to the invention, but the process is particularly suitable for pickling aluminum or aluminum alloys and also for copper or copper alloys.
  • the metal surface is pickled while applying an electrical voltage.
  • the metal to be polished is connected as an anode.
  • current densities of 0.5 to 10 A / dm 2 are advantageously sufficient, while higher current densities are required when using electrolytes based on methanesulfonic acid but a water content of more than 28% and when using other acids.
  • the mass removal when using the formulations according to the invention for pickling and electropolishing is very low.
  • specular gloss is achieved even with typical mass losses of less than 2.5 mg / cm 2 , while technically customary processes entail a mass loss of in some cases more than 5 mg / cm 2 .
  • the method for treating metallic surfaces may also be tin plating of printed circuit boards.
  • the printed circuit board which has bare copper interconnects on its surface, is immersed in a formulation according to the invention based on methanesulfonic acid and amine and subsequently in molten solder (for example tin and tin alloys).
  • the flux etches the Cu surface, making it wettable to the liquid solder.
  • Fluxes based on methanesulfonic acid and amine can replace aqueous fluxes, and they allow a wide design freedom for the formulation, since they can be anhydrous and in them also water-sensitive reagents can be used.
  • the method according to the invention may furthermore be the electrolytic or chemical deposition of metals on metallic surfaces.
  • metals include the deposition of Sn, Ag 1 Cu, Al, Si, Ni, Zn, Ge 1 As, Ga and their alloys.
  • These metals and alloys are used as decorative, functional or protective coatings, as reflective coatings, in semiconductor and printed circuit board technology, in printing plate production, in electrical engineering and electronics, in the manufacture of resistors and capacitors, in the automotive industry Device construction.
  • Particularly suitable for this are formulations with a high proportion of methanesulfonic acid, typically from 90 to 100% by weight, preferably from 95 to 100% by weight, and more preferably anhydrous methanesulfonic acid.
  • non-noble metals can advantageously also be deposited without difficulty. It is also positive that the corrosiveness of the formulation and the tendency to form toxic vapors are reduced compared to electrolytes based on AlCIs / amine.
  • the method according to the invention may furthermore be stripping, ie the removal of paint layers from metallic surfaces.
  • Preferred for this purpose are mixtures with a very high proportion of methanesulfonic acid of 80 to 100% by weight, preferably 90 to 100% by weight and more preferably 95 to 100% by weight.
  • the process according to the invention is particularly suitable for paint stripping of steel, Al 1 Cu and alloys of Al or Cu.
  • the advantage lies in the speed of the process and, on the other hand, in the fact that the metal to be stripped is not or only slightly attacked.
  • the process according to the invention may also be an acidic purification. Acid cleaners include acid as well as surfactants and other adjuvants. The production of highly acidic cleaners often causes problems because most of the thickeners do not work in a strongly acidic environment or are not storage-stable.
  • a mixture of methanesulfonic acid, one or more amines and auxiliaries is used for acidic cleaning.
  • water can also be used.
  • Particularly suitable amines for this application are, for example, aminopropylimidazole or hydroxyethylpiperazine and preferably mixtures of the two.
  • thickeners can be dispensed with in comparison to conventional acidic cleaners. The desired (high) viscosity can be adjusted solely by the choice of the type and amount of the amines to the value suitable for the particular application.
  • the method according to the invention can furthermore also be used for the temporary corrosion protection of metals, in particular of steel.
  • formulations containing amines are suitable for this purpose.
  • Aqueous agents can lead to the formation of condensation and waterlogging, which in turn can lead to corrosion at sites which have not or not sufficiently come into contact with the aqueous corrosion protection formulation.
  • a high viscosity can be achieved by selecting suitable amines, such as tridecylamine.
  • suitable amines such as tridecylamine.
  • Such a formulation is therefore also suitable as a corrosion-inhibiting lubricant.
  • the mixture is also easy to rinse off with water alone and without surfactants.
  • formulations which are prepared from readily biodegradable amines (for example diethanolamine) and also readily biodegradable methanesulfonic acid are likewise readily biodegradable in sewage treatment plants. This is an advantage over many other metal treatment agents.
  • the process according to the invention can also be a step in a multistage process for the treatment of metallic surfaces.
  • These processes may be particularly advantageously used in which methanesulfone-containing formulations are used in each of several stages, and wherein at least one of the stages uses the inventive sparse methanesulfonic acid formulations.
  • the method according to the invention may also be the masking of metals for the purpose of corrosion protection.
  • corrosion-protection oils based on mineral oils have conventionally been used for this purpose.
  • the metallic surface is covered with a formulation based on methanesulfonic acid and amine.
  • the metallic surface may also be the surface of a molten metal, such as the surface of molten tin-based solders.
  • the methanesulfonic acid should generally be substantially neutralized with the amine. The metallic surface is thereby protected against the ingress of atmospheric oxygen and / or moisture.
  • the rinsing of the formulation used according to the invention can be carried out without surfactants and only with water.
  • salts of methanesulfonic acid and amine have a very low vapor pressure and a lower flash point than mineral oils, which is a significant advantage in terms of occupational safety when handling hot and liquid metals.
  • One example involves such multi-stage processes in which the metallic surface is pickled, electropolished or cleaned in a first process step by means of the formulation used according to the invention, and then in a second step electrolytically or chemically a metal layer is deposited on the metal surface by means of a methanesulfonic acid-containing electrolyte ,
  • the particular advantage of the methods according to the invention is that the rinsing steps between the treatment steps can be made less expensive or completely eliminated, because there is no sensitivity due to contamination with the acid of the other bath between baths based on methanesulfonic acid.
  • excess methanesulfonic acid in the process according to the invention can also be removed very particularly elegantly from the surface by blowing off by means of a suitable gas stream, for example an air stream.
  • a suitable gas stream for example an air stream.
  • the rinsing can be omitted or, if rinsed, at least less methanesulfonic acid passes into the rinse water.
  • no interfering, volatile constituents eg HCl, HF or NO 2 ) are released as with the use of conventional acids.
  • An aluminum sheet (AI 99.96) is immersed for 5 min at 90 0 C in the pickling, blown off after retrieving and rinsed with water.
  • the pickling effect was assessed visually.
  • Shiny copper sheet is 15 seconds at 6O 0 C in methanesulfonic moved be ⁇ 100%, rinsed with deionized water and blown dry.
  • the degree of gloss increases from 120 to 130 units due to the treatment with methanesulfonic acid (Reflectometer REFO 3, Dr. Lange at 85 °), the weight loss is less than 1 ⁇ g / cm 2 .
  • the gloss of the sheet can not be increased although a weight loss of 18 ⁇ g / cm 2 occurs.
  • Electrolyte A Methanesulfonic acid 100% + 1 g / l aluminum chloride anhydrous, life after addition of aluminum chloride 24 h
  • Electrolyte B methanesulfonic acid 100% + 8g / l aluminum powder, service life electrolyte after addition of aluminum powder 24h Comparative tests:
  • Electrolyte C formulation of 69.5% by weight of methanesulfonic acid and 30.5% by weight
  • AIMgI plates (40 cm2 area) is one minute (60g / L) stained at about 60 0 C and connected min as an anode at a voltage of 16 V for 40 and thereby electropolished in sodium hydroxide solution.
  • the degree of gloss is determined before and after the treatment (Reflectometer REFO 3 from Dr. Lange, irradiation angle of 85 °).
  • the induced by the electropolishing mass removal is determined. The results are shown in Figures 1 and 2.
  • Fig. 1 electropolishing of aluminum in methanesulfonic acid of different concentration. Gloss level and mass removal after 20 min.
  • Fig. 2 Electropolishing of aluminum in methanesulfonic acid 98%. Gloss level and mass decrease depending on the treatment time.
  • Methanesulfonic acid 100% is heated to 60 0 C.
  • 1 .mu.m copper is deposited at a bath voltage of 2.5 V within 10 min.
  • An aluminum sheet painted with commercial 2K automotive refinish paint is immersed in 100% methanesulfonic acid at 20 ° C. for 2 minutes. The paint dissolves over a large area. The aluminum sheet is not attacked.
  • Tridecylamine and methanesulfonic acid are mixed in a molar ratio of 1: 1.
  • Steel sheets are dipped in the tridecylammonium methanesulfonate thus prepared and stripped off with a rubber wiper.
  • the steel sheets are treated together with untreated steel sheets in a salt spray chamber according to DIN 50017. Subsequently, the proportion of the corroded area is determined. corroded surface up-treated sheets 100% treated sheets 40 - 50%
  • the example shows that the formulations according to the invention are also suitable for the temporary corrosion protection of steel.
  • the formulations according to the invention are also suitable for the temporary corrosion protection of steel.
  • temporary corrosion inhibitors alkaline alkanolamines
  • stage II and III The process produces smooth, shiny parts from heavily textured and scratched workpieces. Between stage II and III, no rinsing is required, as would be the case with commercially available decorating and shining baths.

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

Abstract

L'invention concerne un procédé de traitement de surfaces métalliques consistant à utiliser des formulations d'acide méthanesulfonique qui présentent une teneur en eau inférieure à 28 % en poids et contiennent éventuellement des amines et/ou d'autres composants.
PCT/EP2005/009838 2004-09-16 2005-09-14 Procede de traitement de surfaces metalliques au moyen de formulations a base d'acide methanesulfonique a faible teneur en eau WO2006029823A2 (fr)

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DE200410045297 DE102004045297A1 (de) 2004-09-16 2004-09-16 Verfahren zum Behandeln von metallischen Oberflächen unter Verwendung von Formulierungen auf Basis von wasserarmer Methansulfonsäure
DE102004045297.0 2004-09-16

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Cited By (4)

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WO2007096711A3 (fr) * 2005-12-12 2008-03-20 Vitech International Inc Compositions nettoyantes, non corrosives et polyvalentes, et leurs procedes d'utilisation
EP2231843B1 (fr) 2008-11-28 2015-07-22 Arkema France Utilisation d'acide alcane sulfonique pour elimination de la rouille
US9502146B2 (en) 2013-03-08 2016-11-22 Horst-Otto Bertholdt Process for dissolving an oxide layer
CN116083917A (zh) * 2023-02-23 2023-05-09 深圳美荣达技术有限公司 酸性清洗剂、制备方法和清洗方法

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DE102006045221B3 (de) * 2006-09-25 2008-04-03 Poligrat Gmbh Elektropolierverfahren für Kobalt und Kobaltlegierungen und Elektrolyt
DE102006050317B3 (de) * 2006-10-25 2008-06-19 Poligrat Gmbh Elektrolyt zum Elektropolieren von Edelstahl (Eisen-Chrom- und Chrom-Eisen-Legierungen) und Elektropolierverfahren für Edelstahl
EP2474649A1 (fr) * 2011-01-05 2012-07-11 Voestalpine Stahl GmbH Procédé de traitement de surface d'un substrat ayant un revêtement de protection
DE102014105823A1 (de) * 2014-04-25 2015-10-29 Harting Kgaa Nachreinigungsverfahren von metallischen Kontaktelementen
CN104060308B (zh) * 2014-06-30 2016-09-14 句容市博远电子有限公司 一种降低露铜现象的纯锡电镀液及其应用
FR3070694B1 (fr) * 2017-09-01 2020-07-03 Arkema France Inhibiteurs de corrosion metallique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007096711A3 (fr) * 2005-12-12 2008-03-20 Vitech International Inc Compositions nettoyantes, non corrosives et polyvalentes, et leurs procedes d'utilisation
US8450257B2 (en) 2005-12-12 2013-05-28 Vitech International, Inc. Multipurpose, non-corrosive cleaning compositions and methods of use
US8859476B2 (en) 2005-12-12 2014-10-14 Vitech International, Inc. Multi-purpose, non-corrosive cleaning compositions and methods of use
EP2231843B1 (fr) 2008-11-28 2015-07-22 Arkema France Utilisation d'acide alcane sulfonique pour elimination de la rouille
US9502146B2 (en) 2013-03-08 2016-11-22 Horst-Otto Bertholdt Process for dissolving an oxide layer
CN116083917A (zh) * 2023-02-23 2023-05-09 深圳美荣达技术有限公司 酸性清洗剂、制备方法和清洗方法
CN116083917B (zh) * 2023-02-23 2024-04-05 深圳美荣达技术有限公司 酸性清洗剂、制备方法和清洗方法

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