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
  • C23C22/78—Pretreatment of the material to be coated
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
  • C09D5/12—Wash primers
• • 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
• • 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
  • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
  • C23C22/53—Treatment of zinc or alloys based thereon
• • 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
  • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
  • C23C22/56—Treatment of aluminium or alloys based thereon
• • 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
  • C23C22/73—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 characterised by the process
  • C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment
  • B05D3/0272—After-treatment with ovens
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
  • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more

Definitions

• the present invention relates to a process for passivating metallic surfaces by treating the surface with an acidic, aqueous preparation of a carboxylate-containing copolymer.
• the invention further relates to passivation layers and metallic surfaces obtainable by means of the method.
• the metal strips are cut and formed by means of suitable techniques such as punching, drilling, folding, profiling and / or deep drawing to the desired moldings. Larger components, such as automobile bodies are optionally joined together by welding several items.
• the corrosion protection treatment of such metallic materials is usually carried out in multi-stage processes, and the surface of treated metals has several different layers.
• Anti-corrosive treatment can be performed at various points in the manufacturing process. This can be both temporary corrosion protection as well as permanent corrosion protection. A temporary protection is applied, for example, only for storing or transporting a metal strip or other metallic workpiece and removed again before the final processing.
• the protection of metallic components against corrosion has great economic importance. Particularly important technically and economically is the corrosion protection treatment of aluminum surfaces and the surfaces of galvanized metals, in particular of galvanized or hot-dip galvanized iron or steel.
• the corrosion protection of zinc is based on the fact that it is less noble than the metallic material itself and therefore first itself corroded. The metallic material itself remains intact as long as it is still covered with zinc throughout. In the presence of atmospheric oxygen, a thin oxide layer forms on the surface of Zn or Zn alloys, Al or Al alloys, which more or less slows down the corrosive attack on the underlying metal, depending on the external conditions.
• Passivation layers are comparatively thin and usually have a thickness of not more than 3 ⁇ m.
• additional (paint) layers are generally applied to the passivation layer. It is usually a combination of several layers of paint, each serving different purposes. They serve to protect the passivation layer and the metal from corrosive gases and / or liquids but also from mechanical damage, such as rockfall and of course also aesthetic purposes. Coating layers are usually much thicker than passivation layers. Typical thicknesses range from 2 ⁇ to 8,400 ⁇ .
• the passivation can be used for permanent corrosion protection or even for temporary corrosion protection.
• a temporary protection is used only for storing or transporting a metal sheet or other metallic workpiece and is removed before the final processing.
• passivation layers on zinc or aluminum surfaces have usually been obtained by treating the workpiece to be protected with aqueous, acidic solutions of CrO 3 .
• the mechanism of such passivation is complex.
• metallic Zn or Al is released from the surface and precipitates again in the form of amorphous zinc chromium oxides or aluminum chromium oxides.
• the layers may also contain foreign ions and / or further components from the treatment solution.
• Cr (VI) is also incorporated into the passivation layer.
• treatment of metallic surfaces with acidic aqueous Cr (III) solutions has been proposed.
• DE-A 195 16 765 discloses a chromium and fluoride-free process for producing conversion coatings on metallic surfaces of Zn or Al.
• the acidic solution used for passivation comprises a water-soluble polymer, phosphoric acid and Al chelate complexes.
• DE-A 197 54 108 discloses a chromium-free aqueous corrosion inhibitor, but which comprises toxic hexafluoro anions of Ti (IV) and / or Zr (IV), vanadium ions, cobaltions and phosphoric acid.
• still further different film-forming polymers can be added, including carboxyl-containing copolymers such as acrylic acid / maleic acid copolymers.
• WO 2004/074372 A1 relates to an acidic aqueous preparation comprising copolymers of from 50 to 99.9% by weight of (meth) acrylic acid, from 0.1 to 50% by weight of acidic comonomers, such as, for example, ethylenically unsaturated dicarboxylic acids, and / or polymerizable phosphoric and / or phosphonic acids and their use in a process for passivating metal surfaces.
• the treatment of the metal surface is carried out by a spraying, rolling or dipping method.
• the available passivation layer can be overcoated with one or more paint layers.
• WO 2006/021309 A1 discloses a process for passivating metallic surfaces using an acidic aqueous preparation containing itaconic acid homo- or copolymers.
• the itaconic acid polymers are prepared at a polymerization temperature of less than 120 ° C, whereby a better corrosion protection against acrylic acid-maleic acid copolymers is achieved.
• the process may also be a continuous process for treating strip metals.
• the available passivation layer may be a temporary or permanent corrosion protection and may be overcoated with one or more paint layers.
• the above-described chromium-free processes are still in need of improvement in terms of corrosion protection, but also in terms of process technology, in particular in the so-called coil coating of strip metals.
• the galvanizing and passivating of such metal strips is carried out on an industrial scale in continuous installations
• the metal strip is first driven for galvanizing by a device for galvanizing, for example a trough with molten zinc, and subsequently by a passivating device, for example As a rule, further process steps are carried out continuously, for example cleaning or rinsing steps or else the application of a first coat of varnish to the passivation layer
• the object of the invention is therefore to provide an improved, preferably heavy metal-free, in particular chromium-free, and preferably fluorine-free process without the use of organic solvents and / or toxic ingredients for passivating metallic surfaces of Zn, Zn alloys, Al or Al alloys , which offers improved corrosion protection compared to the prior art and in which a satisfactory result nevertheless only short contact times between the metallic surface and the preparation used for passivation are required.
• the process should also be able to be carried out continuously, in particular for the passivation or pretreatment of strip metals.
• an acidic, aqueous preparation comprising at least one copolymer (A) synthesized from (a1) (meth) acrylic acid or its salts and (a2) at least one other of (a1) different monoethylenically unsaturated monomer which has acidic groups, and
• the invention relates to a method for passivating metallic surfaces, characterized in that the surface in alternating layers with a) an acidic, aqueous preparation containing at least one water-soluble copolymer (A) composed of
• an aqueous preparation comprising at least one water-soluble and / or water-dispersible species (B) which has cationic and / or cationic groups, preferably at least one water-soluble cationic and / or prokationic polymer (B1); is treated, where a) is always the first and the last layer.
• water-soluble in the sense of this invention is intended to mean that the copolymers (A) or cationic and / or prokationic species (B) used are preferably to be homogeneously water-soluble.
• copolymers (A) or cationic and / or procionic species (B) used should preferably be completely miscible with water, even if this is not absolutely necessary in every case. But they must be water-soluble at least to such an extent that the passivation by means of the method according to the invention is possible.
• the copolymers (A) or cationic and / or prokationic species (B) used should have a solubility of at least 50 g / l, preferably 100 g / l.
• the inventive method also includes the use of aqueous dispersions of the species (B).
• aqueous dispersions of the species (B) It is known to the polymer expert that the solubility of both acid group-containing (anionic) polymers and of cationic and / or prokationic species in water can be dependent on the pH. As a reference point, therefore, each of the desired for the particular application pH should be selected. A polymer which at one pH has insufficient solubility for its intended use may have sufficient solubility at another pH. Acrylic acid and / or methacrylic acid or mixtures thereof can be used as the monomer (a1) for the copolymer (A) used according to the invention, with acrylic acid being preferred.
• the amount of (meth) acrylic acid (a1) in the copolymer (A) is preferably 20 to 90% by weight, more preferably 30 to 70% by weight and most preferably 35 to 65% by weight, which specification is based on the sum of all monomers in the polymer.
• the acidic groups of the at least one monoethylenically unsaturated monomer (a2) are preferably selected from the group of carboxyl groups, sulfonic acid groups, phosphoric and / or phosphonic acid groups. Particular preference is given to carboxyl groups, phosphorus and / or phosphonic acid groups. Of course, several different monomers (a2) can be used.
• Examples of such monomers include crotonic acid, vinylacetic acid, C 1 -C 4 -haloesters of monoethylenically unsaturated dicarboxylic acids, styrenesulfonic acid, vinylsulfonic acid, acrylamidopropanesulfonic acid, vinylphosphonic acid, phosphoric acid monovinyl ester, maleic acid, fumaric acid or itaconic acid.
• the amount of the monomers (a2) in the copolymer (A) is preferably 10 to 70 wt .-%, particularly preferably 20 to 65 wt .-% and most preferably 30 to 60 wt .-%, each based on the sum of all monomers in the polymer.
• the monomers (a2) are preferably monoethylenically unsaturated dicarboxylic acids having 4 to 7 carbon atoms (a21) and / or monoethylenically unsaturated phosphoric and / or phosphonic acids (a22).
• Examples of monomers (a21) include maleic acid, fumaric acid, methyl fumaric acid, methylmaleic acid, dimethylmaleic acid, methylenemalonic acid or itaconic acid. If appropriate, the monomers can also be used in the form of the corresponding cyclic anhydrides. Preference is given to maleic acid or maleic anhydride, fumaric acid and itaconic acid, particular preference to itaconic acid.
• the copolymer (A) is preferably composed of monomer units of acrylic acid (a1) and itaconic acid (a21).
• monomers (a22) include vinylphosphonic acid, monovinyl phosphoric acid ester, allylphosphonic acid, monoesters of phosphoric acid, 3-butenylphosphonic acid, phonic acid, mono (3-butenyl) phosphoric acid, (4-vinyloxybutyl) phosphoric acid, (phosphonoxyethyl) acrylate, phosphonoxyethyl methacrylate, phosphoric mono (- 2-hydroxy-3-vinyloxy-propyl) ) esters, phosphoric acid mono- (1-phosphonoxymethyl-2-vinyloxy-ethyl) esters, phosphoric mono (3-allyloxy-2-hydroxypropyl) esters, phosphoric mono-2- (allylox-1-phosphonoxymethyl-ethyl) esters, 2 -Hydroxy-4-vinyloxymethyl-1,3,2-
• ethylenically unsaturated monomer (a3) other than (a1) and (a2) can be used.
• no other monomers are used.
• the monomers (a3) serve to finely control the properties of the copolymer (A).
• monomers (a3) can be used. They are selected by the skilled person depending on the desired properties of the copolymer and further with the proviso that they must be copolymerizable with the monomers (a1) and (a2).
• (a1) and (a2) are monoethylenically unsaturated monomers.
• monomers with several polymerizable groups can be used.
• the copolymer can be crosslinked to a small extent.
• Suitable monomers (a3) include in particular alkyl esters or hydroxyalkyl esters of (meth) acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or butanediol-1,4-monoacrylate.
• alkyl esters or hydroxyalkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate or butanediol-1,4-monoacrylate.
• vinyl or allyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, 2-ethyl hexyl vinyl ether, vinyl cyclohexyl ether, vinyl 4-hydroxybutyl ether, decyl vinyl ether, 2- (diethylamino) ethyl vinyl ether, 2- (di-n-butylamino) ethyl vinyl ether or methyl diglycol - vinyl ethers or the corresponding allyl compounds.
• vinyl esters such as vinyl acetate or vinyl propionate.
• alkoxylated monomers in particular ethoxylated monomers. Especially suitable are alkoxylated monomers which are derived from acrylic acid or methacrylic acid.
• crosslinking monomers include molecules having several ethylenically unsaturated groups, for example di (meth) acrylates such as ethylene glycol.
• di (meth) acrylate or butanediol-1,4-di (meth) acrylate or poly (meth) acrylates such as trimethylolpropane tri (meth) acrylate or else di (meth) acrylates of oligo- or polyalkylene glycols such as di-, tri or tetraethylene glycol di (meth) acrylate.
• Further examples include vinyl (meth) acrylate, allyl (meth) acrylate, divinylethyleneurea or butanedivinyl divinyl ether.
• di- and oligo-allyl ethers of polyhydroxy compounds for example pentaerythritol tri or tetraallyl ether.
• the amount of all monomers (a3) used together amounts to 0 to 55 wt .-% based on the total amount of the monomers used.
• the amount is preferably 0 to 30 wt .-%, particularly preferably 0 to 20%.
• crosslinking monomers (a3) are present, their amount should generally not exceed 5%, preferably 2% by weight, based on the total amount of all monomers used for the process. It may for example be 10 ppm to 1 wt .-%.
• the copolymer (A) comprises (a1) at least one monomer (a21) and at least one monomer (a22). With particular preference, in addition to the monomers (a1), (a21) and (a22), no further monomers (a3) are present.
• Each of (a21) and (a22) can be only one monomer (a21) or (a22), or else in each case two or more different monomers (a21) or (a22).
• the amount of (a1) is 40 to 50 wt%, the amount of (a21) is 35 to 45 wt%, the amount (a22) is 5 to 25 wt%, and the amount of (a3 ) 0 to 10 wt .-%.
• the copolymer (A) is composed of monomer units of acrylic acid (a1), itaconic acid (a21) and vinylphosphonic acid (a22) in the abovementioned amounts.
• the components (a1), (a2) and optionally (a3) can be polymerized together in a manner known in principle. Corresponding polymerization techniques are known to the person skilled in the art.
• the copolymers (A) are preferably prepared by free-radical polymerization of the stated components in aqueous solution. In addition, small amounts of water-miscible organic solvents may still be present and optionally small amounts of emulsifiers. Details of performing a radical polymerization are those skilled in the art are known and are described, inter alia, in the publications WO 2004/074372 A1 and WO 2006/021309 A1, to soft reference is made.
• the synthesized copolymers (A) can be isolated from the aqueous solution by conventional methods known to those skilled in the art, for example by evaporation of the solution, spray drying, freeze drying or precipitation. Preferably, however, the copolymers (A) are not isolated from the aqueous solution at all after the polymerization but the resulting polymer solution is used as such.
• the molecular weight M w (weight average) of the copolymers (A) used for the process according to the invention is determined by the person skilled in the art according to the desired application. For example, copolymers (A) having a molecular weight M w of 3,000 to 2,000,000 g / mol can be used.
• Copolymers having a molecular weight of from 5000 g / mol to 500 000 g / mol, preferably from 10 000 g / mol to 250 000 g / mol, more preferably from 15 000 to 100 000 g / mol and very particularly preferably from 20 000 to have proven particularly useful 75 000 g / mol.
• an acidic, aqueous preparation (a) of the copolymers (A) is used.
• the preparation (a) preferably comprises only water. It may also comprise water-miscible organic solvents. Examples include monoalcohols such as methanol, ethanol or propanol, higher alcohols such as ethylene glycol or polyether polyols and ether alcohols such as butyl glycol or methoxypropanol. As a rule, however, the amount of water is at least 80% by weight, preferably at least 90% by weight and very particularly preferably at least 95% by weight. The data refer to the total amount of all solvents.
• the polymer-containing solutions which result from the polymerization which are optionally further diluted, can be used directly.
• the amount of aqueous solvent used for the polymerization should be from the beginning sized so that the concentration of the copolymer (A) in the solvent is suitable for the application.
• the concentration of the copolymers (A) in the preparation (a) is determined by the person skilled in the art according to the desired application.
• the thickness of the passivation layer depends on the chosen process technology, but it can also depend on the viscosity of the composition used for passivation. In general, a concentration of 0.01 g / l to 500 g / l, preferably 0.1 g / l to 200 g / l, and more preferably 1 g / l to 100 g / l has proven.
• the specified concentrations relate to the ready-to-use preparation. As a rule, it is possible first to prepare a concentrate which is first diluted to the desired concentration with water or optionally other solvent mixtures on site.
• the preparation (a) used according to the invention is acidic. It generally has a pH of 0.5 to 6, depending on the substrate and method of application and duration of exposure of the preparation on the surface tighter pH ranges may be selected.
• the pH for treating aluminum surfaces is preferably set in the range of 2 to 4, and in the case of treating zinc or galvanized steel, preferably in the range of 0.5 to 5.
• the pH of the preparation (a) can be controlled on the one hand by the nature and concentration of the acid groups of the polymers or copolymers and thus results automatically. It should be noted that the acid groups in the polymer due to production u.U. can also be completely or partially neutralized.
• the preparation (a) may optionally also comprise at least one inorganic or organic acid or mixtures thereof.
• suitable acids include phosphorus-, sulfur- or nitrogen-containing acids such as phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acids such as methanesulfonic acid, sulfamic acid, p-toluenesulfonic acid, m-nitrobenzenesulfonic acid nitric acid, hydrochloric acid, formic acid, oxalic acid, lactic acid or acetic acid and derivatives thereof and / or or corresponding alkali metal, alkaline earth metal, transition metal (in particular Zn, Zr, Ti) or ammonium salts.
• the acid is selected from the group consisting of HN0 3 , H 2 S0 4 , H 3 PO 4 , formic acid, acetic acid, oxalic acid or lactic acid.
• H 3 PO 4 and / or HNO 3 Particularly preferred are H 3 PO 4 and / or HNO 3 .
• Very particular preference is given to H 3 PO 4 and its salts.
• mixtures of different acids can be used.
• phosphonic acids examples include 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBTC), (2,4,4-trimethylpentyl) phosphonic acid, bis (2,4 , 4-trimethylpentyl) phosphinic acid, aminotri (methylenephosphonic acid) (ATMP), ethylenediaminetetra (methylenephosphonic acid) (EDTMP) or diethylenetriaminpenta (methylenephosphonic acid) (DTPMP).
• HEDP 1-diphosphonic acid
• PBTC 2,4-tricarboxylic acid
• ATMP aminotri
• ETMP ethylenediaminetetra
• DTPMP diethylenetriaminpenta
• the type and concentration of the acid in the preparation (a) is determined by the person skilled in the art according to the desired application and pH. In general, a concentration of 0.01 g / l to 30 g / l, preferably 0.05 g / l to 20 g / l, and particularly preferably 0.1 g / l to 10 g / l has proven.
• the preparation (a) can also optionally comprise further components in addition to the stated components.
• the optionally present components can be, for example, transition metal ions and compounds, for example Ce, Ni, Co, V, Fe, Zn, Zr, Mn, Mo, W, Ti, Zr, Hf, Bi, and / or the lanthanides act. It may also be compounds of main group elements, such as Si and / or Al, Ca, Mg. The compounds may be used for example in the form of salts or in the form of the respective aqua complexes. However, they can also be complexes with other ligands, for example oxometalates, for example MoO 4 2 " or WO 4 2" , lactates or oxalates.
• transition metal ions and compounds for example Ce, Ni, Co, V, Fe, Zn, Zr, Mn, Mo, W, Ti, Zr, Hf, Bi, and / or the lanthanides act. It may also be compounds of main group elements, such as Si and / or Al, Ca, Mg. The compounds may be used for example in the form of salts
• EDTA ethylenediaminetetraacetic acid
• DTPA diethylenetriaminepentaacetic acid
• HEDTA hydroxyethylethylenediaminetriacetic acid
• NTA nitrilotriacetic acid
• MGDA methylglycinediacetic acid
• optional components include surface-active compounds, corrosion inhibitors or typical electroplating aids.
• corrosion inhibitors include benzotriazole and / or tolyltriazole.
• the passivation is preferably a passivation that is essentially free of chromium. This should mean that at most small amounts of chromium compounds could be added for fine control of the properties of the passivation layer.
• the amount should not exceed 2 wt .-%, preferably 1 wt .-% and particularly preferably 0.5 wt .-% chromium with respect to all components of the composition. If chromium compounds are to be used, preference should be given to using Cr (III) compounds. In any case, the Cr (VI) content should be kept so low that the Cr (VI) content on the passivated metal does not exceed 1 mg / m 2 .
• the preparation used (a) contains no Cr compounds.
• chromium-free does not exclude that indirect and intrinsically unintentional small amounts of chromium are introduced into the process If, by means of the process according to the invention, alloys are passivated which comprise chromium as an alloy constituent, for example Cr-containing steel, it is always As far as possible, it is possible for small amounts of chromium in the metal to be treated to be dissolved by the preparation used for the process and accordingly to be inadvertently introduced into the preparation itself the process is to be regarded as "chromium-free.”
• it is more preferably a fluorine-free passivation, which comprises water-soluble and / or water-dispersible species (B), which are cationic and / or plastic.
• cationic groups are cationic and / or prokationische polymers or macromolecules (eg linear and / or branched homo- and / or copolymers, biomacromolecules, etc.), cationic and / or prokatonische polymeric colloids, cationic and / or cationic metal colloids or .nanoparticles, optionally with only cationic and / or prokationischen ligands, cationic and / or pro-cationic metal or Halbmetalloxidkolloide or -nanopitate optionally with only cationic and / or prokationischen ligands, as well as cationic and / or prokationische small molecules, like eg tetraaminocyclohexane derivatives and their protonated forms, porphyrin e and their protonated form.
• cationic and / or prokationische polymers or macromolecules eg linear and / or branched homo- and / or copo
• the cationic and / or pro-cationic species (B) should preferably be non-toxic. Preference is given to water-soluble cationic and / or prokationische polymers (B1).
• a cationic and / or prokational polymer (B1) is meant a polymer containing structural units having at least one cationic or cationic group which may be an integral part of or attached to the polymer backbone. This may not necessarily be present in each repeat unit of the polymer.
• Pro-cationic groups are those which are capable of producing protons, e.g. by reaction with acids to form salt.
• the cationic or prokationischen groups of the species (B) are preferably nitrogen or sulfur-containing groups, particularly preferably nitrogen-containing groups.
• Typical cationic nitrogen-containing groups are quaternary ammonium salts, diazonium salts and the salts of tertiary, secondary and / or primary amines.
• Typical pro-cationic groups are for example tertiary, secondary and / or primary amines.
• suitable cationic and / or prokationischen polymer (B1) containing structural units having quaternary ammonium salt groups are as preferred compounds Polyallylalkylammoniumalze as Po ly (diallyldimethylammonium chloride), Lugaivan ® P, polymers having vinyl structural units and quaternized heteroaromatics such as imidazole, pyrazole, triazole, Pyridine etc. in the Side chain such as poly (2-vinyl-1-methylpyridinium bromide) and polymers with Trialkylammoniumsalz Philosoph in the side chain such as poly (2-methacryloxyethyltrimethylammoniumbromid) called.
• the preferred compounds are poly (diallylmethylamine hydrochloride) and polymers having vinyl structural units and nitrogen-containing heteroaromatics such as imidazole, pyrazole, triazole, pyridine etc. in the side chain such as poly (4-vinylpyridine) and their protonated form called.
• the preferred compound is linear and / or branched polyethylenimine and its protonated form.
• suitable cationic and / or prokationischen polymers (B1) containing structural units with primary amines and their salts are mentioned as preferred compounds polyvinylamine, polyallylamine hydrochloride, polylysine and polylysinhydrochlorid.
• the salts exemplified above are not limited to the listed counter ions, that is, chloride or bromide are interchangeable (and among each other) and may be replaced by other common acid anions such as e.g. Phosphate, hydrogen phosphate, acetate, hydrogen sulfate, etc. are replaced.
• Cationic and / or prokationische polymers (B1) containing structural units with quaternary ammonium salt groups are preferred. Particularly preferred is Lugaivan ® P, a BASF commercial product.
• cationic and / or prokationische polymers are polymers containing structural units with positively charged sulfur groups, for example based on sulfur-containing heteroaromatics such as oxidized poly (3,4-ethylenedioxythiophene), which is also known as PEDOT.
• the cationic and / or prokationische polymer (B1) may also be a copolymer containing various of the aforementioned repeating units.
• copolymers which, in addition to the abovementioned structural units of cationic or prokationic monomers, contain various structural units of other monomers (c).
• these monomers (c) must not change the previously defined character of the cationic and / or prokationic polymers (B1).
• suitable comonomer mers (c) may be mentioned as examples of styrene and / or vinyl alcohol.
• Examples of corresponding copolymers of the cationic and / or prokationischen polymer (B1) are copolymers based on allylamine hydrochloride and styrene and / or vinyl alcohol and copolymers based on diallyldimethylammonium chloride and styrene and / or vinylalcohol, without being limited thereto.
• the proportion of comonomers (c) in the cationic and / or prokationischen polymer (B1) can be 0 to 50 wt .-%.
• the cationic and / or prokationic polymers (B1) used according to the invention can be obtained by customary methods known to the person skilled in the art, such as by radical polymerization or by polycondensation. The skilled person will choose the appropriate method depending on the chemical constitution of the monomer.
• the molecular weight M w (weight average) of the cationic and / or procaryic polymer (B1) used for the process according to the invention is determined by the person skilled in the art according to the desired application.
• M w is generally 5000 to 2000000 g / mol.
• the preparation (b) with the cationic and / or prokationischen species (B) preferably comprises only water. It may also comprise water-miscible organic solvents. Examples include monoalcohols such as methanol, ethanol or propanol, higher alcohols such as ethylene glycol or polyether polyols and ether alcohols such as butyl glycol or methoxypropanol. As a rule, however, the amount of water is at least 80% by weight, preferably at least 90% by weight and very particularly preferably at least 95% by weight. The data refer to the total amount of all solvents.
• Dispersions of the cationic and / or prokationic species (B) in the form of e.g. Colloids in the above solvents are also included in the term "solution".
• the solutions with the cationic and / or prokationischen species (B), preferably with the cationic and / or prokationischen polymer (B1) are used, resulting from the synthesis (eg polymerization), which are optionally further diluted.
• the amount of aqueous solvent used in the synthesis should be from the start sized so that the concentration of the cationic and / or prokationic species (B) in the solvent is suitable for the application.
• the concentration of the cationic and / or prokationischen species (B) in the preparation (b) is determined by the expert according to the desired application.
• the thickness of the passivation layer depends on the chosen process technology, but it may also depend on the viscosity of the passivation composition.
• a concentration of 0.01 g / l to 500 g / l, preferably 0.1 g / l to 200 g / l, and more preferably 1 g / l to 100 g / l has proven.
• the concentrations given refer to the ready-to-use preparation. As a rule, it is possible first to prepare a concentrate which is first diluted to the desired concentration with water or optionally other solvent mixtures on site.
• the preparation (b) used according to the invention generally has a pH of from 1 to 12, wherein, depending on the substrate and the mode of application and the duration of exposure of the preparation to the surface, narrower pH ranges may be selected.
• the pH of the preparation (b) can be controlled by the type and number of (per) cationic groups of the species (B) and thus results automatically.
• the pH of the aqueous preparation (b) can be adjusted by adding acids or bases.
• the addition of acids is particularly advantageous for weak polybases such as polyethyleneimine.
• the preparation (b) may therefore optionally also comprise at least one inorganic or organic acid or mixtures thereof and their derivatives or salts, or at least one base or mixtures thereof and derivatives or salts thereof.
• Suitable and preferred acids are also those mentioned in this connection for the preparation (a).
• Suitable bases are generally alkali or alkaline earth hydroxides, amines or ammonia.
• the type and concentration of the acid or base in the preparation (b) is determined by the skilled person according to the desired application and pH.
• the preparation (b) may, in addition to the components mentioned, optionally comprise further components. These include surface active compounds, corrosion inhibitors or typical electroplating aids.
• the person skilled in the art will make an appropriate selection of the possible optional components as well as their quantities depending on the desired application.
• the metallic surfaces which can be passivated by means of the method according to the invention are, in particular, the surfaces of base metals. It may be, for example, the surface of iron, steel, Zn, Zn alloys, Al or Al alloys, Mg or Mg alloys.
• the steels can be both low-alloyed and high-alloyed steels.
• the inventive method is particularly suitable for passivation of metallic surfaces of Zn, Zn alloys, Al or Al alloys. These may be the surfaces of bodies or workpieces consisting entirely of the said metals or alloys. However, they may also be the surfaces of Zn, Zn alloy, Al or Al alloy coated bodies, which bodies may be made of other materials such as other metals, alloys, polymers or composites. In particular, it may be the surface of galvanized iron or steel. Of course, the term "galvanized" also includes coating with a zinc alloy.
• Zn or Al alloys are known to the person skilled in the art. Depending on the desired application, the skilled person will select the type and amount of alloying components. Typical components of zinc alloys include in particular Al, Mg, Pb, Si, Mg, Sn, Cu or Cd. It may also be Zn / Mg or Al / Zn alloys in which Zn and Mg or Al and Zn are present in approximately the same amount.
• the coatings may be substantially homogeneous coatings or even coatings having concentration gradients. For example, it may be galvanized steel which has been additionally vapor-deposited with Mg. As a result, a surface Zn / Mg alloy can arise.
• typical constituents of aluminum alloys include Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.
• the metallic surfaces to be treated may, of course, also have thin oxidic / hydroxidic and / or carbonic surface layers or layers of similar construction. Such layers usually form spontaneously on metallic surfaces in contact with the atmosphere, and are included in the term "metallic surface.”
• the "metallic surface” may be the surface of piece goods (drumware, racks, etc.) or who trade in ribbon metals.
• the surface of a strip metal preferably of aluminum or aluminum alloys or iron or steel, in particular strips of electrolytically galvanized or hot-galvanized steel.
• the surface of the metal is treated alternately with the acidic, aqueous preparation (a) and the aqueous preparation (b), the preparation (a) always being applied first and last. The process can be repeated until a passivation layer with the desired layer thickness has formed on the metallic surface.
• the application of the preparations (a) or (b) used in the process according to the invention can be carried out, for example, by spraying, dipping or rolling. After a dipping process, you can drain the workpiece to remove excess treatment solution; in the case of metal sheets, metal foils or the like, excess treatment solution, for example, can also be squeezed off or a brakein.
• excess treatment solution for example, can also be squeezed off or a brakein.
• at least parts of the copolymers (A) used are chemisorbed from the surface of the metal so that a firm bond between the surface and the components is achieved.
• the treatment with the preparation (a) or (b) is usually carried out at room temperature or temperatures above room temperature without that lower temperatures should be excluded in principle. In general, the treatment is carried out at 20 to 90 ° C, preferably 20 to 60 ° C.
• the bath can be heated with the preparation (a) or (b), but an elevated temperature can also be set automatically by immersing warm metal in the bath.
• the treatment with the preparation (a) or (b) at room temperature is very particularly preferred.
• the treatment may also be a so-called "no-rinse" process, in which the treatment solution is dried directly in a drying oven immediately after application without rinsing
• the treatment of the metal surface with the preparation (a) or (b) A continuous process is particularly suitable for treating strip metals
• the metal strip is in this case by a pan or a spray device with the preparation (a), and a pan or spray device with the preparation (b), and optionally passed through further pre- or post-treatment or the preparation (a) or (b) is rolled with a coater on the metal strip.
• the duration of treatment is determined by the person skilled in the art according to the desired properties of the layer, the composition used for the treatment and the technical conditions. It can be significantly less than a second or several minutes. In the continuous process, it has proven particularly useful to contact the surface with the preparation for a period of 1 to 60 seconds.
• the solvent used is removed.
• the removal can be carried out at room temperature by simple evaporation in air at room temperature.
• the removal of the solvent can also be assisted by suitable auxiliaries, for example by heating and / or by passing gas streams, in particular air streams.
• the evaporation of the solvent can be supported, for example by IR emitters, or also, for example, by drying in a drying tunnel.
• the drying at the aforementioned elevated temperatures is preferably carried out after each of the applied layers, but can also be done only after application of the complete multilayer.
• the abovementioned method steps are initially carried out with the preparation (a) and are repeated several times in alternation with the preparation (b) and then completed with the preparation (a).
• the process according to the invention may optionally comprise one or more pretreatment steps.
• the metallic surface may be cleaned prior to passivation, e.g. to remove fats or oils.
• it can also be pickled prior to passivation to remove oxide scale, scale, temporary corrosion protection and the like.
• the surface must also be optionally rinsed with water after and between such pretreatment steps in order to remove the residues of rinsing solutions or pickling solutions.
• the passivation layer can additionally be crosslinked.
• a crosslinker may be added to the preparation (a) or (b) used, provided that it does not already react in the particular preparation.
• Suitable crosslinkers should be water-soluble or at least soluble in the said aqueous solvent mixture.
• suitable crosslinkers include, in particular, those which have at least 2 crosslinking groups selected from the group of azirane, oxirane or thiirane groups. Further details on suitable crosslinkers are disclosed in the publication WO2005 / 042801 A1, which is expressly referred to here.
• a passivation layer on a metallic surface is obtainable, which is likewise the subject of the invention.
• the exact structure and composition of the passivation layer is not known. However, in addition to the usual amorphous oxides of aluminum or zinc and optionally further metals, it also comprises the reaction products of the copolymer (A), and optionally of the crosslinker and / or further components of the preparation (a), and the reaction products of the cationic and / or prokationischen Species (B) and optionally further components of the preparation (b).
• the layer sequence is (a), (b), n times ((a), (b)) and finally (a).
• metallic surfaces having a passivation layer of 3 to 7 layers according to the sequence described above are preferred, metallic surfaces having a passivation layer of 3 layers having the sequence (a), (b), (a) are particularly preferred.
• the thickness of the passivation layer is adjusted by the person skilled in the art according to the desired properties of the layer. As a rule, the thickness is 0.01 to 3 ⁇ , preferably 0.02 to 1 ⁇ , and particularly preferably 0.03 to 0.2 ⁇ .
• the thickness can be influenced, for example, by the type and amount of the applied components, the number of repetitions of the application process, and the exposure time. Furthermore, it can be influenced by process parameters, for example by doctoring off or rolling off too much applied treatment solution.
• the thickness of the layer is determined by differential weighing before and after the action of the composition according to the invention on the metal surface under the Assuming that the layer has a specific gravity of 1 kg / l.
• layer thickness is always understood to mean a size determined in this way, regardless of which specific density the layer actually has.
• the passivation layer is directly on the actual metal surface In a preferred embodiment, it is a strip metal made of steel, which comprises a coating of Zn or a Zn alloy, on which a passivation layer according to the invention is applied.
• the metallic surface with the passivation layer according to the invention can be overcoated in a manner known in principle with one or more paint layers (primer, topcoat).
• paint layers primary, topcoat
• Typical coatings, their composition and typical layer sequences in the case of several layers of paint are known in principle to the person skilled in the art.
• the passivation layer according to the invention can also be used as a temporary passivation, which is subsequently passivated or phosphated by other processes.
• the process according to the invention is particularly suitable for the pretreatment of strip metals in the area of "pre-treatment / eoil-coating.”
• passivation layers which are obtainable by the process according to the invention are used as pretreatment layer on strip metals.
• Test plates made of hot-dip galvanized steel (Gardobond OE HDG 3, from Chemetal) were used.
• the sheets were first degreased with ethanol and ethyl acetate and then immersed in an alkaline cleaning solution (eg Ridoline C72, Fa. Henkel, 4.3 g / L at 60 ° C for 1 minute), rinsed immediately with deionized water and then dried with nitrogen ,
• an alkaline cleaning solution eg Ridoline C72, Fa. Henkel, 4.3 g / L at 60 ° C for 1 minute
• the cleaned sheets were immersed at room temperature for 2-3 seconds in formulation (a) and squeezed with a roller system. These operations were repeated with the preparation (b) and then again with the preparation (a).
• the cleaned sheets were immersed at room temperature for 2-3 seconds in preparation (c) and squeezed with a roller system.
• the sheets were dried for 15-20 s at 160 ° C in a drying oven.
• the peak metal temperature during drying did not exceed 50 ° C.
• Each 2 plates were coated.
• the sheets with pretreatment layer and a commercially available sheet pretreated with Gardo TP10475 (Chemetall, Cr-free, F-containing), which is used as a reference sheet, were coated by means of a spiral doctor with the respective primer (see Table 1) and after Brand information baked in the oven, briefly dipped in deionized water and dried with compressed air. Subsequently, the respective topcoat (see Table 1) was also applied according to the manufacturer's instructions by means of a spiral doctor blade, baked in the oven, then the plates were immersed briefly in deionized water and dried vertically.
• the result of a salt spray test according to DIN 50021 serves as a measure of the corrosion-inhibiting effect.
• the salt spray test was carried out with the completely coated metal sheets (step 1 -3) with a well-defined 0.3 mm wide, 1 1 cm long vertical centric scratch (through the paint layers and the Zn coating); the storage time was 6 weeks.
• the results of the tests are summarized in Table 1.
• the corrosion infiltration is the average half-sided broadening of the original scratch.
• the average value of the examined sheets was formed.
• the T-bend test was carried out according to DIN EN ISO 1519: 2003 with the completely coated sheets (step 1 -3).
• the test result is summarized in Table 1 and indicates the minimum distances that are possible between the two sides of the bent sheet so that no delamination phenomena occur.
• the values are listed in relative units normalized to the sheets with the commercially available pretreatment Gardo TP10475, from Chemetall. The average value of the examined sheets was formed.
• the tape test was carried out according to DIN EN ISO 1519: 2003 with the completely coated metal sheets (step 1 -3).
• the test result is summarized in Table 1 and indicates the minimum distances that are possible between the two sides of the bent sheet so that no tape delamination phenomena occur at the bending edge.
• the values are listed in relative units normalized to the sheets with the commercially available pretreatment Gardo TP10475, from Chemetall. The average value of the examined sheets was formed.

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