EP3044348B1 - Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion - Google Patents

Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion Download PDF

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EP3044348B1
EP3044348B1 EP14771781.3A EP14771781A EP3044348B1 EP 3044348 B1 EP3044348 B1 EP 3044348B1 EP 14771781 A EP14771781 A EP 14771781A EP 3044348 B1 EP3044348 B1 EP 3044348B1
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Prior art keywords
treatment solution
iii
chromium
ions
coating layer
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EP3044348A1 (fr
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Thomas Nitzsche
Julian Hoffmann
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Hillebrand Chemicals GmbH
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Hillebrand Chemicals GmbH
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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
    • 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
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • 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
    • C23C22/17—Orthophosphates containing zinc cations containing also 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
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the present invention relates to a treatment solution for a method for producing an anti-corrosive coating layer, a concentrate of such a treatment solution and a method for producing an anti-corrosive coating layer.
  • Processes for producing a corrosion-protective coating layer on a metallic surface are known from practice, in which the surface to be treated is brought into contact with a treatment solution.
  • multistage processes are predominantly used, which include passivation, rinsing steps (cascade rinsing) and, if necessary, subsequent sealing.
  • the passivation is followed by at least one rinsing step, in which the salt load required to create an insoluble conversion layer, which would otherwise lead to reduced corrosion protection, is removed from the surface of the workpiece to be treated. Wastewater contaminated with heavy metals is the result, which must be clarified at a corresponding cost.
  • the subsequent sealing is usually carried out in a separate system and is therefore expensive.
  • film-forming polymers In the case of single-stage processes, either insufficient protection against corrosion is achieved or the use of film-forming polymers is necessary. Film-forming polymers, i.e. those which are used for surface filming, however, tend to stick together, which means that these processes are not suitable for all geometric shapes of bulk goods or for strip coatings. In addition, the use of film-forming polymers leads to inhomogeneities within the coating layer and thus to a reduced barrier effect of the anti-corrosive coating layer.
  • the WO 2011/000969 A1 discloses a method of corrosion treatment for zinc and zinc alloy surfaces.
  • An aqueous treatment solution of chromium (III) ions and phosphate is used for this.
  • Silanes of a specifically defined type are used here. It can be assumed that the treatment solution contains microscopic or even macroscopic organic particles which shorten the service life of the coating bath and / or lead to a reduction in quality on the surface of the workpiece.
  • EP 2 014 793 A2 for corrosion treatment is based on the use of a conversion layer on which the coating layer is produced.
  • JP-2005-023372 A and WO 2012/137680 A1 disclose a method for producing a chromium (III) -containing protective layer. This is also based on the use of a conversion layer on which the coating layer is produced.
  • the object of the present invention is therefore to provide effective protection against corrosion on metallic surfaces.
  • a versatile method is to be made available, which is preferably one-stage - that is, without subsequent rinsing steps and possibly separate sealing - and with one
  • a large number of metallic surfaces which contain, for example, aluminum, magnesium, nickel, cadmium, zinc, tin, manganese, magnesium and / or their alloys, can be used.
  • a treatment solution for such a method and a concentrate of such a treatment solution are to be proposed.
  • the invention is based on the knowledge that avoiding the in WO 2011/000969 A1 specifically described silanes in the treatment solution also prevents their entry into the coating layer to be produced. It has been recognized that silanes of this type can lead to pores and defects in the coating layer and thus reduce the quality of the coating layer to be produced. As a result, the use of silanes WO 2011/000969 A1 is dispensed with, the dried, anti-corrosive coating layer has a more homogeneous structure and, thanks to the improved barrier effect, inhibits the diffusion of attacking agents to a greater extent.
  • the anti-corrosive coating layer produced with the method according to the invention has little redissolution in aqueous media in the dried state. Furthermore, it shows a surprisingly high degree of flexibility, which avoids cracks and breaks when the metallic surface moves.
  • disadvantages of conventional passivation processes can be avoided according to the invention, namely that insufficient drying properties are achieved during drying and thus the salts (containing water of crystallization) greatly reduce the corrosion protection and contaminate and irreversibly damage any subsequent solvent-based coating media.
  • a sealing layer can be achieved which makes downstream rinsing steps superfluous, with which excellent corrosion protection can be achieved and negative influences on subsequent coating media, in particular water entry into solvent-based coating media, can be avoided.
  • the anti-corrosive coating layer applied according to the invention combines the functionalities of a chromium (III) ion-containing passivation layer and a high-quality sealing layer.
  • the method according to the invention allows passivation and sealing in one treatment step without subsequent rinsing steps.
  • silanes like those in the WO 2011/000969 A1 show a strong tendency to coagulation in the neutral or alkaline pH range
  • the storage stability of the treatment solution is due to the omission of the silanes WO 2011/000969 A1 clearly improved.
  • the stability in the alkaline also enables the use of a base solution according to the invention as an alkaline auxiliary in paint compositions.
  • the invention also allows the use of toxic and environmentally hazardous chromium (VI) ions to be dispensed with.
  • the treatment solution according to the invention behaves in a stable manner with regard to additives that adjust the coefficient of friction, that is to say lubricants, and other functionally required components.
  • a “treatment solution” within the meaning of the present invention can be an aqueous solution, i.e. one which predominantly contains water as a solvent.
  • the treatment solution can also be a non-aqueous one, that is to say one which predominantly contains at least one organic solvent as solvent.
  • the treatment solution is an aqueous solution.
  • the proportion of water in the total solvent is preferably more than 50% by weight, preferably more than 65% by weight, more preferably more than 80% by weight and particularly preferably more than 90% by weight. If, on the other hand, the treatment solution is a non-aqueous solution, the proportion of water in the total solvent is less than 5% by weight, preferably 1 to 3% by weight.
  • chromium (III) ion source is understood to mean at least one compound which, in the treatment solution, releases chromium (III) ions, preferably in complexed form.
  • source of phosphate in the context of the present invention stands for at least one compound which releases phosphate in the treatment solution.
  • a “zinc ion source” in the context of the present invention is at least one compound which releases zinc ions, preferably in complexed form, in the treatment solution.
  • citrate source stands for at least one compound which releases citrate in the treatment solution.
  • phosphate in particular stands for unprotonated orthophosphate, singly protonated orthophosphate (hydrogen phosphate) and doubly protonated orthophosphate (dihydrogen phosphate) and orthophosphoric acid.
  • citrate includes, in particular, unprotonated, singly protonated and doubly protonated citrate and citric acid.
  • a “ lubricant” within the meaning of the present invention describes a dispersion of micronized particles which reduce the frictional resistance of two contact surfaces moving relative to one another and which is preferably able to set a defined coefficient of friction.
  • the lubricant has no film-forming properties.
  • the term “metallic surface” also includes those surfaces made of metal to which one or more non-metallic organic and / or inorganic coatings, in particular a conversion layer, have already been applied.
  • the “molar ratio” is the ratio of the relative amount of one substance in the treatment solution in mol of the substance / kg of treatment solution to the relative amount Amount of another substance in the treatment solution in mol of the substance / kg treatment solution.
  • the treatment solution according to the invention contains a chromium (III) ion source, a phosphate source, a zinc ion source and a citrate source.
  • the molar ratio of chromium (III) ions to zinc ions is 1: at least 1.65 and the molar ratio of chromium (III) ions to citrate is 1: at least 1.4.
  • the molar ratio of chromium (III) ions to zinc ions is therefore at most 0.61 and the molar ratio of chromium (III) ions to citrate is at most 0.72.
  • the molar percentage of zinc ions outweighs the molar percentage of chromium (III) ions by at least 1.65 times and the molar percentage of citrate compared to the molar percentage of chromium (III) ions by at least 1.4 times.
  • the treatment solution is also essentially free of silanes WO 2011/000969 A1 .
  • "Essentially free of any of the silanes WO 2011/000969 A1 means that the treatment solution contains less than 10 g / l, preferably less than 5 g / l, more preferably less than 1 g / l and particularly preferably less than 0.1 g / l of silanes WO 2011/000969 A1 contains.
  • the treatment solution particularly preferably does not contain any silanes at all WO 2011/000969 A1 .
  • the chromium (III) ion source contained in the treatment solution is preferably selected from the group consisting of inorganic chromium (III) salts, chromium (III) salts of organic acids and chromium (VI) compounds, from which chromium ( III) ions can be generated in situ, preferably in complexed form, and mixtures of these. Chromium (VI) compounds are particularly preferably used.
  • Suitable inorganic chromium (III) salts are, for example, basic chromium (III) sulfate, chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) chloride, chromium (III) nitrate, potassium chromium (III) Sulfate and mixtures of these.
  • Chromium (III) hydroxide, chromium (III) dihydrogen phosphate, chromium (III) nitrate or potassium chromium (III) sulfate are preferably used.
  • Suitable chromium (III) salts of organic acids are, for example, chromium (III) methanesulfonate, chromium (III) citrate, chromium (III) tartrate, chromium (III) acetate and mixtures of these.
  • Suitable chromium (VI) compounds for the in situ generation of chromium (III) ions are, for example, chromium (VI) oxide, chromates such as potassium or sodium chromate, dichromates such as potassium or sodium dichromate, and mixtures of these.
  • Suitable reducing agents for the in situ generation of chromium (III) ions are, for example, sulfites such as sodium sulfite, sulfur dioxide, phosphites, hypophosphites such as sodium hypophosphite, phosphorous acid, hydrogen peroxide, alcohols such as methanol, hydroxycarboxylic acids, hydroxydicarboxylic acids such as gluconic acid or malic acid, citric acid, and mixtures of this.
  • sulfites such as sodium sulfite, sulfur dioxide, phosphites, hypophosphites such as sodium hypophosphite, phosphorous acid, hydrogen peroxide, alcohols such as methanol, hydroxycarboxylic acids, hydroxydicarboxylic acids such as gluconic acid or malic acid, citric acid, and mixtures of this.
  • the Phosphatquellle contained in the treating solution is selected from the group consisting of ortho-phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid and their salts, in all possible protonation, di -Phosphorpentoxid and mixtures thereof.
  • Orthophosphoric acid is particularly preferably used.
  • the source of zinc ions contained in the treatment solution is preferably a zinc salt.
  • Suitable zinc salts are, for example, zinc sulfate, zinc chloride, zinc phosphate, zinc oxide, zinc hydroxide, zinc citrate and mixtures of these. Zinc oxide or zinc phosphate is particularly preferably used.
  • the citrate source contained in the treatment solution is preferably selected from the group consisting of citric acid and salts of citric acid, that is to say salts with unprotonated, singly or doubly protonated citrate.
  • Suitable salts of citric acid are monosodium citrate, disodium citrate, trisodium citrate, ammonium citrate and potassium citrate.
  • the phosphate concentration in the treatment solution is preferably between 1 g / l and 110 g / l, more preferably between 5 g / l and 50 g / l and particularly preferably between 10 g / l and 35 g / l (calculated as orthophosphate) .
  • the treatment solution preferably has a molar ratio of chromium (III) ions to phosphate between 1: 1.5 and 1: 5, preferably between 1: 2 and 1: 4.5 and particularly preferably between 1: 3 and 1: 4.
  • the molar ratio of chromium (III) ions to zinc ions in the treatment solution is between 1: 1.65 and 1: 2.35, preferably between 1: 1.75 and 1: 2.25, more preferably between 1 : 1.85 and 1: 2.15 and most preferably about 1: 2.
  • the molar ratio of chromium (III) ions to citrate is in the treatment solution between 1: 1.4 and 1: 1.8, preferably between 1: 1.45 and 1: 1.75, more preferably between 1: 1.5 and 1: 1.7 and particularly preferably around 1: 1, 6th
  • the molar ratio of chromium (III) ions to zinc ions in the treatment solution is particularly preferably matched to the molar ratio of chromium (III) ions to citrate, so that the molar ratio of chromium (III) ions to zinc ions is between 1: 1.65 and 1: 2.35 and that of chromium (III) ions to citrate is between 1: 1.4 and 1: 1.8, the molar ratio of chromium (III) ions to zinc ions is preferably between 1: 1.75 and 1: 2.25 and that of chromium (III) ions to citrate is between 1: 1.45 and 1: 1.75, more preferably the molar ratio of chromium
  • illustration 1 serves to illustrate the concentration ratios resulting from the use of the formula (1) and the formula (2).
  • the concentration ratios correspond to the length ratios of the respective lines of the triangle shown.
  • the concentration of the chromium (III) ions in the treatment solution is preferably between 0.2 g / l and 27 g / l, preferably between 0.2 g / l and 20 g / l, more preferably between 0.5 g / l and 15 g / l and particularly preferably between 1 g / l and 10 g / l.
  • the concentration of zinc ions in the treatment solution is preferably between 0.5 and 66 g / l, preferably between 0.5 and 49 g / l, more preferably between 1.2 and 37 g / l and particularly preferably between 2.5 and 25 g / l.
  • the concentration of the citrate in the treatment solution is between 1.1 and 154 g / l, preferably between 1.1 and 114 g / l, more preferably between 2.8 and 85 g / l and particularly preferably between 5.7 and 57 g / l.
  • the concentrations of the chromium (III) ions, the zinc ions and the citrate in the treatment solution are matched to one another in such a way that the concentration of the chromium (III) ions is between 0.2 and 27 g / l, that of the zinc ions between 0.5 and 66 g / l and that of the citrate between 1.1 and 154 g / l, preferably the concentration of chromium (III) ions between 0.2 and 20 g / l, that of zinc ions between 0, 5 and 49 g / l and that of the citrate is between 1.1 and 114 g / l, more preferably the concentration of the chromium (III) ions between 0.5 and 15 g / l, that of the zinc ions between 1.2 and 37 g / l and that of the citrate is between 2.8 and 85 g / l and particularly preferably the concentration of chromium (III) ions between 1 and 10 g
  • Table 1 combination Chromium (III) ions to zinc ions Chromium (III) ions to citrate Chromium (III) ions to phosphate #1 1: 1.65 to 1: 2.35 1: 1.4 to 1: 1.8 1: 1.5 to 1: 5 # 2 1: 1.65 to 1: 2.35 1: 1.4 to 1: 1.8 1: 2 to 1: 4.5 # 3 1: 1.65 to 1: 2.35 1: 1.4 to 1: 1.8 1: 3 to 1: 4 # 4 1: 1.65 to 1: 2.35 1: 1.45 to 1: 1.75 1: 1.5 to 1: 5 # 5 1: 1.65 to 1: 2.35 1: 1.45 to 1: 1.75 1: 2 to 1: 4.5 # 6 1: 1.65 to 1: 2.35 1: 1.45 to 1: 1.75 1: 3 to 1: 4 # 7 1: 1.65 to 1: 2.35 1: 1.5 to 1: 1: 7 1: 1.5 to 1: 1: 7 1: 1.5 to 1: 1: 7 1: 1.5 to 1: 1: 7 1: 1.5 to 1:
  • the treatment solution preferably additionally contains at least one surfactant, preferably at least one nonionic, anionic or amphoteric surfactant, or particularly preferably a combination thereof, for example a combination of a nonionic with an anionic surfactant, a combination of a nonionic with an amphoteric surfactant, a combination of an anionic with an amphoteric surfactant or a combination of a nonionic, an anionic and an amphoteric surfactant.
  • the addition of surfactants can promote the film formation of the treatment solution on the metallic surface to be treated.
  • the total concentration of surfactant is preferably between 0.01 and 30 g / l, preferably between 0.1 and 15 g / l, more preferably between 0.2 and 8 g / l particularly preferably between 0.3 and 3 g / l.
  • the “total concentration of surfactant” is understood to mean the ratio of the sum of the weights of the surfactants present in the treatment solution in relation to the volume of the treatment solution.
  • the treatment solution contains at least one nonionic and at least one anionic surfactant in a mass ratio of 4: 1 to 1: 8, preferably from 2: 1 to 1: 6, more preferably from 1: 1 to 1: 4 and particularly preferred from 1: 1 to 1: 2.
  • the treatment solution contains at least one nonionic, at least one anionic and at least one amphoteric surfactant in a mass ratio of 1: 1: 1 to 1: 5: 1, preferably 1: 2: 1 to 1: 4: 1 and particularly preferably from about 1: 3: 1.
  • Preferred nonionic surfactants are Alkyloxethylate as Lutensol ON 50 ® (BASF), alkyl polyglucosides, such as Triton TM CG-110 (Dow Chemicals), polyalkylene glycol ethers, Guerbet alcohol as Lutensol ® XL 40 (BASF), Fettaminoethoxylate and mixtures thereof.
  • Preferred anionic surfactants are fatty alcohol polyglycol (oxyethylene) sulfonates as Ralufon ® F 11-13 (Raschig), arylsulfonates such as K-Na cumene sulfonate, fatty alcohol sulfates, alkyl carboxylates, alkylbenzene sulfonates and mixtures thereof.
  • Preferred amphoteric surfactants are alkyl betaine, dipalmitoyl lecithin and mixtures of these.
  • the aqueous treatment solution additionally contains at least one organophosphate and / or organophosphonate. This can lead to a higher degree of crosslinking of the anti-corrosive coating layer produced and thus to improved anti-corrosive properties.
  • the aqueous treatment solution preferably contains at least one organophosphonate, preferably at least one aminophosphonate.
  • Preferred aminophosphonates here are aminotris (alkylphosphonic acid) with a chain length of C1 to C8 for the alkyl group, dimethylaminoethanediphosphonic acid (DMAEDP), 1-aminoethanediphosphonic acid (AEDP), diethylenetriaminepenta (methylenephosphonic acid), (DTPxyMP), ethylenediamine-tetra () methylene-phosphonic acid (EDPXMP), ethylenediamine-tetra (methylene-phosphonic acid) -amino-di (methylenephosphonic acid) (HEMPA) and mixtures of these.
  • DMAEDP dimethylaminoethanediphosphonic acid
  • AEDP 1-aminoethanediphosphonic acid
  • DTPxyMP diethylenetriaminepenta
  • EDPXMP ethylenediamine-tetra () methylene-phosphonic acid
  • HEMPA ethylenediamine-tetra (methylene-phosphonic
  • the total concentration of aminophosphonate is preferably between 0.05 g / l and 8 g / l, preferably between 0.1 g / l and 5 g / l and particularly preferably between 0.3 g / l and 3 g / l and am most preferably between 0.4g / l and 1.5g / l.
  • the incorporation of polymers into the anti-corrosion coating layer leads to a reduced barrier effect and thus also to reduced corrosion protection of the coating layer.
  • the latter is also due to the fact that the cathodic partial reaction of corrosion is less inhibited.
  • the passivation step is usually followed by a sealing step in the prior art.
  • a corrosion-protective coating layer can be produced which is essentially free of polymers. This can be achieved by using a treatment solution which is essentially free of certain polymers and copolymers which are soluble in water and / or organic solvents.
  • “Essentially free from” means that the treatment solution has less than 10 g / l, preferably less than 5 g / l, more preferably less than 1 g / l and particularly preferably less than 0.1 g / l of the corresponding polymers or copolymers contains.
  • polymers and copolymers are, in particular, so-called film-forming polymers, i.e. those which promote the formation of a film in the anti-corrosive coating layer and therefore also build into the layer under the selected reaction conditions, which leads to imperfections in the barrier. They usually become part of the treatment solution directly added as a powder or as a preliminary solution.
  • the treatment solution is very particularly preferably essentially free from film-forming polymers.
  • silanes are suitable for this and are preferably to be avoided according to the invention.
  • the treatment solution is therefore preferably not only essentially free from silanes WO 2011/000969 A1 but also essentially free of silanes in general.
  • the treatment solution is essentially free from silanes, particularly preferably essentially free from silanes, polyvinylpyrrolidone, polyvinyl alcohol and their copolymers and particularly preferably free from silanes, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycols, polyitaconic acids, polyacrylates and their copolymers.
  • the anti-corrosive coating layer is a tribologically functional cover layer.
  • the treatment solution additionally contains 0.01 to 50% by weight, preferably 0.05 to 30% by weight and particularly preferably 0.1 to 15% by weight of at least one lubricant.
  • Preferred lubricants are those substances which are insoluble in water and / or organic solvents, that is, insoluble in the treatment solution used, and have no film-forming properties, for example due to the high melting temperatures.
  • the at least one lubricant is preferably selected from the group consisting of polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene (ETFE), perfluorinated polyethers (PFPE), polyvinylidene fluoride (PVDF), tetrafluoroethylene / hexafluoroethylene copolymer (FEP), perfluoroalkoxy copolymer (PFA) , Polysulfones, MoS2, WS2, TiS2, BN graphite and micro-encapsulated lubricants.
  • PTFE polytetrafluoroethylene
  • ETFE ethylene-tetrafluoroethylene
  • PFPE perfluorinated polyethers
  • PVDF polyvinylidene fluoride
  • FEP tetrafluoroethylene / hexafluoroethylene copolymer
  • PFA perfluoroalkoxy copolymer
  • the pH value of the treatment solution can be set in a range from 2 to 11.5 and must be adapted to requirements depending on the area of application and design or condition of the surface. For parts to be treated with optical demands on the metal surface and to achieve the best possible, a mildly acidic pH value of the treatment solution is preferably set. If the treatment solution is used to create an intermediate layer for layer combinations with topcoats, a lower pH value of less than 4 reduces the application time. When used as an additive to increase corrosion protection or when adding alkaline lubricant additives to functionalize the dry layer, a pH value above 7 must be set.
  • the treatment solution can be prepared by diluting a concentrate, that is to say a correspondingly more highly concentrated base solution.
  • the mass fraction of the base solution in the finished treatment solution is preferably 1 to 100%, more preferably 1 to 50%, further preferably 1 to 25%, further preferably 1 to 15% and very particularly preferably 3 to 12%.
  • the concentrate according to the invention of a treatment solution for a method for producing a corrosion-protective coating layer on a metallic surface, in which the surface to be treated is brought into contact with a treatment solution, can be obtained by removing at least part of the solvent from the treatment solution according to the invention.
  • the method according to the invention for producing a corrosion-protective coating layer on a metallic surface provides that the surface to be treated is brought into contact with the treatment solution according to the invention.
  • the process parameters such as treatment temperature, treatment time, drying temperature and total drying time are to be adapted to the requirements depending on the area of application and design or condition of the surface.
  • the treatment temperature is preferably in the range from 10 to 90.degree. C., more preferably from 15 to 80.degree. C. and particularly preferably from 25 to 60.degree.
  • the treatment time i.e. the time during which the treatment solution is in contact with the surface before drying, is preferably in the range from 1 s to 60 min, preferably from 5 s to 40 min, more preferably from 10 s to 30 min and particularly preferably from 20 s to 15 min.
  • the drying temperature i.e. the temperature during the subsequent drying of the treated surface, is preferably in the range from 20 (room temperature) to 250 ° C, preferably from 50 to 200 ° C and particularly preferably from 80 to 180 ° C.
  • Active drying can be carried out by induction, infrared or hot air.
  • the total drying time i.e. the time for active and passive drying, can vary between 10 s and 96 h.
  • rinsing steps are not required.
  • the drying can therefore take place after the treatment of the metallic surface with the treatment solution without previous rinsing steps.
  • the anti-corrosive coating layer produced according to the invention can serve on the one hand as a cover layer and on the other hand as an intermediate layer (intermediate barrier or vapor barrier and / or adhesion-promoting layer) on both metal-containing layers cathodically protecting the substrate and on all-metal goods. In addition, it can also act as a modification of the surface of ⁇ m-scaled metal particles.
  • the metallic surface can be preconditioned in a suitable manner.
  • a suitable preconditioning is, in particular, the activation of the metallic surface by bringing it into contact with an acid that is highly diluted with water, coordinated acid combinations or salts of suitable acids.
  • the metallic surface can have a conversion layer.
  • a “conversion layer” is preferably understood to mean a layer which is created by a chemical reaction of a (in particular aqueous) treatment solution with a metal substrate.
  • the function as an adhesion promoter between the metal substrate and a further layer is preferably in the foreground as opposed to any further functions.
  • a passivation layer can also function as a conversion layer.
  • the conversion layer is preferably a chromium (III) -containing conversion layer.
  • Such conversion layers can be produced, for example, with GC Multipass and DDPass (both products from Hillebrand Chemicals GmbH).
  • the treatment solution according to the invention is used as a post-immersion solution and the method according to the invention thus leads to further improved protection against corrosion.
  • the anti-corrosive coating layer according to the invention serves in this case as a seal with post-passivating properties and can also function as an additional primer for further layer structures.
  • the metallic surface does not have a conversion layer.
  • the aggressiveness of the mechanism of action is much lower than that of passivation, prolonged contact of the metallic surface with the treatment solution does not lead to overpassivations (dissolving back of the passivation layer) and thus to a loss of corrosion protection.
  • the salt load on the surface dries to form a barrier-tight layer and is therefore not disruptive.
  • the present invention therefore also relates to a method for producing a corrosion-protective coating layer on a metallic surface, the surface to be treated not having a conversion layer, the passivation and sealing of the surface to be treated taking place in one step and without an intervening rinsing step and the coating layer formed in Essentially free from silanes WO 2011/000969 A1 is.
  • the metallic surface to be treated is a material applied to a steel substrate which, in relation to the steel substrate, has a less noble electrochemical potential.
  • the metallic surface is the surface of a tape product.
  • Bulk or rack goods, coated with galvanically deposited layers of zinc or zinc alloy layers such as ZnFe, ZnSn, ZnMn, ZnCd, ZnNi and ternary systems, can be immersed in the treatment solution according to the invention to increase the corrosion protection.
  • the treatment solution is preferably adjusted to a pH value of 4 to 5 and the goods are preferably actively dried at 80 ° C. for 10 minutes.
  • the top layer produced has no tendency to stick, which leads to very good coating results, especially when used on bulk goods.
  • Surface areas with an extremely wet layer thickness of the treatment solution dry without the occurrence of flakes to form a flexible film.
  • the pH value can be reduced to values down to pH 3, which results in a shorter treatment time and / or a stronger passivation effect.
  • the treatment solution according to the invention is preferably adjusted to a pH of 3 to 6.
  • a lower pH value of the treatment solution can reduce the Treatment temperature can be lowered to room temperature, which can save energy, especially with large bath surfaces. If the hot, already quenched, hot-dip galvanized goods are brought into contact with the treatment solution, a closed layer is formed due to the reactivity of the active substances, which dries due to the residual heat of the part body without additional energy input.
  • Zinc or aluminum surfaces applied by flame spraying can be treated with the treatment solution according to the invention, preferably at pH values between 3 and 6.
  • the process-related residual heat can also be used here to completely dry the post-treatment layer.
  • thermodiffusion-galvanized surfaces Another area of application of the treatment solution according to the invention is the coating of thermodiffusion-galvanized surfaces.
  • the combination of passivation and sealing results in the advantage that, despite the high iron content of the diffusion layer, the punctual red rust breakthroughs that typically occur early can be prevented for a long time. Bulk goods can be handled without any problems due to the universal applicability of the passivation solution.
  • a particularly wide range of pH values for setting the process chemistry enables different layer properties on thermal diffusion zinc. For example, by setting a mild pH value of 4 to 5, the original surface coloration can be retained, whereas a pH value of 2.5 to 3.5 produces dark layers.
  • Mechanically galvanized goods are coated with the treatment solution according to the invention, preferably in the pH range from 4.3 to 4.6, to increase corrosion.
  • the typical surface color is retained.
  • By lowering the pH value below 4 dark layers can be achieved.
  • Bulk goods, which are typical for this process, can easily be coated and actively or dried at room temperature without the goods sticking.
  • the method according to the invention is also suitable for the treatment of metal goods which have metal dispersion dry layers (MDTS).
  • MDTS typically have a layer thickness of 5 to 25 ⁇ m.
  • MDTS can be produced on metallic surfaces by bringing the surface to be treated into contact with a special dispersion and then drying it.
  • the dispersion contains an organic and / or inorganic binding matrix as well as ⁇ m-scaled metal particles in spherical and / or lamellar form.
  • the ⁇ m-scaled metal particles are zinc, aluminum, magnesium, manganese, tin, nickel, iron, molybdenum and / or vanadium particles and / or particles which consist of an alloy of the metals mentioned.
  • the ⁇ m-scaled metal particles can also contain the smallest amounts of rare earths or their alloys.
  • the treated metal goods preferably consist of materials which have an electrochemically more noble potential than the MDTS surrounding them.
  • Modern MDTS can have a metallic silver or dark gray to black surface.
  • the treatment solution can be applied to an untreated, clean MDTS.
  • the coating layer obtained after drying then functions at the same time as a layer-forming passivation and a corrosion-protecting cover layer, preferably with sealing properties. Tribological properties can also be adjusted by means of lubricants integrated into the anti-corrosive coating layer.
  • An optional black colored treatment solution supports the look of black MDTS. In the case of visually higher quality parts with MDTS, the treatment solution should not be applied with a pH value below 4.4.
  • the treatment solution therefore has a mild pH value, preferably between 4 and 11.5, preferably between 4.5 and 10 and particularly preferably between 5 and 7.5.
  • the corrosion-protecting coating layer can also be used as an adhesion-promoting intermediate layer, in particular as a passivation and vapor barrier for further organic and / or inorganic top coatings.
  • a lower pH value of the treatment solution reduces the treatment time.
  • the treatment solution thus has an acidic pH value, preferably between 2 and 7, preferably between 3 and 6 and particularly preferably between 3.5 and 5.
  • the temperature is preferably in the range from 15 to 80.degree. C., more preferably from 25 to 60.degree.
  • the treatment time is preferably in the range from 1 second to 5 minutes, preferably from 5 seconds to 3 minutes, more preferably from 10 seconds to 2 minutes and particularly preferably from 20 to 90 s
  • the drying temperature is preferably in the range from 80 to 180 ° C.
  • the total drying time is preferably in the range from 5 minutes to 96 hours, preferably from 5 minutes to 3 hours and particularly preferably from 10 to 30 minutes.
  • the treatment solution according to the invention is used for coating metallic materials, preferably consisting of zinc, aluminum, manganese, magnesium, tin, silicon and their alloys to increase corrosion protection, optimize the overall process and / or adjust functional properties.
  • the metallic surface is preferably selected from the group consisting of full metal surfaces, preferably containing zinc, aluminum, magnesium or an alloy of zinc, aluminum and / or magnesium with preferred trace elements, zinc die-cast surfaces, preferably containing a zamak alloy, preferably ZL0400, ZL0410 or ZL0430, surfaces of ⁇ m-scaled metal particles and plated aluminum surfaces.
  • the treatment solution according to the invention is used, for example, on fully metallic surfaces made of zinc or zinc alloys, of aluminum or aluminum alloys with silicon, manganese, magnesium and / or copper and of magnesium or magnesium alloys with aluminum, zinc, manganese, silicon and / or zirconium for optical and / or surface modification.
  • the treatment solution is preferably used with a pH value below 3.5.
  • the treatment solution is adjusted to a preferred pH value of just above 4 in order to produce anti-corrosive and / or functional cover layers.
  • Zinc die-cast goods preferably made of zamak alloys such as ZL0400, ZL0410 and ZL0430, both as drum goods and in basket application, are dipped into the treatment solution and either actively dried or at room temperature.
  • the treatment solution By setting the treatment solution to a pH value of 3.5 to 4.2 and a temperature of over 45 ° C, the layer can be darkened without destroying the cast skin of the component, which results in extreme losses in corrosion protection would result.
  • a milder pH value of 4.4 to 5 and a lower temperature of the treatment solution of below 40 ° C are set, the previously existing surface color can be retained. Particularly when it comes to basket application, there is an advantage in drying overcoated areas to form flexible, non-shimmering films.
  • the coating layer produced by means of the treatment solution according to the invention serves as a passivation and adhesion promoter. If metal particles pretreated in this way are used in the production of a metal dispersion, extremely positive effects result with regard to the service life of the dispersion, binding of the modified metal particles in the binder matrix and the course of layer corrosion.
  • the treatment solution should preferably be adjusted to a pH of 2.5 to 6.
  • a mild pH value of approx. 5 in combination with a longer treatment time of over 4 minutes leads to a significant improvement in terms of anchoring with the binder system used, with the appearance of the metal particle surface being changed only to a very small extent.
  • a pH value of the treatment solution in the range from 2.5 to 6.5 is preferably set in order to increase the corrosion protection or other functional properties such as heat distribution or reflectivity. In doing so, optical features for finalizing the surface treatment are obtained in particular through higher pH values. Lower pH values and thus a stronger attack on the sealing passivation, on the other hand, offer the advantage of increased adhesion for other coatings such as industrial paints.
  • a concentrate according to the invention is used as an additive for seals and topcoats. These are liquid and contain water and / or organic solvents as solvents. By treating a metallic surface with a seal modified in this way or a topcoat modified in this way, a more adhesive and barrier-tight cover layer can be produced, which also has a passivating effect.
  • the mixture of concentrate according to the invention with the seal or the topcoat is thus the treatment solution according to the invention.
  • Seals are, by definition, organic and / or inorganic coatings with a dry film thickness of less than 2 ⁇ m and their solutions for production. Topcoats are the counterpart with dry film thicknesses of over 2 ⁇ m.
  • a concentrate according to the invention preferably an aqueous concentrate, is adjusted to be alkaline, preferably to a pH of 7.5 to 11.5, and added in small amounts, preferably 1 to 3% by volume, to a sealant or a topcoat. These then represent a treatment solution within the meaning of the present invention and can be used to produce a more adhesive, barrier-tight layer with passivating properties.
  • the treated metallic surfaces are protected by passivation and a barrier effect, which leads to increased protection against corrosion.
  • the additive also increases the adhesion of the top coat to the treated metallic surfaces.
  • strip goods with electrodeposited layers or full metal surfaces such as zinc, aluminum, magnesium, tin and alloys made from these main components are refined with the treatment solution. Due to the reactive properties of the treatment solution, only very short treatment times are necessary, so that effective corrosion protection can be achieved at high speeds of the belts through the baths.
  • the tape Due to the temperature resistance of the treatment solution, increased temperatures of up to 250 ° C can be used for faster drying of the surface, which can be generated by induction, infrared or hot air. Due to the poor adhesion properties of the treated surfaces, the tape can be rolled up again into coils immediately after the drying process.
  • the corrosion protection values in the following exemplary embodiments relate to production goods that have been subjected to mechanical loads that are customary in the process.
  • the corrosion protection values were determined in an NSS (neutral salt spray) according to DIN EN ISO 9227. In the corrosion protection results, "WR” stands for the time until white rust occurs (zinc corrosion) and “RR” stands for the time until red rust occurs (iron corrosion of the base metal).
  • aqueous solution of the following composition was used as the treatment solution: component Concentration [g / l] Cr 3+ 5.5 PO 4 3- 16 Zn 2+ 13.6 Citrate 3- 31.3 DTPMP 0.4 Lutensol ® ON 50 0.1 Ralufon ® F 11-13 0.3 Triton TM CG-110 0.15
  • a base aqueous solution of the composition component Concentration [g / l] Cr3 + 50 PO43- 350 Zn2 + 120 Citrate3- 280 DTPMP 5 was added to an acrylic seal as a 1% additive.
  • the result was a treatment solution which had the following concentrations: component Concentration [g / l] Cr 3+ 0.5 PO 4 3- 3.5 Zn 2+ 1.2 Citrate 3- 2.8 DTPMP 0.05
  • aqueous solution of the following composition was used as the treatment solution: component Concentration [g / l] Cr 3+ 5.0 PO 4 3- 20th Zn 2+ 12.3 Citrate 3- 28.4 DTPMP 0.4 Lutensol ® XL 40 0.4 K-Na-cumene sulfonate 0.2
  • Zinc die-cast wicker was first hot-degreased, rinsed twice, activated and rinsed twice again. Then the goods were at 35 ° C and a pH of 4.6 dipped in the treatment solution for 75 s and dried at room temperature. The following corrosion protection result was obtained in the NSS: WR: > 504 h
  • aqueous solution of the following composition was used as the treatment solution: component Concentration [g / l] Cr 3+ 5.0 PO 4 3- 20th Zn 2+ 12.3 Citrate 3- 28.4 DTPMP 0.4 Lutensol ® XL 40 0.4 K-Na-cumene sulfonate 0.2
  • aqueous solution of the following composition was used as the treatment solution: component Concentration [g / l] Cr 3+ 14.5 PO 4 3- 96 Zn 2+ 35.7 Citrate 3- 82.4 g / l EDTMP 0.8 q / l
  • a blasted steel surface with a 7 ⁇ m thick MDTS (lamellar zinc and aluminum particles and a titanium oxide / silicon oxide binder system) was subjected to a dip / spin application without a subsequent rinsing step.
  • the steel surface was wetted with the treatment solution for 50 s at 40 ° C. and a pH of 4.4 and then dried at 80 ° C. for 10 min.
  • aqueous solution of the following composition was used as the treatment solution: component Concentration [g / l] Cr 3+ 5 PO 4 3- 15th Zn 2+ 12th Citrate 3- 28 DTPMP 0.4 Lutensol ® ON 50 0.1 Ralufen ® F 11-13 0.2
  • a blasted steel surface with a 7 ⁇ m thick MDTS (lamellar zinc and aluminum particles and a titanium oxide / silicon oxide binder system) was subjected to a dip / spin application without a subsequent rinsing step.
  • the steel surface was wetted with the treatment solution for 50 s at 35 ° C. and a pH of 5.5 and then dried at 80 ° C. for 10 min.

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Claims (13)

  1. Solution de traitement pour un procédé destiné à générer une couche de revêtement inhibitrice de corrosion sur une surface métallique, lors duquel la surface à traiter est mise en contact avec une solution de traitement, laquelle contient
    - une source d'ions chrome(III),
    - une source de phosphate,
    - une source d'ions zinc et
    - une source de citrate,
    le rapport molaire des ions chrome(III) avec les ions zinc étant 1: au moins 1,65 et le rapport molaire des ions chrome(III) avec le citrate étant 1: au moins 1,4 et la solution de traitement contenant moins de 10 g/l de polymères qui peuvent être obtenus par réaction
    - d'un ou de plusieurs alcoxysilanes de la formule R4-xSi(OR1)x
    les résidus R étant identiques ou différents les uns des autres et représentant respectivement un groupe hydrocarboné substitué ou non substitué avec 1 à 22 atomes de carbone, x étant égal à 1, 2 ou 3 et R1 constituant un groupe hydrocarboné substitué ou non substitué avec 1 à 8 atomes de carbone, et
    - d'un ou de plusieurs alcoxydes de la formule Me(OR2)n
    Me représentant Ti, Zr, Hf, Al, Si et n représentant le degré d'oxydation de Me et R2 constituant un groupe hydrocarboné substitué ou non substitué avec 1 à 8 atomes de carbone.
  2. Solution de traitement selon la revendication 1, le rapport molaire des ions chrome(III) avec le phosphate se situant entre 1:1,5 et 1:5, de préférence entre 1:2 et 1:4,5 et mieux encore entre 1:3 et 1:4.
  3. Solution de traitement selon la revendication 1 ou 2, le rapport molaire des ions chrome(III) avec les ions zinc se situant entre 1:1,65 et 1:2,35 et celui des ions chrome(III) avec le citrate entre 1:1,4 et 1:1,8.
  4. Solution de traitement selon l'une des revendications précédentes, la concentration des ions zinc dans la solution de traitement étant calculée à partir de la concentration des ions chrome(III) dans la solution de traitement selon la formule Zn 2 + mol kg = Cr 3 + mol kg sin 30,5 ° ∗ sin   97 °
    Figure imgb0007
     et/ou la concentration du citrate dans la solution de traitement est calculée à partir de la concentration des ions chrome(III) dans la solution de traitement et de la concentration des ions zinc dans la solution de traitement selon la formule Citrat 3 − mol kg = Cr mol kg 2 + Zn mol kg 2 − 2 ∗ Cr mol kg ∗ Zn mol kg ∗ cos   52,5 °
    Figure imgb0008
  5. Solution de traitement selon l'une des revendications précédentes, la concentration des ions chrome(III) dans la solution de traitement se situant entre 0,2 et 27 g/l, celle des ions zinc dans la solution de traitement entre 0,5 et 66 g/l et/ou celle du citrate dans la solution de traitement entre 1,1 et 154 g/l.
  6. Solution de traitement selon l'une des revendications précédentes, la solution de traitement contenant au moins un tensioactif.
  7. Solution de traitement selon l'une des revendications précédentes, la solution de traitement contenant au moins un aminophosphonate et la concentration totale en aminophosphonate se situant entre 0,05 et 8 g/l, de préférence entre 0,1 et 5 g/l, mieux encore entre 0,3 et 3 g/l et mieux encore entre 0,4 et 1,5.
  8. Solution de traitement selon l'une des revendications précédentes, la solution de traitement contenant moins de 10 g/l de silanes.
  9. Solution de traitement selon l'une des revendications précédentes, la couche de revêtement inhibitrice de corrosion étant une couche de recouvrement fonctionnelle tribologique et la solution de traitement contenant en outre 0,1 à 50 % du poids, de préférence 1 à 30 % du poids et mieux encore 3 à 15 % du poids d'au moins un lubrifiant.
  10. Solution de traitement selon l'une des revendications précédentes, la solution de traitement étant produite en ajoutant une solution de base aqueuse d'une valeur pH de 7,5 à 11,5 aux vitrifications ou couches de finition.
  11. Concentré d'une solution de traitement pour un procédé destiné à générer une couche de revêtement inhibitrice de corrosion sur une surface métallique, lors duquel la surface à traiter est mise en contact avec une solution de traitement, que l'on peut obtenir par soustraction d'au moins une partie du solvant de la solution de traitement selon l'une des revendications 1 à 10.
  12. Procédé destiné à générer une couche de revêtement inhibitrice de corrosion sur une surface métallique, lors duquel la surface à traiter est mise en contact avec une solution de traitement selon l'une des revendications 1 à 10.
  13. Utilisation d'une solution de traitement selon l'une des revendications 1 à 10 destinée à générer une couche de revêtement inhibitrice de corrosion sur une surface métallique.
EP14771781.3A 2013-09-13 2014-09-15 Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion Active EP3044348B1 (fr)

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DE102013015113.9A DE102013015113A1 (de) 2013-09-13 2013-09-13 Behandlungslösung für ein Verfahren zum Erzeugen einer korrosionsschützenden Überzugsschicht, Konzentrat einer solchen Behandlungslösung und Verfahren zum Erzeugen einer korrosionsschützenden Überzugsschicht
PCT/EP2014/002486 WO2015036124A1 (fr) 2013-09-13 2014-09-15 Solution de traitement contenant du chrome (iii) pour un procédé de production d'une couche de revêtement de protection anticorrosion, concentré d'une telle solution de traitement et procédé de production d'une couche de revêtement de protection anticorrosion

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EP3569734A1 (fr) * 2018-05-18 2019-11-20 Henkel AG & Co. KGaA Composition de passivation à base de chrome trivalent
CN111996522B (zh) * 2020-08-03 2022-08-16 鞍钢股份有限公司 一种锌铝镁钢板环保钝化剂及制备使用方法
EP3964609A1 (fr) 2020-08-28 2022-03-09 Coventya SAS Produit électroplaqué et procédé de préparation de tels produits par traitement à haute température

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DE19615664A1 (de) * 1996-04-19 1997-10-23 Surtec Produkte Und Systeme Fu Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
DE19638176A1 (de) 1996-09-18 1998-04-16 Surtec Produkte Und Systeme Fu Chrom(VI)freie Chromatschicht sowie Verfahren zu ihrer Herstellung
JP4625244B2 (ja) 2003-07-02 2011-02-02 ディップソール株式会社 ３価クロメート皮膜用仕上げ剤組成物及び３価クロメート皮膜の仕上方法
EP2014793B1 (fr) 2007-06-14 2013-11-20 Atotech Deutschland GmbH Traitement anti-corrosion pour couches de conversion
EP2281923A1 (fr) 2009-07-03 2011-02-09 ATOTECH Deutschland GmbH Traitement de protection anticorrosion pour surfaces en zinc et alliages de zinc
TWI555880B (zh) * 2011-04-01 2016-11-01 迪普索股份有限公司 ３價鉻化學轉換被膜用整理加工劑及黑色３價鉻化學轉換被膜之整理加工方法

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DE19814605A1 (de) * 1998-04-01 1999-10-07 Kunz Gmbh Mittel zur Versiegelung von metallischen, insbesondere aus Zink oder Zinklegierungen bestehenden Untergründen

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CY1124966T1 (el) 2023-01-05
EP3044348A1 (fr) 2016-07-20
PT3044348T (pt) 2022-02-03
DK3044348T3 (da) 2022-02-07
ES2905136T3 (es) 2022-04-07
WO2015036124A1 (fr) 2015-03-19

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