EP1206589B1 - Catalyseur pour la phosphatation de surfaces metalliques - Google Patents

Catalyseur pour la phosphatation de surfaces metalliques Download PDF

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Publication number
EP1206589B1
EP1206589B1 EP00958432A EP00958432A EP1206589B1 EP 1206589 B1 EP1206589 B1 EP 1206589B1 EP 00958432 A EP00958432 A EP 00958432A EP 00958432 A EP00958432 A EP 00958432A EP 1206589 B1 EP1206589 B1 EP 1206589B1
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Prior art keywords
phosphating
ions
phosphating solution
carbon atoms
zinc
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EP00958432A
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German (de)
English (en)
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EP1206589A2 (fr
Inventor
Bernd Schenzle
Franz-Adolf Czika
Peter Kuhm
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C23C22/05—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
    • C23C22/36—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 phosphates
    • C23C22/364—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 phosphates containing also manganese cations
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • 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
    • C23C22/36—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 phosphates
    • C23C22/364—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 phosphates containing also manganese cations
    • C23C22/365—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 phosphates containing also manganese cations containing also zinc and nickel cations

Definitions

  • the invention relates to a phosphating solution, a phosphating concentrate and a Process for phosphating metal surfaces with aqueous, acidic Phosphating.
  • This can be iron phosphating or act a zinc phosphating.
  • the method particularly concerns one Zinc phosphating, which is used as a pretreatment for the metal surfaces a subsequent painting, in particular an electro-dip painting.
  • the method is applicable for the treatment of surfaces made of steel, galvanized or galvanized steel, aluminum, aluminized or alloy aluminum steel.
  • the phosphating of metals pursues the goal on the metal surface to produce firmly grown metal phosphate layers that are in themselves Improve corrosion resistance and in conjunction with paints and others organic coatings for a significant increase in adhesion and Resistance to infiltration when exposed to corrosion.
  • Such phosphating processes have long been known in the prior art.
  • For pretreatment before painting is particularly suitable for low-zinc phosphating processes, where the phosphating solutions are comparatively low zinc ion contents of e.g. B. 0.5 to 2 g / l.
  • the parameter in these low-zinc phosphating baths is the weight ratio Phosphate ions to zinc ions, which is usually in the range> 12 and values can accept up to 30.
  • DE-A-40 13 483 discloses phosphating processes with which similar good ones Corrosion protection properties as achieved with the trication process can. These processes do without nickel and use copper instead in low concentrations, 0.001 to 0.03 g / l.
  • German Patent application DE 42 10 513 modifies this process in that as modifying agent for the morphology of the phosphate crystals formed hydroxylamine, its salts or complexes in an amount of 0.5 to 5 g / l Hydroxylamine can be added.
  • hydroxylamine and / or its compounds for Influencing the shape of the phosphate crystals is one of a number of Disclosure known.
  • EP-A-315 059 gives the as a special effect Use of hydroxylamine in phosphating baths indicates the fact that Then steel the phosphate crystals in a desired column or Knot-like form arise when the zinc concentration in the phosphating bath exceeds the range customary for low-zinc processes.
  • Hydroxylamine has the great procedural advantage that it is in generally in the phosphating bath and in phosphating concentrates not by themselves decomposed. This makes phosphating bath concentrates and supplementary solutions for Phosphating baths can be produced that directly contain the required accelerator quantities contain. A complex separate replenishment, such as in the use of nitrite or hydrogen peroxide as accelerators is required can be omitted. Contains the phosphating solution, however Copper ions, which is currently a technical trend, is decomposing Hydroxylamine gradually under the catalytic influence of these ions. In this In this case, the accelerator must be separated from the phosphating bath and raised Amounts are added.
  • the object of the invention is to provide further phosphating processes to provide the benefits of hydroxylamine accelerated processes, however not its disadvantages with regard to decomposition in the presence of copper ions exhibit.
  • the phosphating process is said to be in spray, dip or Diving procedures may be applicable.
  • the invention accordingly relates to an acidic, aqueous phosphating solution containing 0.2 to 3 g / l zinc ions 3 to 50 g / l phosphate ions, calculated as PO 4 3- and 0.5 to 5 g / l at least one organic nitro compound as accelerator, characterized in that the organic nitro compound is selected from nitroarginine, its esters with alcohols having 1 to 4 carbon atoms and from 5-nitro-2-furfurylidene dicarboxylates of the general formula (I) where R is an alkyl group having 1 to 3 carbon atoms.
  • this compound is amphoteric, i.e. H. she can both form salts with acids as well as bases.
  • acidic phosphating solution to be expected that the compound is in a cationic form. This is regardless of whether the compound as such, as a salt with a base, for example as an alkali metal salt, or as a salt with an acid, for example was used as the hydrochloride.
  • esters with alcohols with 1 up to 4 carbon atoms can be used.
  • methyl and Ethyl ester preferred. Since the acid function is blocked by the ester formation, the esters cannot exist as salts with a base. Due to the However, amino groups continue to form salts with acids. Therefore the esters in the acid phosphating solution are also largely cations available. They can be used as a neutral compound, but also in salt form the phosphating solution are introduced. For example, hydrochloride be used.
  • the organic nitro compound is selected from 5-nitro-2-furfuryl dicarboxylates of the general formula (I), the diacetate is special prefers. This means that R in the general formula (I) is preferably one Represents methyl group.
  • the phosphating solution preferably contains 0.8 to 3 g / l of the organic Nitro compound.
  • phosphating baths usually contain sodium, potassium and / or Ammonium ions to adjust the free acid.
  • free Acid is familiar to the person skilled in the art of phosphating. The one in this writing selected method of determining free acid and total acid is in Sample part specified. Free acid values between 0 and 1.5 points and the total acidity between about 15 and about 35 points is technically usual range and are suitable in the context of this invention.
  • the zinc contents are preferably in the range from 0.4 to 2 g / l and in particular from 0.5 to 1.5 g / l, as are customary for low-zinc processes.
  • the weight ratio of phosphate ions to zinc ions in the phosphating baths can fluctuate within wide limits, provided it is in the range between 3.7 and 30 lies. A weight ratio between 10 and 20 is particularly preferred
  • the phosphating solution according to the invention preferably additionally contains one or more of the following cations: 0.1 up to 4 g / l manganese (II), 0.2 up to 2.5 g / l magnesium (II), 0.2 up to 2.5 g / l calcium (II), 0,002 up to 0.2 g / l copper (II), 0.1 up to 2 g / l cobalt (II).
  • the phosphating solutions can additionally contain nickel ions contain.
  • the lowest possible levels of nickel ions have or, if desired, can also be nickel-free.
  • the phosphating solution according to the invention in a preferred Embodiment except zinc ions as additional cations 0.1 to 4 g / l Manganese ions and 0.002 to 0.2 g / l copper ions and not more than 0.05 g / l, in particular not more than 0.001 g / l nickel ions.
  • Phosphating baths which in addition to zinc ions 0.1 to 4 g / l Manganese ions and additionally 0.1 to 2.5 g / l nickel ions.
  • the cations are introduced into the phosphating baths without Concern. It is particularly useful as a source of cations oxides and / or To use carbonates.
  • nitrate content of the phosphating bath When phosphating zinc-containing surfaces, it has proven to be advantageous limit the nitrate content of the phosphating bath to a maximum of 0.5 g / l. This suppresses the problem of so-called speck formation and the Corrosion protection especially when using nickel-free phosphating baths improved. Phosphating baths which contain no nitrate are particularly preferred.
  • phosphating baths can be made by dissolving the individual components produced in water in the desired concentration range directly on site become.
  • concentrates that contain individual components in the desired ratio and from which can be used on site by diluting it with water is produced or as a supplementary solution a working phosphating bath be added to compensate for the consumption of the active components.
  • phosphating concentrates are strongly acidic for stabilization set. After dilution with water, the pH value must be checked frequently and / or the free acid can be blunted to the desired range.
  • alkaline substances such as caustic soda are used or sodium carbonate or basic salts or hydroxides of Ca, Mg, Zn added.
  • the invention also relates to an aqueous concentrate according to Dilute with water by a factor between 10 and 100 and if necessary Adjust the pH to a working range between 2.5 and 3.6 a Phosphating solution according to one or more of claims 1 to 6.
  • the invention further comprises a method for phosphating Metal surfaces made of steel, galvanized or alloy galvanized steel and / or made of aluminium.
  • the materials mentioned can be used in automotive engineering is becoming increasingly common to also exist side by side. You bring them Metal surfaces by spraying or dipping or by a combination thereof in contact with the phosphating solution according to the invention.
  • the temperature the phosphating solution is preferably in the range between about 40 and about 60 ° C.
  • the phosphating process can be used to phosphate steel or steel strips galvanized steel can be used in conveyor systems.
  • the phosphating times are thereby in the range from about 3 to about 20 seconds.
  • the procedure can be used especially in automobile construction, where treatment times between 1 and 8 minutes are common. It is particularly used to treat the mentioned metal surfaces before painting, especially before cathodic electrophoretic coating.
  • the phosphating process is as To see part of the technically usual pretreatment chain. In this chain are the steps of cleaning / degreasing, rinsing and activation upstream, the activation usually with titanium phosphate-containing activating agents.
  • the phosphating according to the invention can, if necessary after an intermediate rinse, a passivating Follow-up treatment.
  • the organic nitro compounds to be used as accelerators according to the invention not only have a positive effect on the formation of the corrosion protection layer in the case of the zinc phosphating which forms the layer, but also in the case of the iron phosphating which is termed “non-layering”. Accordingly, in a generalized aspect, the invention relates to the use of organic nitro compounds selected from nitroarginine, its esters with alcohols having 1 to 4 carbon atoms and from 5-nitro-2-furfurylidene dicarboxylates of the general formula (I). where R is an alkyl group with 1 to 3 carbon atoms, as an accelerator in phosphating solutions.
  • the new phosphating accelerators according to the invention have Hydroxylamine has the advantage of not being catalytic in the presence of copper be decomposed. This reduces the consumption of accelerators copper-containing phosphating baths compared to the standard hydroxylamine.
  • Nitroarginine and its esters safer to handle nitroguanidine decomposes explosive at 102 ° C, nitroarginine only at 195 ° C.
  • Nitroarginine methyl ester hydrochloride is good in the acidic range (pH about 3.3) soluble and can therefore be used as an internal accelerator.
  • a corrosion test VDA 621415 over 10 rounds and a stone chip test VDA 621427 were carried out as corrosion tests.
  • the results are summarized in Table 2.
  • Results of the corrosion tests: U paint infiltration (half scratch width, mm), K value phosphating substratum U K value Comp. 1 CRS 1.6 3 Beisp.1 CRS 1.3 3 Ex. 2 CRS 1.2 3 Comp. 2 CRS 1.5 4 Comp. 3 CRS 1.5 4 Ex. 3 CRS 1.7 3-4 Ex. 4 CRS 1.7 4 Comp. 5 CRS 1.0 3 Comp. 6 CRS 1.3 3 Ex. 5 CRS 1.2 3-4 Ex.

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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 (9)

  1. Solution de phosphatation acide, aqueuse contenant :
    de 0,2 à 3 g/l d'ions zinc
    de 3 à 50 g/l d'ions phosphate calculé en tant que PO4 3- et
    de 0,5 à 5 g/l d'au moins un composé nitro organique comme accélérateur,
    caractérisée en ce que
    le composé nitro organique est choisi parmi la nitroarginine, ses esters avec des alcools ayant de 1 à 4 atomes de carbone et parmi les 5-nitro-2- furfurylidène dicarboxylates de formule générale (I)
    Figure 00180001
    dans laquelle R signifie un groupe alkyle ayant de 1 à 3 atomes de carbone.
  2. Solution de phosphatation selon la revendication 1,
    caractérisée en ce qu'
    elle renferme de 0,8 à 3 g/l de composé nitro organique.
  3. Solution de phosphatation selon l'une ou les deux des revendications 1 et 2,
    caractérisée en ce qu'
    elle renferme en supplément un ou plusieurs des cations suivants :
    de 0,1 à 4 g/l de manganèse (II)
    de 0,2 à 2,5 g/l de magnésium (II)
    de 0,2 à 2,5 g/l de calcium (II)
    de 0,002 à 0,2 g/l de cuivre (II)
    et de 0,1 à 2 g/l de cobalt (II).
  4. Solution de phosphatation selon la revendication 3,
    caractérisée en ce qu'
    elle renferme de 0,1 à 4 g/l d'ions manganèse et de 0,002 à 0,2 g/l d'ions cuivre et pas plus de 0,05 g/l d'ions nickel.
  5. Solution de phosphatation selon la revendication 3,
    caractérisée en ce qu'
    elle renferme de 0,1 à 4 g/l d'ions manganèse ainsi qu'en supplément de 0,1 à 2,5 g/l d'ions nickel.
  6. Solution de phosphatation selon l'une ou plusieurs des revendications 1 à 5,
    caractérisée en ce qu'
    elle renferme de 0,4 à 2g/l, de préférence de 0,5 à 1,5 g/l d'ions zinc.
  7. Concentré aqueux qui se produit après dilution avec de l'eau d'un facteur compris entre 10 et 100, et le cas échéant après ajustement de la valeur du pH à une zone de travail comprise entre 2,5 et 3,6, d'une solution de phosphatation selon l'une ou plusieurs des revendications 1 à 6.
  8. Procédé de phosphatation des surfaces métalliques en acier, en acier zingué ou en acier zingué par alliage et/ou en aluminium,
    dans lequel on met en contact les surfaces par pulvérisation ou immersion, ou par une combinaison des deux pendant une durée comprise entre 3 secondes et 8 minutes, avec une solution de phosphatation conformément à l'une ou plusieurs des revendications 1 à 6.
  9. Utilisation des composés nitro organiques, choisis parmi la nitroarginine, ses esters avec des alcools ayant de 1 à 4 atomes de carbone et parmi les 5-nitro-2-furfurylidènedicarboxylates de formule générale (I),
    Figure 00200001
    dans laquelle R signifie un groupe allyle ayant de 1 à 3 atomes de carbone,
    comme accélérateurs dans des solutions de phosphatation.
EP00958432A 1999-08-20 2000-08-11 Catalyseur pour la phosphatation de surfaces metalliques Expired - Lifetime EP1206589B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19939519A DE19939519A1 (de) 1999-08-20 1999-08-20 Beschleuniger für die Phosphatierung von Metalloberflächen
DE19939519 1999-08-20
PCT/EP2000/007850 WO2001014613A2 (fr) 1999-08-20 2000-08-11 Catalyseur pour la phosphatation de surfaces metalliques

Publications (2)

Publication Number Publication Date
EP1206589A2 EP1206589A2 (fr) 2002-05-22
EP1206589B1 true EP1206589B1 (fr) 2003-04-16

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EP00958432A Expired - Lifetime EP1206589B1 (fr) 1999-08-20 2000-08-11 Catalyseur pour la phosphatation de surfaces metalliques

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EP (1) EP1206589B1 (fr)
JP (1) JP2003507579A (fr)
AU (1) AU6995000A (fr)
DE (2) DE19939519A1 (fr)
WO (1) WO2001014613A2 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10155666A1 (de) * 2001-11-13 2003-05-22 Henkel Kgaa Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren
DE102014005444A1 (de) * 2014-04-11 2015-10-15 Audi Ag Verfahren zur Passivierung einer metallischen Oberfläche

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2884351A (en) * 1956-01-25 1959-04-28 Parker Rust Proof Co Method of cold rolling ferrous strip stock

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Publication number Publication date
WO2001014613A2 (fr) 2001-03-01
DE50001815D1 (de) 2003-05-22
JP2003507579A (ja) 2003-02-25
AU6995000A (en) 2001-03-19
EP1206589A2 (fr) 2002-05-22
WO2001014613A3 (fr) 2001-12-13
DE19939519A1 (de) 2001-02-22

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