ZA200302864B

ZA200302864B - Method for pretreating and/or coating metallic surfaces with a paint-like coating prior to forming and use of substrates coated in this way.

Info

Publication number: ZA200302864B
Application number: ZA200302864A
Authority: ZA
Inventors: Christian Jung; Toshiaki Shimakura; Norbert Maurus; Heribert Domes; Klaus Bittner; Thomas Kolberg; Marcus Schinzel
Original assignee: Chemetall Gmbh
Priority date: 2000-10-11
Filing date: 2001-10-10
Publication date: 2004-04-13
Also published as: ZA200302862B

Description

The invention relates to a method of coating metallic surfaces and also to the use of the coated substrates produced by the method of the invention in particular in vehicle construction, especially in the line manufacture of automobiles, and for the production of components or bodywork parts or premounted elements in the vehicle, air travel or space travel industry. It relates in particular to new possibilities for the preparation and assembly of motor vehicles which no longer involve the current standard practice of assembling the various parts of the body, cieaning and phosphating them and only then painting them with the paint system as a whole.

There is a need for even greater rationalization of the manufacture of vehicle bodies and their individual parts and also of paneling for vehicles and aircraft.

The anticorrosion layer(s) ought to be readily formable together with the paint or a paintlike layer and ought also to exhibit, after forming, effective corrosion protection and effective paint adhesion.

Additionally, depending on the joining technique, it may be necessary for said layer(s) to be readily clinchable as well without showing a greater tendency toward corrosion as a result.

For producing paint-coated metal sheets there are already methods similar to the production methods for metal sheets precoated on the strip, which are used for household appliances, metal architectural panels, and furniture. The requirements imposed on these sheets, however, are much less stringent than the requirements in particular in automobile engineering and aircraft construction. This is because the requirements in the vehicle, air travel or space industry in terms of the strength of the coated sheets, the joining technologies, the paint system, and the properties of the paint layers, such as brightness, gloss, corrosion resistance, scratch resistance, paint adhesion, and stonechip resistance, are markedly different and influence the complex manufacturing process. The high-grade properties of these sheets must still be sufficiently high in the region of the formed and joined portions in particular. Normally, the same exacting requirements as those imposed at present are imposed on a different manufacturing process and a different layer structure, even when individual layers are thinner than 4 um. The composition of the coating used for this purpose, comprising polymers and particles, is also novel, to the knowledge of the applicant.

The basecoat for metal architectural panels on the outside presently often contains chromate, in order to provide increased corrosion resistance at a relatively low layer thickness; applied to the basecoat there is normally a topcoat with a thickness in the range from 10 to 20 ym. The same or in particular in automobile engineering and aircraft construction. This is because the requirements in the vehicle, air travel or space industry in terms of the strength of the coated sheets, the joining technologies, the paint system, and the properties of the paint layers, such as brightness, gloss, corrosion resistance, scratch resistance, paint adhesion, and stonechip resistance, are markedly different and influence the complex manufacturing process. The high- grade properties of these sheets must still be sufficiently high in the region of the formed and joined portions in particular. Normally, the same exacting requirements as those imposed at present are imposed on a different manufacturing process and a different layer structure, even when individual layers are thinner than 4 um. The composition of the coating used for this purpose, comprising polymers and particles, is also novel, to the knowledge of the applicant.

The basecoat for metal architectural panels on the outside presently often contains chromate, in order to provide increased corrosion resistance at a relatively low layer thickness; applied to the basecoat there is normally a topcoat with a thickness in the range from 10 to 20 um. The same or similar baseccats as on the facing side are often applied to the inside of metal architectural panels, as a reverse-face coating, with a thickness in the range from 6 to 15 um, as a single paint layer. To date, however, to the knowledge of the applicant, there has been no use of UV-cured paint materials in the coating of strips in the household appliance and architectural segments.

The strip line which is utilized in each case may be a galvanizing line, a coil coating line and/or another kind of coating line, such as, for example, a painting line in, for example, an automobile plant, on which cut strip which has been pretreated beforehand on a strip

- 3 = line is painted with a paint and/or with a paintlike coating.

By prephosphating is meant a temporary protection of metallic surfaces, it being possible for the substrates thus coated to be subsequently subjected, where appropriate, to oiling, temporary storage, forming, joining (after deoiling) by clinching, adhesive bonding and/or welding, for example, and/or pretreated again with phosphate, for example, before the paint system is applied.

Pretreatment prior to painting is nowadays carried out, particularly in the European automobile industry, sometimes without deliberate addition of chromium and sometimes with addition of chromium. In principle, however, it is preferred to operate without chromium or substantially without chromium, in particular without chromium to the extent that no chromium is deliberately added, in order to avoid this toxic heavy metal.

Nevertheless, the addition of chromium has a particular corrosion protection effect, given that a self-healing effect may come about at a site which has been damaged.

The pretreatment solutions are preferably also free from or contain low levels in each case of cobalt, copper, nickel and/or other heavy metals. Amounts of nickel in particular, however, are still particularly advantageous and are therefore virtually always present in phosphate coats, for example. The pretreatment solutions can be applied either by the rinse method or by the no-rinse method. In the case of the rinse method, the application of the solution, which can take place in particular by spraying and/or dipping and during which the pretreatment layer is formed, is followed by rinsing. In the case of the no-rinse method, the solution is applied with a roll coater, for example, and is dried immediately without rinsing.

By a basecoat is meant a paint or a paintlike coating which replaces the cathodic dip coat (electrocoat) that is commonly used in bodywork construction. It may be a primer, in particular a lubricant primer, welding primer or pretreatment primer, or another kind of coating, based for example on silane/siloxane. When necessary, an intermediate paint layer may be applied between the basecoat and the surfacer (i.e., color coating). The surfacer is normally followed by at least one clearcoat, which intensifies the brightness and is also referred to as the topcoat.

The coating which is developed with a lubricant primer can be formed very effectively and easily owing to the good slip properties, its low friction, and its flexibility. A welding primer and the coating produced from it includes such a high fraction of electrically conductive substance, in particular of electrically conductive particles, that two metal sheets can be welded together without substantially increased effort even when this involves contacting through two paintlike coats. A pretreatment primer is a primer or a corresponding coating which may also replace the corrosion protection properties of a pretreatment layer. All of these are paintlike coatings.

The invention further relates to a method of coating metallic surfaces with an aqueous composition comprising polymer and fine inorganic particles. The invention additionally relates to such an aqueous composition and also to the use of the substrates coated by the method of the invention.

The processes used most frequently to date for the surface treatment or pretreatment prior to painting of metals, particularly of metal strip, are based on the use of chromium(VI) compounds together with diverse additives. Owing to the toxicological and environmental risks which such processes entail and, moreover, owing to the foreseeable statutory restrictions on the use of chromate-containing processes, the search has been on for some time already for alternatives to these processes in all fields of metal surface treatment.

Resin mixtures are known for which resins are blended with inorganic acids in order thus to obtain a pickling attack as well and hence a better contact of the resin coat directly with the metallic surface. These compositions have the drawback that, owing to the pickling attack, contamination occurs during the contacting of the treatment liquid (dispersion) to the substrate. This leads to the accumulation of metals in the treatment liquid and, as a result, to a permanent change in the chemical composition of the treatment liquid, thereby significantly impairing the corrosion protection. These metals are dissolved by the pickling attack out of the metallic surface of the substrate to be treated.

Another drawback is that, especially in the case of aluminum and aluminum-containing alloys, the surfaces darken, discoloring in certain circumstances to a dark gray to anthracite color. The darkened metal surfaces cannot be used for decorative applications, since the discoloration is undesirable on esthetic grounds alone.

Depending on the thickness of the applied layer, the darkening is visible with varying intensity.

The object was therefore to overcome the drawbacks of the prior art and in particular to propose a method of coating metallic surfaces which is also suitable for high ccating speeds, such as are used for strips; which can be employed substantially or entirely free from chromium (VI) compounds; which as far as possible is also free from organic and inorganic acids; and which can be employed industrially.

It is an object of the invention to propose a method of coating metallic substrates which are also suitable for the coating of strips running at speed and with which it is possible to apply organic, sufficiently flexible, and at the same time sufficiently corrosion-resistant coatings, which allow the production of a basecoat and, where appropriate, of the subsequent layers as well.

This method ought to be suitable for economic and very environmentally friendly industrial implementation.

A further object was to propose a method for producing parts, in particular for the assembly of automobile bodies, with which it is possible to perform a longer part of the manufacturing operation of the parts, where appropriate still in the form of a strip, than was hitherto the case in a strip line.

The object is achieved by a method of coating a metallic strip, the strip, or where appropriate strip sections produced from it, in the subsequent operation, being first coated with at least one anticorrosion layer and then with at least one layer of a paintlike, polymer-containing layer, the strip, after coating with at least one anticorrosion layer or after coating with at least one layer of a paintlike coating, being divided into strip sections, the coated strip sections then being formed, joined and/or coated with at least one (further) paintlike layer and/or paint layer, the paintlike coating being formed by coating the surface with an aqueous dispersion which comprises besides water a) at least one organic film former comprising at least one water-soluble or water-dispersed polymer having an acid number in the range from 5 to 200, b) at least one inorganic compound in particle form, having an average particle diameter, measured in a scanning electron microscope, in the range from 0.005 up to 0.3 pm diameter, and c) at least one lubricant and/or at least one corrosion inhibiteor, the metallic surface coated with at least one anticorrosion layer being contacted with the aqueous composition and a particle- containing film being formed on the metallic surface, and subsequently dried and, as the case may be, additionally cured, the dried and, as the case may be, additionally cured film having a thickness in the range from 0.01 to 10 um.

The object is further achieved by a method of coating a metallic strip, the strip being coated with at least one layer of a paintlike, polymer-containing coat without an anticorrosion layer being applied beforehand, the strip, after coating with at least one layer of a paintlike coating, being divided into strip sections, the coated strip sections then being formed, joined and/or «coated with at least one (further) paintlike layer and/or paint layer, the paintlike coating being formed by coating the surface with an aqueous dispersion which comprises besides water a) at least one organic film former comprising at least one water-soluble or water-dispersed polymer having an acid number in the range from 5 to 200, b) at least one inorganic compound in particle form, having an average particle diameter, measured 1n a scanning electron microscope, in the range from 0.005 up to 0.3 um diameter, and c) at least one lubricant and/or at least one corrosion inhibitor, the clean metallic surface being contacted with the aqueous composition and a particle-containing film being formed on the metallic surface, and subsequently dried and, as the case may be, additionally cured, the dried and, as the case may be, additionally cured film having a thickness in the range from 0.01 to 10 um.

The surfaces coated 1n these methods are metallic surfaces in particular of aluminum, iron, copper, magnesium, nickel, titanium, tin, zinc or alloys of aluminum, iron, copper, magnesium, nickel, titanium, tin and/or zinc. The aqueous composition used may in this case be substantially or entirely free from

Claims

1. A method of coating a metallic strip, the strip, or where appropriate strip sections produced from it, in the subsequent operation being first coated with at least one anticorrosion layer and then with at least one layer of a paintlike, polymer- containing layer, the strip, after coating with at least one anticorrosion layer or after coating with at least one layer of a paintlike coating, being divided into strip sections, the coated strip sections then being formed, Joined and/or coated with at least one (further) paintlike layer and/or paint layer, the paintlike coating being formed by coating the surface with an aqueous dispersion which comprises besides water a) at least one organic film former comprising at least one water-soluble or water-dispersed polymer having an acid number in the range from 5 to 200, b) at least one inorganic compound in particle form, having an average particle diameter, measured in a scanning electron microscope, in the range from 0.005 up to 0.3 um diameter, and c) at least one lubricant and/or at least one corrosion inhibitor, the metallic surface coated with at least one anticorrosion layer being contacted with the aqueous composition and a particle-containing film being formed on the metallic surface, and subsequently dried and, as the case may be, additionally cured, the dried and, as the case may be, additionally cured film having a thickness in the range from 0.01 to 10 pm.

2. A method of coating a metallic strip, the strip being coated with at least one layer of a paint- like, polymer-containing layer without an anti- corrosion layer being applied beforehand, the strip, after coating with at least one layer of a paintlike coating, being divided into strip sections, the coated strip sections then being formed, Joined and/or coated with at least one (further) paintlike layer and/or paint layer, the paintlike coating being formed by coating the surface with an aqueous dispersion which comprises besides water a) at least one organic film former comprising at least one water-soluble or water- dispersed polymer having an acid number in the range from 5 to 200, Db) at least one inorganic compound in particle form, having an average particle diameter, measured in a scanning electron microscope, in the range from 0.005 up to 0.3 pm diameter, and c) at least one lubricant and/or at least one corrosion inhibitor, the clean metallic surface being contacted with the agueous composition and a particle-containing film being formed on the metallic surface, and subsequently dried and, as the case may be, additionally cured, the dried and, as the case may be, additionally cured film having a thickness in the range from

0.01 to 10 um.

3. The method of claim 1 or 2, characterized in that a surface of aluminum, iron, copper, magnesium, nickel, titanium, tin, zinc or alloys of aluminum, iron, copper, magnesium, nickel, titanium, tin and/or zinc is coated.

4. The method of any of the above claims, characterized in that aqueous composition is substantially or entirely free from chromium(VI) compounds.

5. The method of any of the above claims, characterized in that the element to be coated - in particular a strip or strip section - is subjected to forming after having been coated.

yr. ] -1llla - .

5. The method of any of the above claims, characterized in that the element to be coated is subjected to forming after having been coated. AMENDED SHEET AMENDED SHEET 2004 -06- 2 9 h : - 112 -

6. The method of any of the above claims, characterized in that aqueous composition comprises at least one organic solvent, one silane and/or siloxane 3 calculated as silane, at least one crosslinking agent, and/or at least one chromium (VI) compound.

7. The method of any of the above claims, characterized in that the organic film former is in the form of a solution, dispersion, emulsion, microemulsion and/or suspension.

8. The method of any one of the above claims, characterized in that organic film former is at least one synthetic resin.

9. The method of any of the above claims, characterized in that the organic film former is a synthetic resin mixture and/or addition copolymer which includes synthetic resin based on acrylate, epoxide, ethylene, urea-formaldehyde, phenol, polyester, polyurethane, styrene and/or styrene- butadiene, and from which, during or after the emission of water and other volatile constituents, an organic film is formed.

10. The method of any of the above claims, : characterized in that the organic film former comprises synthetic resing and/or polymers and/or derivatives, copolymers, polymers, mixtures and/or addition copolymers based on acrylate, epoxide, : phenol, polyethyleneimine, polyurethane, polyvinyl alcohol, polyvinylphenol, polyvinylpyrrolidone : AMENDED SHEET 04 gs. 5 I and/or polyaspartic acid, especially copolymers with a phosphorus-containing vinyl compound.

11. The method of any of the above claims, characterized in that the molecular weights of the synthetic resins, copolymers, polymers and/or derivatives thereof, mixtures and/or addition copolymers are in the region of at least 1000 u.

. 12. The method of any of the above claims, characterized in that the pH of the organic film former in an aqueous formulation, without the addition of further compounds, is in the range from 1 to 12.

13. The method of any of the above claims, characterized in that the organic film former contains only water-soluble synthetic resins and/or polymers. :

14. The method of any of the above claims, characterized in that the organic film former contains synthetic resin and/or polymer which contain carboxyl groups.

15. The method of any of the above claims, characterized in that the acid groups of the synthetic resins have been stabilized with or ammonia, with amines and/or with alkali metal compounds:

16. The method of any of the above claims, characterized in that the aqueous composition AMENDED SHEET 5004 -06- 2 9 contains from 0.1 to 1000 g/L of the organic film former.

17. The method of any of the above claims, characterized in that the aqueous composition comprises at least one partly hydrolyzed or completely hydrolyzed silane.

18. The method of any of = the above claims, characterized in that at least one aminosilane, epoxysilane, vinylsilane and/or at least one corresponding siloxane is present.

19. The method of any of the -~ above claims, characterized in that the amount of at least one silane and/or siloxane, calculated as silane, in the aqueous composition is from 0.1 to 50 g/L.

20. The method of any of the above claims, : characterized in that as inorganic compound in particle form a finely divided powder, a dispersion or a suspension is added. :

21. The method of any of the above claims, characterized in that as inorganic compound in particle form particles having an average gize in the range from 8 nm to 150 nm are used.

22. The method of any of the above claims, characterized in that as inorganic compound in particle form particles based on at least one compound of aluminum, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zinc and/or zirconium are added. AMENDED SHEET 2004 -06- 2 9

23. The method of any of the above claims, characterized in that as inorganic compound in particle form particles based on alumina, barium sulfate, cerium dioxide, silica, silicate, ' 5 titanium oxide, "yttrium oxide, zinc oxide and/or . zirconium oxide are added.

24. The method of any of the above claims, characterized in that the aqueous composition comprises from 0.1 to 500 g/L of the at least one inorganic compound in particle form.

25. The method of any of the above claims, characterized in that the aqueous composition comprises at least one corrosion inhibitor, at least one conductive ~ polymer and/or at least one thiol.

26. The method of any of the above claims, characterized in that the aqueous composition comprises at least one crosslinking agent based on a basic compound.:

27. The method of any of the above claims, characterized in that the aqueous composition is free from inorganic acids and/or organic carboxylic acids. :

28. The method of any of the above claims, characterized in that as organic solvent for the organic polymers at least one water-miscible and/or water-soluble alcohol, one glycol ether or N-methylpyrrolidone and/or water is used, in the case of the use of a solvent mixture a mixture of at least one long-chain alcohol, an ester alcohol, a ‘glycol ether and/or butanediol with water. AMENDED SHEET 2004 -06- 2 9

29. The method of any of the above claims, characterized in that the amount of organic solvent is from 0.1 to 10% by weight.

30. The method of any of the above claims, characterized in that as lubricant at least one wax selected from the group consisting of paraffins, polyethylenes, and polypropylenes is used.’

31. The method of claim 30, characterized in that the melting point of the wax used as lubricant is in the range from 40 to 160°C.

32. The method of any of the above claims, characterized in that additionally a conductive polymer is added.

33. The method of any of the above claims, characterized in that additionally at least one photoinitiator is added in order to allow curing by exposure to actinic radiation.

34. The method of claim 33, characterized in that the coating is cured partly by actinic radiation and . partly by drying and filming or thermal : crosslinking. :

35. The method of any of the above claims, characterized in that the aqueous composition comprises where appropriate in each case at least one biocide, defoamer and/or wetting agent. AMENDED SHEET 2004 -06- 2 9

36. The method of any of the above claims, characterized in that an aqueous composition having a pH in the range from 0.5 to 12 is used.

37. The method of any of the above claims, characterized in that the aqueous composition is applied with a temperature in the range from 5 to 50°C to the metallic surface.

38. The method of any of the above claims, characterized in that the metallic surface is held at temperatures in the range from 5 to 120°C on application of the coating.

39. The method of any of the above claims, characterized in that the coated metallic surface is dried at a temperature in the range from 20 to 400°C PMT (peak metal temperature).

40. The method of any of the above claims, characterized in that the coated strips are wound to a coil, where appropriate after cooling to a temperature in the range from 40 to 70°C.

41. The method of any of the above claims, characterized in that the aqueous composition is applied by rolling, flowcoating, knifecoating, spraying, squirting, brushing or dipping and, where appropriate, by subsequent squeezing off with a roll.

42. The method of any of the above claims, characterized in that the dried and also, where appropriate, cured film has a pendulum hardness of from 30 to 190 s, measured with a Kénig pendulum hardness tester in accordance with DIN 53157.

43. The method of any of the above claims, characterized in that the dried and also, where appropriate, cured film has a flexibility such that bending over a conical mandrel in a mandrel bending test very substantially in accordance with DIN ISO 6860 for a mandrel of from 3.2 mm to 38 mm in diameter - but without scoring of the test area E - produces no cracks longer than 2 mm which are perceptible when subsequently wetted with copper sulfate as a result of color change as a consequence of copper deposition on the cracked metallic surface.

44. The method of any of the above claims, characterized in that in each case at least one coating comprising varnish, polymers, paint, adhesives and/or adhesive backing is applied to the dried and also, where appropriate, cured film.

45. The method of any of the above claims, characterized in that the coated metal parts are formed, painted, coated with polymers, printed, bonded, hot-soldered, welded and/or joined or tone another or to other : / elements by clinching or other joining techniques. :

46. The method of any of the above claims, characterized in that the strip or the strip sections is/are cut, where appropriate, after painting with a paintlike coating and the painted strip sections during cutting and/or then are : formed and thereafter joined, where appropriate, to other shaped parts.

47. The method of any of the above claims, characterized in that at least two or three anticorrosion layers are applied in succession, of which each of these two or three layers is an AMENDED SHEET 2004 ~06- 2 9 anticorrosion layer selected from the group consisting of coatings based in each case on iron- cobalt, nickel-cobalt, at least one fluoride, at least one complex fluoride, an organic hydroxy compound, a phosphate, a phosphonate, a polymer, a rare earth compound, including lanthanum and yttrium compounds, a gsilane/siloxane, a silicate, cations of aluminum, magnesium and/or at least one transition metal selected from the group consisting of chromium, : : iron, hafnium, cobalt, manganese, molybdenum, nickel, titanium, tungsten, and zirconium, or is a coating based on nanoparticles, but it is also possible where appropriate for at least one further anticorrosion layer to be applied.

48. The method of any of the above claims, characterized in that the first anticorrosion layer is applied in a drying method and in that the second anticorrosion layer is applied in a drying method or rinse method.

49. The method of any of the above claims, characterized in that the first anticorrosion - ‘layer is applied by a rinse method and in that the second anticorrosion layer is applied by a drying method or rinse method.

50. The method of any of the above claims, characterized in that the second anticorrosion layer is applied in an after rinsing step.

51. The method of any of the above claims, characterized in that the second anticorrosion layer is applied in a drying method. AMENDED SHEET 2004 -06- 2 g

52. The method of any of the above claims, characterized in that surfaces of aluminum, iron, cobalt, copper, magnesium, nickel, titanium, tin or zinc or alloys comprising aluminum, iron, cobalt, copper, magnesium, nickel, titanium, tin and/or zinc are coated.

1.0

53. The method of any of the above claims, characterized in that coating is carried out with at least one liquid, solution or suspension which is substantially or entirely free from chromium compounds before coating with at least one paint and/or with at least one paintlike polymer- containing layer which comprises polymers, copolymers, crosspolymers, oligomers, phosphonates, silanes and/or siloxanes.

54. The method of any of the above claims, characterized in that no lead, cadmium, chromium, cobalt, copper and/or nickel is added to the - liquid, solution or suspension for the first and/or second anticorrosion layer.

55. The method of any of the above claims, characterized in that because of the at least one anticorrosion layer it is possible to forego at least one of the otherwise customary pretreatment layers, paint layers and/or paintlike polymer-containing layers.

56. The method of any of the above claims, characterized in that the liquid, solution or AMENDED SHEE: 2004 -06- 2g

: suspension for at least one of the anticorrosion layers and/or paintlike polymer-containing layers comprises, in addition to water, at least one organic film former with at least one water- soluble or water-dispersed polymer, copolymer, block copolymer, crosspolymer, monomer, oligomer, derivative (s) thereof, mixture thereof and/or addition copolymer thereof.

57. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers and/or paintlike polymer-containing layers , in addition to water, a total content of i5 : cations, tetrafluoro complexes and/or hexafluoro complexes of cations selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum, and boron and/or free or : otherwise-bound fluorine, from 0.1 to 15 g/L complex fluoride based on Fs.

58. The method of any of the above claims, characterized in that the liquid, solution and/or suspension for at least one of the anticorrosion layers and/or paintlike polymer-containing layers, in addition to water, a total content of free fluorine or fluorine not attached to tetrafluoro or hexafluoro complexes, . from 0.1 to 1000 mg/L calculated as free fluorine.

59. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- ‘containing layers comprises, in addition to water,

at least one inorganic compound in particle form having an average particle diameter, measured under a scanning electron microscope, in the range from 0.003 up to 1 pm diameter.

60. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers or paintlike polymer- containing layers at least one corrosion inhibitor selected from the group consisting of organic phosphate compounds, phosphonate compounds, organic morpholine and thio compounds, aluminates, manganates, titanates, and zirconates, preferably of alkylmorpholine complexes, organic Al, Mn, Ti and/or Zr compounds. _ 25

61. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion : layers, paint layers or paintlike polymer- containing layers comprises at least one compound AMENDED SHEE® 2004 -05- 2 g

C- 123 - for the neutralization of comparatively acidic : mixtures and/or for the corrosion control of . unprotected or damaged portions of the metallic surface. : .

62. The method of any of the above claims, characterized in that the liquid, solution or a suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers in addition to water comprises at least one silane and/or siloxane, calculated as silane, in an amount in the range from 0.1 to 50 g/L.

63. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers in addition to water and/or at least one organic solvent comprises at least one silane and/or siloxane, calculated as silane, in an amount in the range from 51 to 1300 g/L.

64. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion . layers, paint layers and/or paintlike polymer- containing layers where appropriate in addition to water and/or at least one organic solvent comprises at least one silane and/or siloxane, calculated as silane, | in an amount AMENDED SHED: 2004 -06- 2 9 in the range from 0.1 to 1600 g/L.

65. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises an organic film former : in the form of a solution, dispersion, emulsion; microemulsion and/or suspension.

66. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion

15 . layers, paint layers and/or paintlike polymer- containing layers comprises as organic film former at least one synthetic resin.

67. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises as organic film former a synthetic resin mixture and/or addition copolymer comprising synthetic resin based on acrylate, ethylene, urea-formaldehyde, polyester, polyurethane, styrene and/or styrene-butadiene : 35 and/or their derivatives, copolymers, crosspolymers, oligomers, polymers, mixtures and/or addition copolymers, from which an organic film is formed during or after the emission of water and other volatile constituents. AMENDED SHEE: 2004-06-29

68. The method of any of the above claims, characterized in that the liquid, solution Or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises as organic film former synthetic resins and/or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, polymers, mixtures and/or addition copolymers and/or their derivatives based on. acrylate, polyethyleneimine, polyurethane, poly- vinyl alcohol, polyvinylphenol, polyvinyl- pyrrolidine and/or polyaspartic acid.

69. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises a synthetic resin whose acid number is in the range from 5 to 250.

70. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises synthetic resins . and/or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, polymers, mixtures and/or addition copolymers and/or derivatives thereof whose molecular weights are in the range of at least 1000 u.

71. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- AMENDED SHE. 2004 -06- 29 containing layers comprises synthetic resins and/or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, polymers, mixtures and/or addition copolymers and/or derivatives thereof.

72. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises an organic film former whose pH in an aqueous formulation without addition of further compounds is in the range from 1 to 12,

73. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises an organic film former which contains only water-soluble synthetic resins and/or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, polymers, mixtures and/or addition copolymers and/or their derivatives.

74. The method of any of the above claims, characterized in that the liquid, ‘solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises an organic film former whose synthetic resin and/or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, polymers, mixtures and/or addition AMENDED SHEET 2004 -06- 2 9 copolymers and/or their derivatives contain carboxyl groups.

75. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises an organic film former in which the acid groups of the synthetic resins and/or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, polymers, mixtures and/or addition copolymers and/or their derivatives have been stabilized with ammonia, with amines, and/or with alkali metal compounds .

76. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises from 0.1 to 200 g/L of the organic film former.

77. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion : layers, paint layers and/or paintlike polymer- containing layers comprises from 100 to 2000 g/L of the organic film former.

78. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- AMENDED SHEET 2004 -05- 2 g containing layers include a monomer fraction.

79. The method of any of the above «claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises from 0.1 to 50 g/L of cations, tetrafluoro complexes and/or hexafluoro complexes of cations selected from the group consisting of titanium, Zirconium, hafnium, silicon, aluminum, and boron.

80. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises at least one organometallic compound. ]

81. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers includes at least one silane and/or siloxane calculated as silane in the aqueous composition, in a range from 0.2 to 40 g/L.

82. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises at least one partly AMENDED SHEET 2004 -05- 2 g hydrolyzed silane, at least one wholly hydrolyzed silane and/or at least one siloxane.

83. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises at least one partly hydrolyzed and/or nonhydrolyzed silane.

84. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises in each case at least one acyloxysilane, alkylsilane, aminosilane, bis- silyl-silane, epoxysilane, fluoroalkylsilane, glycidyloxysilane, isocyanatosilane, mercapto- silane, (meth)acrylatosilane, mono-silyl-silane, multi-silyl-silane, sulfur-containing silane, ureidosilane, vinylsilane and/or at least one corresponding siloxane.

85. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- : containing layers has added to it as inorganic compound in particle form a finely divided powder, a dispersion or a suspension.

86. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion AMENDED SHEET 2004 -06- 2 9

} layers, paint layers and/or paintlike polymer- containing layers has added to it as inorganic compound in particle form particles having an average size in the range of 4 nm to 150 nm.

87. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers has added to it as inorganic compound in particle form particles based on at least one compound of aluminum, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zinc and/or zirconium. ~~

88. The method of any of the above claims, characterized in that to the liquid, solution or suspension for at least one of the anticorrosion : 20 layers, paint layers and/or paintlike polymer- containing layers comprises from 0.1 to 300 g/L of the at least one inorganic compound in particle form.

89. The method of any of the above claims, characterized in that the liquid, solution or suspension is used . - ’ for at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers as organic solvent for the organic polymers at least one water-miscible and/or water-soluble alcohol, one glycol ether and/or one pyrrolidine and/or water; where a solvent mixture is used, it is a mixture of at least one long-chain alcohol, an ester alcohol, a glycol ether and/or butanediol with water. } AMENDED SHEET 2004 -06- 2g

90. The method of any of the above claims, characterized in that the liquid, solution OF . suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises organic solvent in an amount in the range from 0.1 to 10% by weight.

91. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises as lubricant at least one wax selected from the group consisting of paraffins, polyethylenes, and polypropylenes. -

92. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises a wax lubricant whose melting point is in the range from 40 to 160°C.

93. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises at least one rare earth element compound. AMENDED EHEZY 2004 -06- 29

S4. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises a rare earth element compound of an/or with cerium.

95. The method of any of the above claims, : characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- - containing layers comprises at least one oxidizing agent, at least one accelerator and/or at least one catalyst.

96. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers comprises at least one compound selected from the group of the mono-, bis-, and multi-silanes. AMENDED SHEET 2004 -06- 29 it being possible for the silanes in "each case to be present in hydrolyzed, partly hydrolyzed and/or nonhydrolyzed form in a solution, emulsion and/or suspension.

97. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers comprises at least one compound of the type XYZ, X*Y*Z* and/or X*Y*Z*Y*X+*, where Y is an organic group having 2 to 50 carbon atoms where X and Z, identical or different, are an OH, Ny SH, NH, NHR', CN, CH=CH;, OCN, CONHOH, COOR', acrylamide, epoxide, CH2=CR"-COO, COOH, HSO;, HSO,, AMENDED SHEET 2004 -06- 29

(OH) ;PO, (OH),P0C;, (OH) (OR')PO, (OH) (OR')PO,, SiH; and/or an Si (OH); group, where R' is an alkyl group having 1 to 4 carbon atoms, where R" 1s a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, where the groups X and Z are each attached to the group Y in the terminal position thereof, where Y* is an organic group having 1 to 30 carbon atoms, where X* and Z*, identical or different, are an OH, SH, NH;, NHR', CN, CH=CH,, OCN, CONHOH, COCR’, acrylamide, epoxide, CH,=CR"-COO, COOH, HSOi;, HSO,, (OH) ,PO, (OH),P0O;, (OH) (OR')PO, (OH) (OR')PO,;, SiHj, Si(OH)3;, >N-CH,-PO(OH), and/or an -N-[CH,-PO(CH).]2 group, where R' 1s an alkyl group having 1 to 4 carbon atoms, and where R" is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

98. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers comprises at least one compound of the type XYZ, where X 1s a COOH, HSO;, HSO,, (OH) ,PO, (OH) ,PO,, (OH) (OR')PO or (OH) (OR') PO; group, where Y is an organic group R containing 2 to 50 carbon atoms, of which at least 60% of these carbon atoms are present in the form of CH; groups, where Z is an OH, SH, NH, NHR', CN, CH=CH, OCN, epoxy, CH=CR"-COOH, acrylamide, COOH, (OH) LPO, (OH) ,PO,, (OH) (OR')PO or (OH) (OR') PO; group, where R' is an alkyl group having 1 to 4 carbon atoms, AMENDED SHEET 2004 -08- 2 g

~- 135 - and where R" is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

99. The method of any of the above claims, characterized in that the compound of type XYZ, X*Y*Z* and/or X*Y*Z*Y*X* is suitable for forming self-arranging molecules, which may shape a layer of these self-arranging molecules on the metallic surface.

100. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers comprises at least one of the following compounds of type XYZ, X*Y*Z* and/or X*Y*Z*Y*X*: 1-phosphonic acid-1l2-mercaptododecane, l-phosphonic acid-12- (N-ethylaminododecane) , 1-phosphonic acid-12-dodecene, p-xylylenediphosphonic acid, 1,10-decanediphosphonic acid, '1,12-dodecanediphosphonic acid, 1,14-tetradecanediphosphonic acid, 1-phosphoric acid-12-hydroxydodecane, 1-phosphoric acid-12- (N-ethylamino)dodecane, l-phosphoric acid-12-dodecene, 1l-phosphoric acid-12-mercaptododecane, 1,10-decanediphosphoric acid, 1,12-dodecanephosphoric acid, 1,1l4-tetradecanediphosphoric acid, : p,p'-biphenyldiphosphoric acid, l-phosphoric acid-1l2-acryloyldodecane, 1, 8-octanediphosphonic acid, 1, 6-hexanediphosphonic acid, 1, 4-butanediphosphonic acid, - 1,8-octanediphosphoric acid, AMENDED SHEET ~~ 2004 06- 2 g

1, 6-hexanediphosphoric acid, 1,4-butanediphosphoric acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid.

101. The method of any of the above claims, characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers and/or paintlike polymer- containing layers comprises phosphate and zinc, where appropriate also manganese, nickel and/or copper. .

102. The method of any of the above claims, characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers and/or paintlike polymer- containing layers contains from 0.2 to less than 50 g/L of zinc ions, from 0.5 to 45 g/L manganese ions, and from 2 to 300 g/L phosphate ions, calculated as P,0s.

103. The method of any of the above claims, - characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers and/or paintlike polymer- containing layers comprises phosphate, where : appropriate with nickel content.

104. The method - of any of the above claims, characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers comprises AMENDED SHEET 2004 -06- 29 phosphate, fluoride, tetrafluoride and/or hexa- fluoride.

105. The method of any of the above claims, characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers may comprise phosphonate, tetrafluoride and/or hexafluoride.

106. The method of any of the above claims, : characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers comprises an organic film former, fluoride, tetrafluoride, hexafluoride and/or at least one inorganic compound in particle form, and, where appropriate, at least one silane.

107. The method of any of the above claims, characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers comprises an additive selected from the group consisting of organic binders, biocides, defoamers, corrosion inhibitors, adhesion promoters, wetting agents, . photoinitiators, and polymerization inhibitors.

108. The method of any of the above claims, characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers comprises at least one filler and/or one pigment. AMENDED SHEET 2004 -06- 29

105. The method of any of the above claims, characterized in that prior to the application of an anticorrosion layer, paint layer and/or paintlike polymer-containing layer, an activating treatment is applied.

110. The method of any of the above claims, characterized in that the application of an anticorrosion layer, paint layer or paintlike polymer-containing layer may be followed by application of an afterrinse and/or passivation. i5 :

111. The method of any of the above claims, characterized in that at least one of the liquids, solutions or suspensions for at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers comprises an organic film former which, following application to the metallic substrate, is cured by heat and/or actinic radiation. }

112. The method of any of the above claims, characterized in that at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers may be only partly cured prior to adhesive bonding, welding, and/or forming and not fully cured until after adhesive bonding, welding and/or forming, the first curing before adhesive bonding, welding and/or forming taking place by actinic radiation and the second curing taking place after adhesive bonding, welding and/or forming. AMENDED SHEET 2004 -06- 29

113. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer Co containing layers has a pH in the range from 0.5 to 12.

114. The method of any of the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers is applied to the respective surface at a temperature in the range from 5 to o5°C.

115. The method of any of the above claims, characterized in that the substrate and/or the respective surface are held during application of the anticorrosion layer (s) at temperatures in the range from 5 to 120°C.

116. The method of any of the above claims, characterized in that the coated metallic surface in this case is dried at a temperature in the range from 20 to 400°C PMT (peak metal temperature) .

117. The method of any of the above claims, characterized in that the coated strips are cut up or wound to a coil, where appropriate after cooling to a temperature in the ‘range from 10 to . 70°C.

118. The method of any of the above claims, characterized in that the divided strips, after pressing, cutting and/or punching, are coated in the edge region with a temporarily applied coating to be removed again or with a permanently AMENDED SHEET 2004 <06- 29 protecting coating.

119. The method of any of . the above claims, characterized in that the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer- containing layers is applied by rolling, flowcoating, knifecoating, spraying, squirting, brushing or dipping and, where appropriate, by subsequent squeezing off with a roll.

120. The method of any of the above claims, characterized in that the coating applied in each case with the liquid, solution or suspension for at least one of the anticorrosion layers, paint layers and/or paintlike polymer-containing layers is adjusted to a layer weight in the range from

0.0005 mg/m* to 150 g/m.

121. The method of any of the above claims, characterized in that to the partly or fully cured film there is applied in each case at least one coating of paint or of a paintlike, polymer- containing coating to the partly or fully cured film, the first paint layer or paintlike polymer- containing layer may consist essentially of primer, a thinly (i.e., in the range from 0.1 to 10 pm) applied, organic-polymer-containing - material, a reaction primer, a shop primer or a wash primer.

122. The method of any of the above claims, characterized in that at least one coating of paint, a mixture of or with polymers, varnish, AMENDED SHEET 2004 -06- 29 adhesive and/or adhesive backing to the at least partly painted strip or the strip at least partly coated in a paintlike manner with a polymer- containing layer, or to the at least partly : painted strip section or the strip section coated at least partly in a paintlike manner with a polymer-containing layer is applied.

123. The method of any of the above «claims, characterized in that the clean or cleaned and, where appropriate, activated metallic surface is contacted with the liquid, solution or suspension for one of the anticorrosion layers and at least one film, which where appropriate may also contain particles, may be formed on the metallic surface, which is subsequently dried and, where appropriate, additionally cured, the dried and, where appropriate, also cured film possibly having in each case a thickness in the range from 0.01 to 100 pm. AMENDED SHEET 2004 -06- 29

OZ 00898

124. The method of any of the above claims, characterized in that at least one paint layer as undercoat or one paintlike polymer-containing layer as pretreatment primer, primer, primer as replacement of the cathodic dip coat, lubricating primer, reaction primer, welding primer wash primer, clearcoat and/or topcoat, where appropriate instead of an undercoat is applied.

125. The method of any of the above claims, : characterized in that at least one of the paint layers and/or paintlike polymer-containing layers is cured by heat and/or actinic radiation. :

126. The method of any of the above «claims, characterized in that the coated strips or strip sections are formed, painted, coated with polymers, printed, bonded, hot : 20 soldered, welded and/or joined with one another or with other elements by clinching or other joining techniques.

127. An aqueous composition for pretreating a metallic surface prior to a further coating or for treating that surface, characterized in that the composition comprises in addition to water a) at least one organic film former which comprises at least one water-soluble or water- dispersed polymer having an acid number in the range from 5 to 200, b) at least one inorganic compound in particle form having an average particle diameter, measured AMENDED SHEET AMENDED SHEET 2004 -06- 2.9

. 0zZ 00898 under a scanning electron microscope, in the range from 0.005 up to 0.3 pm diameter, c) at least one lubricant and d) if desired, at least one corrosion inhibitor, e) if desired, at least one organic solvent, f) if desired, at least one silane and/or siloxane, calculated as silane, © g) if desired, at least one crosslinking agent, especially based on a basic compound, and h) if desired, at least one chromium(VI) compound.

128. Use of the substrates coated by the method of at least one of above claims 1 to 126, characterized in that the substrate to be coated is wire winding, wire mesh, steel strip, metal sheet, paneling, shield, vehicle body or part of a vehicle body, part of a vehicle, trailer, recreational vehicle or missile, cover, casing, lamp, light, traffic light element, furniture item or furniture element, an element of a household appliance, frame, profile, molding of complex geometry, guideboard element, radiator element or fencing element, bumper, part of or with at least one pipe and/or profile, window frame, door frame or cycle frame, or a small part, AMENDED SHEET AMENDED SHEET 2004 -06- 2 9

) 0Z 00898 = 144 -

129. The use of the products produced by the method of at least one of claims 1 to 126 in vehicle construction, for producing components or bodywork parts or premounted elements in the vehicle, air travel or space travel industry; as metal sheet, paneling, bodywork or part of a bodywork, as part of a vehicle, trailer, recreational vehicle or missile, as a cover, profile, shaped part of complex geometry, bumper, part of or with at least one pipe and/or profile.

130. A method of coating a metallic strip, the strip, or strip sections produced from it according to claim 1, substantially as herein described with reference to any one of the inventive examples. AMENDED SHEET AMENDED SHEET 2004 -06- 2 9