Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
• • 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
  • 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
  • C23C22/12—Orthophosphates containing zinc cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/07—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
  • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
• • 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
  • 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
  • C23C22/20—Orthophosphates containing aluminium cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
  • C23C22/08—Orthophosphates
  • C23C22/22—Orthophosphates containing alkaline earth metal cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates

Definitions

• the present invention relates to a method for passivating metallic surfaces, an acidic preparation suitable for carrying out the process, which comprises at least water and a copolymer of functionalized (meth) acrylic acid esters, monomers having phosphoric acid and / or phosphonic acid groups, COOH groups comprising monomers and optionally further monomers, as well as said copolymer.
• the metal strips are cut and formed by 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 usually takes place 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. These can be both temporary corrosion protection and 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.
• tapes with a galvanized surface in particular tapes made 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.
• metal strips made of aluminum or aluminum alloys In the presence of atmospheric oxygen forms on the surface of Zn or Zn alloys, Al or Al alloys first a thin oxide layer, the the corrosive attack on the underlying metal slows down more or less depending on the external conditions.
• Al and Zn surfaces are usually subjected to an additional passivation treatment.
• a portion of the metal to be protected dissolves, and is at least partially incorporated into a film on the metal surface.
• This film is similar to the already existing oxide film and usually contains specifically introduced phosphate, heavy metals and / or fluorides. It offers greater protection against corrosion than the zinc-naturally adhering film, which consists predominantly of zinc oxide and zinc carbonate and is commonly referred to as a passivation layer. It also often improves the adhesion of paint coatings applied to the metal.
• passivation layer conversion layer
• pretreatment layer A passivation layer applied to strip steel immediately after galvanizing is sometimes also referred to as a "post-treatment layer”.
• 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.
• paint usually it is a combination of several layers of paint, each serving different purposes. They serve, for example, to protect the passivation layer and the metal from corrosive gases and / or liquids, but also from mechanical damage, such as, for example, falling rocks, and of course also aesthetic purposes.
• Coating layers are usually much thicker than passivation layers. Typical thicknesses range from 4 ⁇ m to 400 ⁇ m.
• passivation layers on zinc or aluminum surfaces have usually been obtained by treating the workpiece to be protected with aqueous, acidic solutions containing chromates. More recently, techniques have also been developed using different polymers for passivation, in place of chromates, including polymers containing phosphoric acid and / or phosphonic acid groups.
• WO 00/55391 discloses the use of vinylphosphonic acid homo- or copolymers in combination with SiO 2 for the treatment of metallic surfaces.
• (meth) acrylic acid, maleic acid or vinylsulfonic acid are mentioned as comonomers, but not (meth) acrylic esters.
• WO 2004/74372 discloses a method for passivating metal surfaces using copolymers of 50 to 99.9% by weight of (meth) acrylic acid, 0.1 to 50% by weight of other acidic comonomers having COOH groups and / or 0.1 to 50% by weight of comonomers containing phosphoric and / or phosphonic acid groups and optionally 0 to 30% by weight of further monomers.
• EP-A-787 830 discloses a chromium-free composition for treating metallic surfaces which comprises an OH-group-containing binder, phosphoric acid and certain metal ions. Some examples disclose copolymers comprising, in addition to OH-containing acrylates, simple acrylates, styrene and (meth) acrylic acid up to 1, 7 wt.% Methacrylic acid (phosphonooxyethyl) ester.
• EP-A 1 146 144 discloses a composition for treating metallic surfaces comprising Al, Mg and Mn, a water-soluble binder, an acid and water.
• An example of this discloses the use of a monomer which comprises 26.7% by weight of hydroxybutyl acrylate, 0.8% by weight of a phosphorus-containing monomer and 72.5% by weight of simple acrylates or styrene.
• US 2005/181225 A1 discloses the use of block copolymers for treating metallic surfaces, where the block copolymers have at least one block comprising phosphoric acid and / or phosphonic acid groups and at least one block different therefrom.
• This may be, for example, a block copolymer in which a block of vinylphosphonic acid and acrylic acid is linked to a polyacrylamide block or a butylacrylate block.
• the polymers which are used in the course of a passivation treatment must meet high requirements. Not only must they effectively protect the surface from corrosion, but they must also have good film-forming and good optical properties, for example, and should provide good adhesion to further paint layers.
• the object of the invention was to provide an improved method for passivation of metallic surfaces.
• passivation layers should be obtained with good optical properties, in particular a low tendency to chalking.
• an acidic preparation for passivating metallic surfaces with a pH ⁇ 5 was found, which is at least water and 0.1 to 50 wt.%, Based on the amount of all components of the preparation, at least one water-soluble or water-dispersible, phosphoric acid and or copolymers comprising phosphonic acid groups, and wherein the copolymer is composed of the following monomeric building blocks:
• R 2a radicals of the general formula - (R 3 -O-) n -R 4 , where n is a natural number from 2 to 40, R 3 each independently represent a divalent, straight-chain or branched alkyl radical having 2 to 4 C atoms and R 4 is H or a straight-chain or branched alkyl radical having 1 to 6 C atoms,
• R 2b radicals of the general formula -R 5 -X m , where R 5 is an (m + 1) -valent, straight-chain or branched alkyl radical having 1 to 10 C atoms, X is a functional group selected from the group of -OH, -OR 6 , -NH 2 , -NHR 6 , -NR 2 6 , -N + HR 2 Y " or -N + R 3 Y " , wherein R 6 is methyl or ethyl, Y is a monovalent cation and m for a natural number of 1 to
• monomer (B) is vinylphosphonic acid.
• the invention relates to the copolymer used to carry out said process as defined above. More specifically, the following is to be accomplished for the invention:
• 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, for example, be the surface of iron, steel, Zn, Zn alloys, Al or Al alloys, Sn and Sn 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 made entirely of said metals or alloys. However, they may also be the surfaces of bodies coated with Zn, Zn alloys, Al or Al alloys, wherein the bodies may consist of other materials, for example of other metals, alloys, polymers or composite materials. In particular, it may be the surface of galvanized iron or steel.
• galvanized also includes coating with a zinc alloy, in particular Zn-Al alloy hot-dip galvanizing and Zn-Ni, Zn-Fe, Zn-Mn and Zn-Co zinc electroplating.
• 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 Al / Zn alloys in which 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 can be galvanized steel, which was additionally vapor-deposited with Mg. As a result, a Zn / Mg alloy can form on the surface.
• Typical constituents of aluminum alloys include in particular Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.
• a band metal preferably of aluminum or aluminum alloys or iron or steel, in particular strips of electrolytically galvanized or hot-galvanized steel.
• moldings which are obtainable by processing operations such as cutting, forming and / or joining of the said band metals.
• Examples include automobile bodies or parts thereof, truck bodies, linings for household appliances such as washing machines, dishwashers, tumble dryers, gas and electric stoves, Microwave ovens, freezers or refrigerators, covers for technical devices or equipment such as machinery, cabinets, computer cases or the like, architectural elements such as wall parts, facade elements, ceiling elements, window or door profiles or partitions, furniture made of metallic materials such as metal cabinets or metal shelves.
• the metallic surfaces to be treated may also have thin oxidic, hydroxidic and / or carbonic surface layers or layers of similar construction. Such layers usually form on metallic surfaces in contact with the atmosphere, of their own accord, and are included in the term "metallic surface".
• the preparation used for passivation comprises one or more water-soluble or water-dispersible, phosphoric acid and / or phosphonic acid-containing copolymers.
• water-soluble in the sense of this invention is intended to mean that the copolymer or copolymers used should be homogeneously soluble in water.
• water-dispersible means that the solution is not completely clear, but the polymer is homogeneously distributed therein and also does not settle.
• copolymers which are water-soluble can be used to carry out the invention.
• the use of aqueous dispersions of crosslinked polymer particles in water-insoluble polymers is not within the scope of this invention.
• the copolymers used should be completely miscible with water, although this is not absolutely necessary in every case. However, they must be water-soluble or water-dispersible at least to such an extent that the passivation by means of the process according to the invention is possible.
• the copolymers used should have a solubility of at least 50 g / l, preferably 100 g / l and more preferably at least 200 g / l in water.
• the copolymers of the invention are each composed of at least one monomer of group (A), (B) and (C).
• monomers (D) can still be present. be his.
• no other monomers are present.
• no monomers (D) are present.
• R 1 is H or methyl.
• R 2 is a radical selected from the group of R 2a , R 2b or R 2c .
• the radicals R 2a are radicals of the general formula - (R 3 -O-) n -R 4 .
• n is a natural number of 2 to 40.
• n is 2 to 20 and particularly preferably 2 to 10.
• the radicals R 3 are each independently a divalent, straight-chain or branched alkyl radical having 2 to 4 C-Ato - men. Examples include, in particular, 1,2-ethylene radicals, 1,2-propylene radicals, 1,2-butylene radicals and 1,4-butylene radicals. Of course, it may also be mixtures of different radicals. It is preferably 1, 2-ethylene and / or 1, 2-propylene radicals. Particularly preferred are only 1, 2-ethyl radicals.
• radicals (R 2a ) which have both 1, 2-ethylene and 1, 2-propylene radicals, where the amount of the ethylene radicals is at least 50%, preferably at least 70% and particularly preferably at least 80%, based on the total number all radicals R 3 is.
• R 4 is H or a straight-chain or branched alkyl radical having 1 to 6 C atoms.
• Preferred radicals R 4 are H, methyl and ethyl groups.
• radicals R 2a include -CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 3 , -CH 2 -CH (CHS) -O-CH 2 -CH (CH 3 ) OH, -CH 2 -CH (CH 3 ) -O-CH (CH 3 ) -CH 2 OH, -CH (CH 3 ) -CH 2 -O-CH (CH 3 ) -CH 2 OH or -CH (CHS) - CH 2 -O-CH 2 -CH (CH 3 ) OH.
• the radicals R 2b are radicals of the general formula -R 5 -X m m is a natural number of 1 to 6, preferably 1 to 4, particularly preferably 1 to 3 and for example 1 or 2.
• the radical R 5 represents an (m + 1) -valent, straight-chain or branched alkyl radical having 2 to 10 C atoms, preferably 2 to 6 C atoms and particularly preferably 2 to 4 C atoms.
• the alkyl group is substituted with at least one functional group X, provided that not more than one functional group X per C atom is present in R 5 .
• X is at least one functional group selected from the group of -OH, -OR 6 , -NH 2 , -NHR 6 , -NR 6 2 , -N + HR 6 2 Y- or -N + R 6 3
• R 6 is methyl or ethyl and Y is a monovalent anion
• suitable anions include, for example, HSO 4 " , HSO 3 " and in particular the anions of organic sulfonic acids such as CH 3 SO 3 " , CF 3 SO 3 " or P-CH 3 (CeH 4 ) SO 3 " or organic sulfates such as CH 3 SO 4 " or CH 3 CH 2 SO 4 " .
• Halide ions are less preferred, although they may be used in special cases.
• radicals R 2b with amino or ammonium groups include -CH 2 -CH 2 - N (CHs) 2 and -CH 2 -CH 2 -N + (CH 3) S- CH 3 SO 4 -.
• the functional group X is an OH group.
• radicals R 2b having OH groups include linear radicals of the general formula - (CH 2 ) m -OH, such as -CH 2 -CH 2 -OH, -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH 2 -CH 2 -OH or -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -OH.
• radicals R 2b for carrying out the invention are radicals selected from the group of -CH 2 -CH 2 -OH, -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (CH 3 ) -OH, -CH (CHs) -CH 2 -OH or -CH 2 -CH (OH) -CH 2 -OH.
• At least one of the radicals R 2b is a branched alkyl radical of the general formula - R 7 -CH (R 8 ) OH.
• R 7 and R 8 each represent a linear or branched alkyl radical having 1 to 8 C atoms, preferably 1 to 6 C atoms and particularly preferably 1 to 4 C atoms, with the proviso that the sum of the C atoms in R 7 and R 8 is not more than 9.
• R 7 and R 8 are each preferably linear alkyl groups. Particularly preferably, R 8 is a methyl group. For example, it may be -CH 2 -CH (CHs) -OH.
• the radicals R 2c are mono- or oligosaccharide radicals, preferably monosaccharide radicals. It can in principle be all kinds of saccharides. Preference is given to using radicals derived from pentoses and hexoses, in particular from hexoses. Examples of suitable monosaccharides include glucose, mannose, galactose, fructose or ribose. Preferably, glucose-derived radicals can be used. They may also be derivatives of the saccharides, for example products resulting from the reduction or oxidation of the saccharides. In particular, these may be sugar acids such as, for example, gluconic acid.
• the amount of all of the monomers (A) used together amounts to 5 to 94% by weight, based on the amount of all monomers polymerized into the polymer.
• the amount is 15 to 80 wt.%, Particularly preferably 25 to 75 wt.%, Very particularly preferably 35 to 72 wt.% And for example 45 to 70 wt.%.
• the monomers (B) are monoethylenically unsaturated monomers which have phosphoric acid and / or phosphonic acid groups. It may also be salts and / or esters thereof. In the case of esters, it is preferably half ester, ie not all of the acidic OH groups of the phosphoric acid and / or phosphonic acid groups are esterified.
• the monomers (B) are particularly preferably the free acids or salts thereof.
• Examples of monomers (B) include vinylphosphonic acid, phosphoric acid monovinyl ester, allylphosphonic acid, phosphoric acid monoallylester, 3-butenylphosphonic acid, mono (3-butenyl) phosphoric acid, (4-vinyloxybutyl) phosphoric acid, (phosphonoxyethyl) acrylate, methacrylic acid (phosphonoxyethyl) ester, mono (- 2-hydroxy-3-vinyloxypropyl) phosphoric acid, phosphoric mono (1-phosphonomoxymethyl-2-vinyloxy-ethyl) ester, phosphoric mono (3-allyloxy-2-hydroxypropyl) mono-2- (allylox-1-phosphonoxymethyl-ethyl) -phosphoric acid, 2-hydroxy-4-vinyloxymethyl-1,3,2-dioxaphosphol, 2-hydroxy-4-allyloxymethyl-1,3,2- dioxaphosphol.
• the amount of all of the monomers (B) used together amounts to 5 to 94% by weight, based on the amount of all monomers polymerized into the polymer.
• the amount is 10 to 75 wt.%, Particularly preferably 15 to 60 wt.% And most preferably 20 to 45 wt.%.
• the monomers (C) are monoethylenically unsaturated monomers which comprise at least one COOH group. They can also be salts thereof.
• monomers (C) include (meth) acrylic acid, crotonic acid, vinylacetic acid, maleic acid, fumaric acid, methylfumaric acid, methylmaleic acid, dimethylmaleic acid, methylenemalonic acid or itaconic acid or also to C 1 to C 4 half esters of said dicarboxylic acids.
• Dicarboxylic acids can also be used in the form of their cyclic anhydrides, provided that the formation of cyclic anhydrides is possible. Of course, mixtures of several different monomers (C) can also be used.
• At least one of the monomers (C) is (meth) acrylic acid, more preferably exclusively (meth) acrylic acid.
• the amount of all the monomers (C) used together amounts to 1 to 90% by weight, based on the amount of all monomers polymerized into the polymer. Prefers the amount is 5 to 70 wt.%, Particularly preferably 10 to 55 wt.% And most preferably 10 to 35 wt.%.
• Monomers (D) In addition to the monomers (A), (B) and (C), it is also possible to use, as an option, other ethylenically unsaturated monomers (D) other than (A) to (C).
• the monomers (D) serve to fine-tune the properties of the copolymer.
• monomers (D) can be used. They are selected by the skilled person depending on the desired properties of the copolymer, with the proviso that they must be copolymerizable with the monomers (A), (B) and (C).
• Suitable monomers (D) include in particular alkyl esters of (meth) acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate.
• alkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate.
• vinyl or allyl ethers e.g.
• vinyl esters such as vinyl acetate or vinyl propionate. It is also possible to use basic comonomers, for example acrylamide and alkyl-substituted acrylamides.
• the monomers (D) may also be crosslinking monomers having a plurality of ethylenically unsaturated groups.
• examples include di (meth) acrylates such as ethylene glycol di (meth) acrylate, butanediol-1,4-di (meth) acrylate, hexanediol-1,6-di (meth) acrylate, methylenebisacrylamide or di (meth) acrylates of polyethylene glycol, tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate and oligo (meth) acrylates.
• the amount of all optionally used monomers (D) together is 0 to 30 wt.% Based on the total amount of monomers used. Preferably, the amount is 0 to 20 wt.%, Particularly preferably 0 to 10%. If crosslinking monomers (D) are present, their amount should generally not exceed 5% by weight, preferably 2% by weight, based on the total amount of all monomers used for the process. It may, for example, be from 10 ppm to 1% by weight. Very particular preference is given to no monomers (D) being present. Preparation of the polymers
• the polymers according to the invention can be prepared directly from the monomers (A), (B), (C) and optionally (D).
• the preparation of the polymers can also be carried out by polymer-analogous esterification or by esterifying or hydrolyzing monomers during the polymerization reaction.
• Variant A direct preparation from the monomers
• the components (A), (B), (C) and optionally (D) can be polymerized together in a manner known in principle.
• Corresponding polymerization techniques are known to the person skilled in the art.
• the copolymers are prepared by free radical polymerization in a suitable solvent. Details for carrying out a radical polymerization are known to the person skilled in the art.
• the polymerization is preferably carried out in aqueous or predominantly aqueous solution. Suitable further solvents besides water are water-miscible organic solvents, especially water-miscible alcohols. The polymerization is preferably carried out in water.
• the free-radical polymerization is preferably started by the use of suitable thermally activatable polymerization initiators.
• suitable thermally activatable polymerization initiators include inorganic peroxo compounds, such as peroxodisulfates, in particular ammonium, potassium and preferably sodium peroxodisulfate, peroxosulfates, hydroperoxides, percarbonates and hydrogen peroxide and the so-called redox initiators.
• inorganic peroxo compounds such as peroxodisulfates, in particular ammonium, potassium and preferably sodium peroxodisulfate, peroxosulfates, hydroperoxides, percarbonates and hydrogen peroxide and the so-called redox initiators.
• mixtures of different initiators for example mixtures of hydrogen peroxide and sodium or potassium peroxodisulfate. Mixtures of hydrogen peroxide and sodium peroxodisulfate can be used in any proportion.
• water-soluble azo compounds such as azobis (2-amidinopropane) dihydrochloride can be used.
• peroxo compounds soluble in organic solvents such as, for example, t-butyl peroctoate.
• Redox initiators contain at least one of the abovementioned peroxo compounds as the oxidizing component. and, for example, ascorbic acid, glucose, sorbitol, ammonium or alkali metal hydrogensulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite, sulfide or sodium hydroxymethylsulfoxylate.
• As reducing component of the redox catalyst it is preferred to use ascorbic acid or sodium pyrosulphite. Relative to the employed in the polymerization amount of monomers used, for example 1 x 10 "5 and 1 mol% of the reducing component of the redox catalyst.
• transition metal catalysts may additionally be used, e.g. Salts of iron, cobalt, nickel, copper, vanadium and manganese. Suitable salts are e.g. Iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, copper (I) chloride.
• the reducing transition metal salt is usually used in an amount of 0.1 to 1000 ppm, based on the sum of the monomers. For example, combinations of hydrogen peroxide and iron (II) salts, such as a combination of 0.5 to
• the amount is determined by the skilled person depending on the desired copolymer. As a rule, 0.05% by weight to 30% by weight, preferably 0.1 to 15% by weight and particularly preferably 0.2 to 8% by weight, of the initiator are used with respect to the total amount of all monomers.
• suitable regulators such as, for example, mercaptoethanol
• mercaptoethanol can also be used in a manner known in principle.
• no controllers are used.
• thermal initiators are used, with water-soluble azo compounds and water-soluble peroxo compounds being preferred.
• water-soluble azo compounds and water-soluble peroxo compounds are preferred.
• the polymerization may be initiated by suitable radiation, for example.
• suitable photoinitiators include acetophenone, benzoin ethers, benzil dialkyls and their derivatives.
• the radical polymerization is preferably carried out at a temperature of less than 130 0 C.
• the temperature may be varied within a wide range by those skilled in the art depending on the type of monomers used, the initiator and the desired copolymer. Has proven itself a minimum temperature of about 60 0 C.
• the temperature can be kept constant during the polymerization or it can also be driven temperature profiles.
• the polymerization temperature is 70 to 125 ° C, particularly preferably 75 to 100 0 C.
• the polymerization can be carried out in conventional free-radical polymerization apparatus. If one works above the boiling point of the water or the mixture of water and other solvents, working in a suitable pressure vessel, otherwise it can be operated without pressure.
• the polymerization times are usually 1-10 h, preferably 2-9 h and in particular 3-8 h.
• Copolymers according to the invention which contain (meth) acrylic acid units as units (C) can therefore also be obtained by using only monomers (A), (B) and, if appropriate, (D) in an aqueous medium for the polymerization, the units ( C) are formed in situ by hydrolysis during the polymerization.
• monomers (A), (B) and, if appropriate, (D) in an aqueous medium for the polymerization, the units ( C) are formed in situ by hydrolysis during the polymerization.
• additional (meth) acrylic acid and / or other monomers (C) can be added from the beginning. This may be advisable if larger amounts of the monomer units (C) are to be incorporated into the copolymer.
• acid ester hydrolysis is a pronounced equilibrium reaction.
• the degree of hydrolysis can be controlled by the conditions under which the polymerization is carried out. The higher the temperature, the longer the reaction time and the lower the concentration of the monomers or copolymers (i.e., the higher the water content), the higher the degree of hydrolysis. Methacrylates generally hydrolyse more slowly than acrylates. Furthermore, the hydrolysis can be slowed down by partial neutralization of the acidic groups of monomers used, that is, at least the acidic groups of the monomers (B) and of any additional monomers (C) used. However, it is not necessary that a state of equilibrium is reached, but during the polymerization, depending on the conditions, no equilibrium state can be achieved.
• Suitable bases for neutralizing are, in particular, ammonia, amines, aminoalkylene or alkali metal hydroxides or soluble basic zinc, magnesium, aluminum or calcium salts, preferably the hydroxides.
• Preferred amines are alkylamines with up to 24 carbon atoms and amino alcohols containing up to 24 carbon atoms and structural units of the type -N-C2H4-O- and -N-C2H4-OH and -N-C2H4-O-CH3. Examples of such amino alcohols include ethanolamine, diethanolamine, triethanolamine and their methylated derivatives.
• the bases can be added before or during the polymerization.
• the degree of neutralization should by no means be too high, but sufficient free acid groups should still be present in the polymer. By free acid groups a particularly good adhesion of the polymers is achieved on the metallic surface. As a rule, not more than 50 mol% of the acid groups present in the copolymer should be neutralized, preferably from 5 to 40 mol%, particularly preferably from 15 to 10 mol%.
• the synthesized copolymers 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.
• the copolymers are preferably not isolated at all from the aqueous solution after the polymerization, but the resulting solutions of the copolymers are used as such for the process according to the invention.
• Variant B polymer-analogous esterification
• the copolymers can be prepared by polymer-analogous esterification.
• the starting material is a polymer of (meth) acrylic acid units, the monomers (B), optionally of (meth) acrylic acid different monomers (C) and optionally monomers (D) ago. This can be done by means of the above-described techniques for radical polymerization. If appropriate, it is also possible to use commercially available polymers for this purpose. For example, acrylic acid-vinylphosphonic acid copolymers (70:30) are commercially available.
• the COOH groups of the (meth) acrylic acid units can be esterified in a separate step after the polymerization with suitable alcohols.
• Alcohols used for the esterification are alcohols of the general formula HO-R 2 , where R 2 is as defined above. In each case, in-situ polymerized units (A) are obtained. If the copolymer also contains other monomers which have COOH groups, these are of course also correspondingly esterified. Exemplary is called maleic acid.
• the alcohol itself as the only solvent.
• the alcohol can also be mixed with other solvents, for example with water or other polar aprotic solvents, such as Ketones, for example acetone or methyl ethyl ketone, ethers, such as dioxane or tetrahydrofuran are used.
• water is used in a mixture with alcohols, the amount should be as low as possible. In general, the amount of water should not be more than 60% by weight with respect to the amount of all solvents, preferably not more than 50% by weight and more preferably not more than 45% by weight.
• Alcohols of the general formula HO-R 7 -CH (R 8 ) OH can preferably be used, where R 7 and R 8 are as defined above.
• R 7 and R 8 are preferably linear alkyl radicals, particularly preferably R 8 is -CH 3.
• a very particularly preferably used alcohol is 1, 2-propylene glycol HO-CH2-CH (OH) -CHs.
• the primary reacts preferentially
• 1, 2-propylene glycol acts simultaneously as a solvent and serves in particular as a solubilizer for other alcohols, in particular for solid and poorly meltable alcohols.
• Preferred reaction temperatures for the esterification are at 70 0 C to 120 0 C, more preferably at 8O 0 C to 100 0 C. Depending on the reaction temperatures is carried out without pressure or under pressure.
• auxiliaries and typical esterification catalysts can be used.
• Examples include mineral acids, ion exchangers, Lewis acids, metal salts, such as zinc acetate, heterogeneous catalysts, such as metal ion-modified silica gels, more amorphous metal hydroxides or titanium compounds of the Ti (O-AlkVl) 4 type .
• the degree of esterification can be controlled in a manner known in principle by the reaction conditions. It is known to the person skilled in the art that acid ester formation or hydrolysis is a pronounced equilibrium reaction. The degree of esterification depends on the one hand on the position of the chemical equilibrium and on whether it is achieved during the reaction time at all. The equilibrium depends inter alia on the ratio of alcohol to COOH groups, the proportion of water in the reaction mixture and, if appropriate, the temperature. Reaction temperature, reaction time and possibly the presence of a catalyst determine whether the equilibrium is reached at all.
• the degree of esterification in the present polymer-analogous esterification is generally about 5 to 60 mol% with respect to the sum of the originally present COOH Groups, provided that the formed reaction water is not removed from the reaction mixture. It is preferably at least 15 mol% and particularly preferably at least 20 mol%. If a higher degree of esterification is desired, the water formed should be removed from the reaction mixture.
• the resulting copolymers can be isolated from the reaction solution as described above. However, the copolymers are preferably not isolated from the solution at all after the polymerization but the solutions of the copolymers obtained are used as such for the process according to the invention. Unreacted alcohols usually do not interfere, they can even have a positive effect through a softening effect.
• the solvents used for the polymerization in this variant are the abovementioned alcohols HO-R 2 and preferably the alcohols also mentioned HO-R 7 -CH (R 8 ) OH or mixtures of these alcohols with water.
• the monomers can be polymerized with one another using the initiators mentioned in the introduction, with the monomer units (A) forming in situ in the course of the polymerization. With regard to the details, reference is made to what has been said under synthesis variant B.
• an acidic, aqueous preparation of said copolymers according to the invention is used.
• This may of course also be a mixture of several, different copolymers of the said type.
• the molecular weight M w (weight average) of the copolymers used for the process according to the invention is determined by the person skilled in the art according to the desired application.
• polymers having a molecular weight Mw of 3000 to 1 000 000 g / mol can be used.
• the preparation preferably comprises 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 polyetherpolyols, and ether alcohols, such as butylglycol or methoxypropanol, and N-methylpyrrolidone.
• alcohols of the general formula HO-R 2 may be present. These may be formed, for example, by hydrolysis of (meth) acrylic acid esters (A) or else they may be unreacted radicals in the course of polymer-analogous esterification.
• the amount of water is at least 65% by weight, preferably at least 75% by weight and very particularly preferably at least 85% by weight.
• the data refer to the total amount of all solvents.
• the polymer-containing solutions resulting from the polymerization and / or the polymer-analogous esterification can be used directly, which can optionally be further diluted before use.
• the concentration of the copolymers used according to the invention in the preparation is from 0.1 to 50% by weight, based on the amount of all components of the formulation.
• the amount is preferably 1 to 40% by weight and more preferably 5 to 35% by weight.
• the concentration and the nature of the polymers used can influence the properties of the preparation, for example its viscosity or its pH.
• the properties of the preparation can thus be optimally adapted to a specific process technology for treatment.
• a concentration of 10 to 25% by weight has proven successful in the case of a technique with pinching, and a concentration of 15 to 25% by weight when applied by means of paint rollers.
• the concentrations given refer to the ready-to-use preparation. It is also possible first to prepare a concentrate which is diluted to the desired concentration on site with water or optionally other solvent mixtures.
• the acidic preparation used according to the invention has a pH of not more than 5, in particular a pH of 0.5 to 5, preferably 0.75 to 3.5 and particularly preferably 0.8 to 2.0.
• the pH of the preparation can be controlled, for example, by the type and concentration of the polymers used according to the invention. Naturally, the degree of neutralization of the polymer plays a decisive role here.
• the preparation used according to the invention may optionally further comprise at least one inorganic or organic acid or mixtures thereof.
• suitable acids include phosphoric acid, phosphonic acid or organic phosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBTC), aminotri (methylenephosphonic acid) (ATMP), ethylenediamine tetra (methylenephosphonic acid) (EDTMP) or diethylenetriaminepenta- (methylenephosphonic acid) (DTPMP), N-2- (hydroxyethyl) iminobis (methylphosphonic acid) (HEIBPS), sulphonic acids such as methanesulphonic acid, amidosulphonic acid, p-toluenesulphonic acid, m-nitrobenzenesulphonic acid and derivatives thereof, ni
• Phosphorus-containing acids such as H3PO4, phosphonic acid
• phosphonic acid are preferably the organic phosphonic acids mentioned, HNO3 and / or methanesulfonic acid, and H3PO4 is particularly preferred.
• the formulation contains only H3PO4 as the acid.
• the (meth) acrylic acid ester units (A) of the copolymer used according to the invention may, depending on the type of ester group, slowly hydrolyze even at room temperature.
• OH groups of the radicals R 2 may also still react with free COOH groups to form crosslinking sites. This can lead to unwanted gelation of the preparation. It may therefore be advisable to partially neutralize the polymers after the reaction with suitable bases, for example with triethanolamine, and to add the desired acid only immediately before use.
• the pH values of such formulations may be significantly higher, for example 3 to 6.
• the preparation may optionally comprise further components in addition to the components mentioned.
• the preparation may optionally comprise at least one dissolved metal ion or metal compound.
• This may be, for example, a metal compound of Al, Mg, Ca, Ni, Co, V, Fe, Zn, Zr, Mn, Mo, W, Ti, Zr.
• the compounds can be used for example in the form of the respective aqua complexes.
• ligands such as fluoride complexes of Ti (IV), Zr (IV) or oxometallates such as MoO 4 2 " or WO4 2"
• the compounds may also be in the form of complexes with typical chelating ligands such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA) or methylglycinediacetic acid (MGDA) can be used.
• EDTA ethylenediaminetetraacetic acid
• DTPA diethylenetriaminepentaacetic acid
• HEDTA hydroxyethylethylenediaminetriacetic acid
• NTA nitrilotriacetic acid
• MGDA methylglycinediacetic acid
• the Passivation according to the invention is therefore preferably a chromium-free passivation, more preferably a chromium- and fluoride-free passivation.
• the preparation comprises at least one soluble metal ion selected from the group of Zn 2+ , Mg 2+ , Ca 2+ or Al 3+ .
• the ions may be in the form of hydrated metal ions, but they may be in the form of dissolved compounds, for example as complex compounds with the above-mentioned complexing agents.
• the ions may have complex bonds to the acidic groups of the polymer. It is preferably Zn 2+ or Mg 2+ and very particularly preferably Mg 2+ .
• the preparation next to it preferably does not comprise any further metal ions.
• the amount of metal ions from the group of Zn 2+ , Mg 2+ , Ca 2+ or Al 3+ is determined by the person skilled in the art according to the desired properties of the preparation. It is generally from 0.01% by weight to 20% by weight, preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight, and very particularly preferably from 1 to 5% by weight, based in each case to the total amount of all copolyme used in the formulation according to the invention.
• the formulation may further comprise at least one dissolved phosphate ion. It preferably contains phosphate ions if metal ions from the group of Zn 2+ , Mg 2+ or Ca 2+ are also present. These can be all types of phosphate ions. For example, these may be orthophosphates or diphosphates. It is clear to the person skilled in the art that in aqueous solution, depending on the pH and concentration, there may be an equilibrium between the different dissociation stages of the ions.
• the amount of phosphate ion in the formulation will be determined by those skilled in the art according to the desired properties of the formulation. It is generally 0.01% by weight to 20% by weight, preferably 0.5 to 20% by weight, particularly preferably 1 to 20% by weight and very particularly preferably 5 to 20% by weight, in each case calculated as orthophosphoric acid and in each case based on the copolymers.
• the metal ions in particular the metal ions from the group of Al 3+ , Zn 2+ , Mg 2+ or Ca 2+ and the phosphate ions can preferably be used in the form of soluble salts which contain both ions.
• examples of such compounds include Zn3 (PO4) 2, ZnH2PÜ4, Mg3 (PO4) 2 or Ca (H2PO4) 2 or corresponding hydrates thereof.
• the ions can also be added separately to one another.
• the metal ions can be used in the form of the corresponding nitrates, and the phosphate ions can be introduced in the form of phosphoric acid in the preparation.
• insoluble or sparingly soluble compounds such as For example, to use the corresponding carbonates, oxides, oxide hydrates or hydroxides, which are dissolved under the influence of acid.
• the excess passivation solution is usually recycled.
• metal ions can also be introduced by partial dissolution of the shaped body to be coated.
• the preparation may further contain at least one wax dispersed in the formulation.
• wax here encompasses both the actual wax and any auxiliary agents which may be used to form a wax dispersion .
• Waxes for use in aqueous dispersions are known to the person skilled in the art and suitable choices are made Oxydated polyethylene waxes based on fluorinated polyethylene such as PTFE or other polymers based on C, H and F.
• polyethylene is also intended to include copolymers of ethylene and other monomers, especially other olefins such as propylene.
• such ethylene copolymers comprise at least 65 weight percent ethylene.
• the amount of optionally used waxes is determined by the skilled person depending on the desired properties of the passivation layer. As a rule, an amount of from 0.01 to 70% by weight, preferably from 0.5 to 25 and particularly preferably from 0.5 to 10% by weight, based in each case on the copolymers used according to the invention, has proven useful.
• the preparation used can also comprise further components.
• examples which may be mentioned are surface-active compounds, corrosion inhibitors, complexing agents, oxidants, typical electroplating aids or also other polymers to be distinguished from the copolymers according to the invention.
• Other possible additives are conventional paint additives, as described in H. Kittel (Ed.) Textbook of Paints and Coatings, Volume 5 - Pigments, Fillers and Colorimetry -2. Aufl. S. Hirzel Verlag, Stuttgart 2003, are described.
• the person skilled in the art will make a corresponding selection among such further optional components and with regard to their quantities, depending on the desired application.
• the amount of such optional components should as a rule amount to not more than 20% by weight, preferably not more than 10% by weight and more preferably not more than 5% by weight, based on the copolymers.
• the preparations to be used for the process according to the invention can be obtained by simply mixing the components. If waxes are used, they are preferably first dispersed separately in water and mixed as a dispersion with the other components. Such wax dispersions are also commercially available.
• the surface of the metal is brought into contact with the preparation, for example by spraying, dipping or rolling.
• preference is given to using only the acidic formulation according to the invention.
• the process technology for performing the passivation there are a number of implementation options. These depend, inter alia, on the shape of the workpiece, for example, whether an unformed, flat metal strip or a metal sheet or a molded body is used, which has, for example, curved surfaces or edges.
• the treatment may also comprise several, individual process steps. It may be continuous or discontinuous. The person skilled in the art makes a suitable choice among the possible methods.
• the treatment can be carried out, for example, by immersion in the preparation or by spraying or brushing with the preparation.
• the preparation can preferably be rolled on. Further preferably, the metal strip can also be driven through a pan or a spray device with the preparation. Excess passivation solution can be removed by nip rolls and returned to the spray device.
• the spray device may generate a continuous spray or else drip the belt with only the preparation. Usual, for example, casting bars, which consist of a tube in which openings are provided at a distance of 2 to 10 cm, through which the preparation is sprayed onto the tape. The running of the preparation and the subsequent squeezing then lead to a sufficient distribution of the product.
• a continuous process for producing steel strips may also comprise a galvanizing station followed by a device for passivating with the preparation.
• the coating agent is usually taken up with a pickup roller from a trough and then transferred to an applicator roll.
• the applicator roll transfers the coating agent to the belt.
• Pick roller and applicator roll may be coupled via an intermediate roller over which the coating agent is transferred.
• the rollers can rotate in the same or opposite directions and run with or against the belt direction.
• the coating result can also be determined by choosing the contact pressure of the roller on the belt and the roughness and hardness of the roller.
• 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 can be done at room temperature or at elevated temperatures.
• the treatment is carried out at 20 to 90 0 C, preferably 25 to 80 0 C and particularly preferably 30 to 60 ° C.
• a bath can be heated with the preparation, but an elevated temperature can also be set automatically by immersing warm metal in a bath.
• 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 i. usually the water 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 inductive heating, or even for example by drying in a drying tunnel.
• IR emitters or inductive heating has proven to dry a temperature of 30 0 C to 210 0 C, preferably 40 ° C to 120 0 C and particularly preferably 40 ° C to 80 ° C. This refers to the peak temperature (PMT) found on the metal, which can be measured by methods familiar to the person skilled in the art (for example non-contact infrared measurement or determination of the temperature with glued-on test strips).
• the dryer temperature must be set higher and will be selected accordingly by the person skilled in the art.
• the process according to the invention may optionally also comprise one or more pretreatment steps.
• the metallic surface can be cleaned prior to passivation with the preparation used according to the invention, 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 according to the invention can be crosslinked.
• Crosslinking can be achieved in particular by selecting (meth) acrylic esters with such radicals R 2 which still have a functional group which is reactive with COOH groups.
• radical R 2 with OH groups very particularly radicals having primary OH groups.
• monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate.
• radicals R 2c such as glucose residues.
• the OH groups of these monomers can react well with COOH groups, especially at relatively high temperatures. The achievable degree of crosslinking naturally also depends on the ratio in which OH groups and COOH groups are present in the copolymer used according to the invention.
• a crosslinked passivation layer can also be obtained by additionally adding a crosslinker to the preparation according to the invention.
• Crosslinkers whose crosslinking mechanism is triggered only by an external impulse (eg, temperature increase, photochemical irradiation) are preferably used for this purpose.
• crosslinkers it is also possible to use more reactive crosslinkers. In order to avoid premature reaction, it is possible, for example, to add such crosslinkers to the formulation only shortly before application to the metallic workpiece. Alternatively, first of all the metal can be treated with a preparation without crosslinker and then the applied layer can be treated with a suitable crosslinker, for example sprayed with the solution of a crosslinker. It is also the reverse approach conceivable.
• Crosslinking can be effected, for example, by adding a di- or polyfunctional reaction partner which can form bonds with functional groups of the monomer AD. Suitable reactions for crosslinking or venation mechanisms may be, for example:
• Covalent crosslinking z. As esterifications, etherifications, reactions of epoxides or aziranes with nucleophiles, amidation, acetalization, urethane formation; b) ionic crosslinking, formation of polyelectrolyte complexes; c) hydrogen bonding, van der Waals bonds; or
• the crosslinking can also be effected by entanglement of the polymer chains (for example by photochemically induced crosslinking of added photosensitive components).
• crosslinkers examples include di- or polyfunctional alcohols, amines, carboxylic acids, aldehydes, thiols, isocyanates, isocyanurates, blocked isocyanates, melamine-formaldehyde condensates, epoxides, carbodiimides or aziranes. It may be low molecular weight, oligomeric or polymeric crosslinkers.
• crosslinkers are used as part of the formulation, they should preferably be water-soluble or water-dispersible, but must be soluble or dispersible at least in the formulation according to the invention.
• Crosslinkers that are used separately from the acidic formulation in the two-stage process described above need not necessarily be water-soluble or water-dispersible.
• crosslinkers examples include water-soluble di- or polycarboxylic acids such as oxalic, malonic, maleic, itaconic, citraconic, mesaconic, succinic, glutaric, adipic, sebacic, corkic, citric and polyhydroxydicarboxylic acids of the type the sugar acids.
• hydroxycarboxylic acids such as, for example, lactic acid, malic acid, tartronic acid, tartaric acid, mandelic acid, citric acid and onklaren the monosaccharides.
• gluconic acid may be mentioned here.
• crosslinking can also be carried out by adding di-, tri- or oligo-alcohols. Preference may be given to using substances which have at least two structural elements of the type -CH 2 OH in the molecule. Examples include 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, pentaerythritol, diethylene glycol, triethylene glycol and polyethylene glycol.
• crosslinkers based on epoxides include low molecular weight compounds having two epoxy groups, such as ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, sorbitol polyglycidyl ether, ethylene or polyethylene glycol.
• glycol diglycidyl ethers polypropylene oxide glycol diglycidyl ethers, glycerol polyglycidyl ethers, polyglycerol glycidyl ethers, phthalic acid diglycidyl ethers or cycloaliphatic compounds such as 3,4-epoxycyclohexanecarboxylic acid 3 ', 4'-epoxycyclohexylmethyl ester.
• Suitable melamine derivatives include, for example, hexamethylolmelamine or hexamethoxymethylmelamine or else optionally modified aminoplast resins.
• Melamine-formaldehyde groups comprehensive crosslinkers are also commercially available, for example, the Luwipal® ® Brand (Fa. BASF AG).
• Isocyanate crosslinkers can preferably be used in the two-stage crosslinking process described above.
• Crosslinkers containing isocyanate groups may be the polyisocyanates conventionally used in polyurethane chemistry, for example aliphatic, aromatic and cycloaliphatic di- and polyisocyanates, the aliphatic hydrocarbon radicals having, for example, 4 to 12 carbon atoms, and the cycloaliphatic or aromatic hydrocarbon radicals, for example 6 to 15 carbon atoms the araliphatic hydrocarbon radicals have, for example, 7 to 15 carbon atoms, with an NCO functionality of at least 1.8, preferably 1.8 to 5 and particularly preferably 2 to 4 in question, and in particular their isocyanurates, biurets, allophanates and uretdiones, oxadiazinetriones, iminooxadiazinedio ne, uretonimine-modified polyisocyanates.
• the diisocyanates are preferably isocyanates having 4 to 20 C atoms.
• Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, Dode camethylendiisocyanat, Tetradecamethylendiisocyanat, esters of Lysindiisocyanates, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexanediisocyanate, cycloaliphatic diisocyanates such as 1, 4- , 3- or 1,2-diisocyanatocyclohexane, trans / trans, the cis / cis and cis / trans isomers of 4,4'- or 2,4'-di (iso
• Isocyanatgrup- pen comprehensive crosslinkers are commercially available, for example under the brand Basonate ® (Messrs. BASF AG). It is also possible to use blocked polyisocyanates as crosslinkers. In blocking, the isocyanate group is reversibly reacted with a blocking agent. The blocking agent is split off again when heated to higher temperatures. Examples of suitable blocking agents are disclosed in DE-A 199 14 896, column 12, line 13 to column 13, line 2. Particular preference is given to using polyisocyanates blocked with ⁇ -caprolactam.
• the amount of crosslinker optionally added is generally not more than 20 mol%, preferably not more than 15 mol% and particularly preferably not more than 10 mol%, in each case based on the monomer A.
• the crosslinking can preferably be carried out with an increase in temperature.
• the crosslinking may be combined with the drying of the layer.
• the degree of crosslinking is determined by the parameters temperature, concentration of the crosslinker, water content and esterification catalyst. The person skilled in the art selects the parameters such that the desired degree of crosslinking results.
• the passivation layer is overpainted, it is also possible to use a baking step for the lacquer layer for the simultaneous crosslinking of the underlying passivation layer.
• a passivation layer or conversion layer in particular on a metallic surface of Zn, Zn alloys, Al or Al alloys is obtainable.
• the copolymers according to the invention superficial dissolving is particularly good, and excellent corrosion protection is obtained.
• the exact structure and composition of the passivation layer is unknown to us.
• it in addition to the usual amorphous oxides of aluminum or zinc and optionally further metals, it also comprises the reaction products of the polymer and optionally of the crosslinker and / or further components of the formulation.
• the composition of the passivation layer is generally not homogeneous, but the components appear to have concentration gradients.
• the thickness of the passivation layer is adjusted by the person skilled in the art according to the desired properties of the layer.
• the thickness is 0.01 to 3 ⁇ m, preferably 0.1 to 2.5 ⁇ m, and particularly preferably 0.2 to 1.5 ⁇ m.
• the thickness can be influenced, for example, by the type and amount of the applied components as well as the exposure time. Furthermore, it can be influence technical parameters, for example by doctoring or rolling over-applied treatment solution.
• the thickness of the layer is determined by differential weighing before and after the action of the composition used according to the invention on the metal surface, assuming that the layer has a specific density of 1 kg / l.
• layer thickness is always understood to mean a size determined independently of the specific density that the layer actually has.These thin layers are sufficient to achieve outstanding corrosion protection.
• a further subject of the present application is a metallic surface which comprises the passivation layer according to the invention.
• the passivation layer is applied directly to the actual metal surface.
• it is a strip metal made of steel, which comprises a coating of Zn or a Zn alloy, and on which a passivation layer according to the invention is applied. It can also be an automobile body, which is coated with the passivation layer according to the invention.
• the metallic surface with passivation layer can be painted over in a preferred embodiment of the invention in a manner known in principle with one or more color or effect paint layers.
• Typical lacquers, their composition and typical layer sequences in the case of several lacquer coats are known in principle to the person skilled in the art. It turns out that the passivation according to the invention improves the paint adhesion and generates an immigration protection.
• the passivation process according to the invention can be used at various processing stages. It can be made for example at a steel manufacturer. In this case, a steel strip can be galvanized in a continuous process and passivated immediately after galvanizing by treatment with the formulation used according to the invention. Passivation at this stage is often referred to by the skilled person as "post-treatment".
• the copolymers can be removed by cleaning with aqueous alkaline solutions back from the surface. But it may also be a permanent corrosion protection treatment, which remains on the belt or the finished molded workpiece and is provided with additional paint layers. Passivation at this stage is often referred to by the skilled person as "pretreatment".
• the indicated reaction temperatures refer to the internal temperature in the reaction vessel.
• the K values were measured according to H. Fikentscher, Cellulose-Chemie, Vol. 13, pp. 58-64 and 71-74 (1932) in 1% strength by weight aqueous solution at 25 ° C. without pH correction.
• the solids contents were determined by heating in a vacuum oven at 120 ° C. for two hours and differential weighing.
• the residual monomer content of vinylphosphonic acid was determined by 31 P-NMR spectra.
• the degree of esterification of the COOH groups was determined by 1 H-NMR spectra immediately after the synthesis. If different monomers A or different alcohols are used, the indication of the degree of esterification refers to the individual components A n or the corresponding alcohols.
• Mw values are determined by gel permeation chromatography (GPC). Calibration of the GPC is performed with a widely distributed Na-PAA mixture whose integral molecular weight distribution curve is determined by SEC laser light scattering according to the calibration method of M.J.R. Cantow et al. (J. Polym. Sci., A-1,
• monomer B (monomers having phosphorus or phosphonic acid groups) is introduced as an aqueous solution (40-95% strength), rendered inert with nitrogen and heated to the reaction temperature.
• An addition of 1 to an aqueous solution of the respectively desired monomer A (mono (meth) acrylic acid ester (100 to 50% strength solution) over 3 to 5 hours, and simultaneously an addition of an aqueous initiator solution over 4 to 6 hours ( 5 to 30% pure) is then stirred for two hours at the reaction temperature, if appropriate diluted with water.
• the monomer units (C) are formed by hydrolysis from the monomer units (A). If additional amounts of the monomers (C) are added, these - if they are homogeneously miscible with the monomers (A) - can be fed together with the monomers (A). If both monomers are incompatible with one another, they are each fed in via a separate feed.
• Table 1 a shows the relationship between the degree of esterification in mol% and the composition of the polymer in% by weight.
• Table 3a shows the relationship between the degree of esterification in mol% and the composition of the polymer in% by weight.
• Table 3a shows the relationship between the degree of esterification in mol% and the composition of the polymer in% by weight.
• composition of the product polymers At a monomer ratio of HPA / VPS of 70/30% by weight, the following results
• composition of the Product Polymers In the case of a monomer mixture of AS / VPS of 61/39% by weight and 100% by mole of the alcohol component (based on COOH groups), the following relationship arises between the degree of esterification and the weight of the composition
• Part B Use of the copolymers according to the invention for passivation
• aqueous solutions of the copolymers were used.
• concentration of the polymers was in each case 15-20% by weight with respect to the sum of all components of the formulation.
• the exact amount is given in Table 4, respectively.
• the formulations may also contain Mg 3 (PC "4) 2, Zn 3 (PC” 4) 2, H 3 PO 4 in the amounts indicated in Table 4.
• Metal test panels were obtained from hot-galvanized steel for the examples and comparative examples (Gardobond ® OE HDG 3, 105 x 190 mm) was used.
• the sheets in an alkaline cleaning solution (Ridoline ® C72, Fa. Henkel) were immersed for 10-20 seconds, immediately rinsed with deionized water and then dried with nitrogen.
• the cleaned sheets were immersed at room temperature for 1 s in the formulations listed in Table 1, squeezed with a roller system and for 12 s at 160 0 C in a drying oven (peak metal temperature in the course of drying did not exceed 50 0 C) dried.
• the condensed water alternating climate test (DIN 51017) consists of one or more climatic cycles, each with two test sections. In the first section, the test specimens are loaded for 8 hours at a temperature of 40 0 C and a relative humidity of 100%, in the second section at a temperature of 18-28 0 C at a humidity of less than 100% (ambient condition). The duration of a cycle is thus 24 hours.
• Chalking refers to a white haze of the coating, and as the level of chalking increases, the coating becomes less transparent.
• This spray test is a corrosion test standardized in DIN 50021, in which finely sprayed sodium chloride solution is allowed to act on the sample. On an inclined sample are sprayed at 35 0 C based on 80 cm 2 area 1, 5 ml / h of the solution using humidified compressed air. As a solution, a 5% NaCl solution was used. The coated samples are submitted intact to the test. The test duration is 48 h each.
• the quality of the corrosion protection in the salt spray test was evaluated in accordance with DIN EN ISO 10289 by assigning rating numbers from 0 to 10 according to specified standards.
• the rating is a measure of the formation of white rust on the sheet. The higher the rating, the lower the amount of corroded area and the better the corrosion protection.
• the allocation of the evaluation numbers was made according to the following table:
• the test series was carried out on an industrial strip galvanizing line.
• the substrate used was a steel strip, which was first provided with a zinc coating of 275 g / m 2 in a hot-dip station. Thereafter, the formulations were applied with a Sprühbalkensystem at a belt speed of 70-80 m / min onto the belt, squeezed with a roll system and dried (peak metal temperature ⁇ 50 0 C).
• Tables 1, 2 and 3 measured experimentally determined degrees of esterification immediately after the synthesis.
• the examples and comparative examples show that by using the copolymers according to the invention with the monomers (A) in combination with monomers (B) and (C), the appearance of the resulting passivation layers compared to polymers which do not contain the functional monomers (A) significantly can be improved.
• Polymers which consist only of the monomers (A) have neither a sufficient corrosion protection effect, nor can layers of sufficient optical quality be achieved. At least 5% of phosphorus-containing monomers (B) are required.

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