EP0760870B1 - Phosphatation ferrique a l'aide d'acides monocarboxyliques substitues - Google Patents

Phosphatation ferrique a l'aide d'acides monocarboxyliques substitues Download PDF

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Publication number
EP0760870B1
EP0760870B1 EP95922451A EP95922451A EP0760870B1 EP 0760870 B1 EP0760870 B1 EP 0760870B1 EP 95922451 A EP95922451 A EP 95922451A EP 95922451 A EP95922451 A EP 95922451A EP 0760870 B1 EP0760870 B1 EP 0760870B1
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EP
European Patent Office
Prior art keywords
phosphating
iron
solution
acid
phosphating solution
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Expired - Lifetime
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EP95922451A
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German (de)
English (en)
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EP0760870A1 (fr
Inventor
Karl-Dieter Brands
Melita Krause
Bernd Mayer
Thomas Molz
Annette Willer
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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
    • C23C22/07—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
    • C23C22/10—Orthophosphates containing oxidants
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • the invention relates to a new phosphating solution for the so-called non-layer-forming phosphating of reactive metal surfaces, in particular Surfaces made of steel, aluminum, zinc or alloys whose Main component of at least one of the metals iron, aluminum or zinc represents.
  • the metal surfaces with acidic solutions (pH range between 3.5 and 6) from Treated phosphates which creates a layer on the metal surface from phosphates and / or oxides, their cations from the metal surface and do not come from other components of the phosphating bath.
  • Processes for iron phosphating are known in the prior art. she are used, for example, as a pretreatment process before painting used in cases where there is no excessive corrosive load of the components is to be expected.
  • the iron phosphate layers have a mass per unit area (layer weight) of above about 0.2 g / m 2 .
  • layer weight the corrosion protection effect increases with increasing layer weight.
  • higher layer weights for example above about 0.8 g / m 2 , there is a risk that the layers become powdery and do not adhere firmly to the metal surface. This leads to an unacceptably poor paint adhesion.
  • Efforts are therefore being made to produce iron phosphate layers which, on the one hand, achieve the highest possible layer weight, for example in the range between approximately 0.5 and approximately 1 g / m 2 , the coverings at the same time being intended to form firmly adhering layers.
  • accelerators are inorganic or organic substances with an oxidizing, more rarely with a reducing effect.
  • Inorganic accelerators are, for example, nitrates, chlorates, bromates, molybdates and tungstates.
  • Known organic accelerators are aromatic nitro compounds such as nitrobenzenesulfonic acid, especially m-nitrobenzenesulfonic acid ("NBS").
  • NBS m-nitrobenzenesulfonic acid
  • An example of an inorganic substance with a rather reducing effect and with good accelerator properties is hydroxylamine and its salts.
  • Phosphating baths containing such accelerator systems are known, for example, from US Pat. No. 5,137,589 and WO93 / 09266. According to the last-mentioned document, particularly good layers are produced when oxidizing and reductive accelerators are combined with one another, here, for example, hydroxylamine with organic nitro compounds, with molybdate or tungstates.
  • the formation of iron phosphate layers is favorably influenced if the phosphating solution chelating complexing agents for iron contains.
  • gluconic acid is used for this particularly suitable.
  • the CA-874944 continues to recommend the use of ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, citric acid, tartaric acid and Glucoheptonic acid.
  • the complexing agents mentioned have in common that they chelating carboxylic acids with at least 4 carbon atoms and with at least 3 represent substituents selected from carboxyl and hydroxyl groups.
  • EP-A-398 203 shows that iron phosphating solutions instead the usual accelerator anionic titanium compounds, preferably in a concentration between 0.05 and 0.2 g / l dissolved titanium can.
  • GB-A-741.050 describes a non-layer-forming phosphating process for Metal surfaces described, in which the acid phosphating baths 0.1 to 3 wt .-% Contain tartaric acid or its salts.
  • This additive makes the formation more powdery Prevents phosphate coatings.
  • the phosphating baths have a pH in the range from 4.2 to 5.8 and are based on phosphate solutions of non-layer-forming metals and Oxidizing agents. It is mentioned that an addition of other compounds, such as Citric acid, lactic acid, glycolic acid, aminoacetic acid and its salts, the formation such powdery coatings not prevented.
  • the invention has for its object an iron phosphating solution with an ecological to provide cheap accelerator system. It was found. that ecologically safe substituted monocarboxylic acids combined lead with the co-accelerator nitrobenzenesulfonic acid to phosphate layers that the meet technical requirements.
  • the amino acids are preferably selected from glycine, alanine, serine, phenylalanine, (hydroxyphenyl) alanine and (dihydroxyphenyl) alanine, with glycine, alanine and serine being particularly preferred.
  • phosphating solutions achieved that contain 0.2 to 0.5 g / l nitrobenzenesulfonic acid. Doing so preferably the m-nitrobenzenesulfonic acid (“NBS”) is used.
  • NBS m-nitrobenzenesulfonic acid
  • substituted carboxylic acids described by the general formula (I) are usually optically active.
  • the acids are in the form of a racemate or in the R or L form available.
  • the acids mentioned, including phosphoric acid, can be used as such or can be used as alkali or ammonium salts.
  • the pH must be correct the phosphating solution to the effective range between about 3.5 and about 6.0 can be set. If necessary, this can be done by adding Acid, preferably phosphoric acid, or of lye, preferably sodium hydroxide solution, respectively. These are under these pH conditions Acids according to their respective pK values partly in undissociated Form before.
  • the iron phosphating baths When incorporated, the iron phosphating baths usually have Iron (II) levels up to about 25 ppm, which has positive bathing properties influence. When it comes to new phosphating solutions, it is recommendable to add iron (II) ions in the ppm range, for example by adding about 20-50 ppm iron (II) sulfate.
  • Total acid content
  • points characterized by their "total acid” content, expressed in points, characterized.
  • Total acid score the consumption in milliliters of 0.1 N sodium hydroxide solution, 10 ml of the solution up to the point of transition of phenolphthalein or titrate up to a pH of 8.5.
  • Technically common areas of Total acid are between about 3 and about 7 points, preferably between about 4 and about 6 points.
  • the temperatures of the treatment solutions are usually between about 30 and 70 ° C.
  • the bath temperature is particularly suitable for cleaning acting baths according to the type and amount of pollution as well as the intended Treatment time.
  • the minimum temperature depends on the foam behavior of the wetting agents used and is preferably above the Cloud point of the wetting agent selected. Usually the temperature is between 50 and 60 ° C.
  • the workpieces to be treated can with the Solution splashed or immersed in the solution. Higher layer weights are usually obtained with immersion processes.
  • the required treatment times are between 15 seconds and 10 minutes, but in practice Treatment times rarely fell below 60 seconds and 5 minutes rarely be exceeded.
  • the invention also relates to a method for phosphating metal surfaces, preferably surfaces made of steel, zinc, aluminum or alloys, the main component of which is at least one of the metals iron, zinc or aluminum, by treating the surfaces with the solutions described above, preferably with a Temperature between 30 and 70 ° C, for a time between 15 seconds and 10 minutes, preferably one to 5 minutes, by immersion in the solution and / or by spraying with the solution.
  • the process parameters are preferably chosen so that phosphate layers with a layer weight in the range of 0.2 to 1 g / m 2 , preferably 0.4 to 0.9 g / m 2 and in particular 0.4 to 0.7 g / m 2 are obtained will.
  • the method can be used in particular for the pretreatment of metal surfaces before applying an organic coating, preferably selected from the group of paints and varnishes and the natural or synthetic rubbers and rubbers.
  • the ready-to-use phosphating solutions can be achieved by dissolving the individual Components in the required concentration in water on site getting produced.
  • the usual procedure is to concentrate who manufactures phosphating solutions based on the application concentration be diluted.
  • Aqueous concentrates are usually made so that the application concentration by dilution with water by a factor between 5 and 200, preferably between 20 and 100, can be adjusted.
  • the invention also includes aqueous concentrates, from which the above by appropriate dilution with water described phosphating solutions can be obtained.
  • powdered concentrates can be used as an alternative to liquid-aqueous concentrates. Their composition is chosen so that when dissolving the powder in water in a concentration between 0.2 and 5 wt .-%, preferably between 0.5 and 3 wt .-% of those described above Receives phosphating solutions.
  • Iron phosphating baths can be based on the pH value, the electrical conductivity or controlled and regulated via the total acid score will.
  • Layer weights were obtained by peeling off the phosphate layer with triethanolamine determined according to DIN 50942.
  • a three-week salt spray test was carried out in accordance with DIN 53167. Here was the paint infiltration on a cut after 21 days of testing measured.
  • the phosphating baths had the following composition: 0.5% Phosphoric acid 75% 0.02% 50% gluconic acid 0.1% Na cumene sulfonate 0.1% P3-Tensopon R 0555 (nonionic surfactant mixture based on fatty alcohol ethoxylate propoxylate, 30% aqueous solution; Henkel KGaA, Düsseldorf) 0.005% FeSO 4 x 7H 2 O

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Claims (12)

  1. Solution aqueuse pour la ferrophosphatation de métaux ayant un pH compris entre 3,5 et 6, contenant
    a) de 1 à 20 g/litre de phosphate dissous,
    b) de 0,02 à 2 g/litre d'acide nitrobenzène sulfonique,
    c) de l'eau et si on le désire d'autres adjuvants,
    caractérisée en ce que
    la solution contient en outre
    d) de 0,01 à 0,8 g/litre d'un ou plusieurs acides monocarboxyliques organiques de formule générale (I)
    Figure 00210001
    dans laquelle
    R = H, CH3, CH2Y, C2H5, C2H4Y, C6H5, C6H4Y ou C6H3Y2,
    X et Y représentent indépendamment l'un de l'autre NH2 ou OH, et
    n = 0, 1 ou 2.
  2. Solution de phosphatation selon la revendication 1,
    caractérisée en ce que
    dans la formule générale (I) n = 0 et X = NH2.
  3. Solution de phosphatation selon la revendication 1,
    caractérisée en ce que
    dans la formule générale (I) X = OH.
  4. Solution de phosphatation selon une ou un plusieurs des revendications 1 à 3,
    caractérisée en ce qu'
    elle contient de 0,1 à 0,8 g/litre d'un ou plusieurs acides carboxyliques de formule générale (I).
  5. Solution de phosphatation selon une ou plusieurs des revendications 1 à 4,
    caractérisée en ce qu'
    elle contient de 0,2 à 0,5 g/litre d'acide nitrobenzène sulfonique.
  6. Solution de phosphatation selon une ou plusieurs des revendications 1 à 5,
    caractérisée en ce qu'
    elle contient comme acide nitrobenzène sulfonique l'acide m nitrobenzène sulfonique.
  7. Solution de phosphatation selon une ou plusieurs des revendications 1 à 6,
    caractérisée en ce qu'
    elle contient un ou plusieurs des -adjuvants suivants :
    e) de 0,05 à 3 g/litre de fluorure libre et/ou lié de manière complexe,
    f) de 0,1 à 6 g/litre d'un acide carboxylique chélatant comportant au moins quatre atomes de carbone et au moins trois substituants choisis parmi les groupes carboxyle et les groupes hydroxy,
    g) de 0,02 à 20 millimole/litre de molybdate et/ou de tungstate.
    h) de 0,05 à 0,2 g/litre d'un composé de titane anionique,
    i) jusqu'à 40 g/litre d'agents tensioactifs,
    k) de 0,05 à 5 g/litre de nitrate.
  8. Procédé de ferrophosphatation de surfaces métalliques choisies parmi les surfaces d'acier, de zinc, d'aluminium ou d'alliages, dont le composant principal représente au moins l'un des métaux fer, zinc ou aluminium, par mise en contact des surfaces avec des solutions selon une ou plusieurs des revendications 1 à 7, à une température comprise entre 30 et 70°C pendant une durée comprise entre 15 secondes et 10 minutes par immersion dans la solution et/ou par pulvérisation avec la solution.
  9. Procédé selon la revendication 8,
    caractérisé en ce qu'
    on produit des couches de phosphate ayant un poids de couche compris entre 0,2 et 1 g/m2.
  10. Procédé selon un ou deux des revendications 8 et 9 de prétraitement de surfaces métalliques avant le dépôt d'un revêtement organique.
  11. Concentré aqueux, qui lorsqu'il est dilué avec de l'eau d'un facteur compris entre 5 et 200 donne une solution de ferrophosphatation selon une ou plusieurs des revendications 1 à 7.
  12. Agent pulvérulent, qui donne lorsqu'on le dissout dans l'eau à une concentration comprise entre 0,2 et 5 % en poids une solution de ferrophosphatation selon une ou plusieurs des revendications 1 à 7.
EP95922451A 1994-05-21 1995-05-12 Phosphatation ferrique a l'aide d'acides monocarboxyliques substitues Expired - Lifetime EP0760870B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4417965A DE4417965A1 (de) 1994-05-21 1994-05-21 Eisenphosphatierung unter Verwendung von substituierten Monocarbonsäuren
DE4417965 1994-05-21
PCT/EP1995/001815 WO1995032319A1 (fr) 1994-05-21 1995-05-12 Phosphatation ferrique a l'aide d'acides monocarboxyliques substitues

Publications (2)

Publication Number Publication Date
EP0760870A1 EP0760870A1 (fr) 1997-03-12
EP0760870B1 true EP0760870B1 (fr) 1998-10-28

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US (1) US5919318A (fr)
EP (1) EP0760870B1 (fr)
JP (1) JPH10500452A (fr)
AT (1) ATE172757T1 (fr)
CA (1) CA2190991A1 (fr)
DE (2) DE4417965A1 (fr)
DK (1) DK0760870T3 (fr)
ES (1) ES2124558T3 (fr)
WO (1) WO1995032319A1 (fr)

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US7144599B2 (en) 2004-07-15 2006-12-05 Birchwood Laboratories, Inc. Hybrid metal oxide/organometallic conversion coating for ferrous metals
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CA3041934A1 (fr) * 2016-11-23 2018-05-31 Chemetall Gmbh Composition et procede de pretraitement sans chrome de surfaces d'aluminium
EP3502311A1 (fr) * 2017-12-20 2019-06-26 Henkel AG & Co. KGaA Procédé de prétraitement de nettoyage et de protection anticorrosion de composants métalliques

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Publication number Publication date
JPH10500452A (ja) 1998-01-13
DE59504085D1 (de) 1998-12-03
ATE172757T1 (de) 1998-11-15
CA2190991A1 (fr) 1995-11-30
EP0760870A1 (fr) 1997-03-12
DE4417965A1 (de) 1995-11-23
DK0760870T3 (da) 1999-07-12
WO1995032319A1 (fr) 1995-11-30
US5919318A (en) 1999-07-06
ES2124558T3 (es) 1999-02-01

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