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    • 专利摘要:
    process for coating metal surfaces with a coating agent containing polymer, the coating agent and use thereof. the invention relates to a process for coating metal surfaces with an aqueous composition as a solution or as a dispersion, in which the composition contains a) at least one phosphate, b) at least 0.1 g / l of at least one compound titanium and / or zinc, c) at least one complexing agent, d) aluminum, chromium (iii) and / or zinc cations and / or at least one compound with an aluminum, chromium (iii) and / or zinc, as well as e) up to 500 g / l of at least one acid-tolerant, organic cationic or non-ionic polymer / copolymer, with respect to the content of the solids and active substances in these additives.
    公开号:BR112013005656B1
    申请号:R112013005656-8
    申请日:2011-09-08
    公开日:2020-05-26
    发明作者:Mike Krüger；Petra Grünberg；Mark Andre Schneider；Heribert Domes
    申请人:Chemetall Gmbh；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report for METAL SURFACE COATING PROCESS, WATER COMPOSITION, COATING, AND USE OF THE SAME.
    The present invention relates to a process for coating metal surfaces with an aqueous composition, which differs from phosphate solutions, the composition containing cationic and non-ionic organic polymer / copolymer, acid tolerant, and the use of coated metal substrates using the process according to the invention.
    DE 102008000600 A1 describes a process for coating metal surfaces with a passivating agent, without specifically mentioning the content of certain organic polymers / copolymers, of the passivating agent, and the use thereof. However, the examples do not mention any organic polymer / copolymer content.
    In the description below, the terms "passivating agent", "composition" and "passivation process" are reserved for aqueous compositions and the process of the present patent application, although in many cases, aqueous compositions and the method are not used for passivation, but, instead, for the purpose of an organic coating, such as an organic coating, which can be formed as a so-called dry lube.
    Phosphate coatings are widely used as corrosion protection layers, as a molding aid and as an adherent surface for varnishes and other coatings. In particular, when they are used as a protective layer for a limited period of time, especially storage, and then varnished, for example, they are referred to as a “pretreatment layer” before varnishing. However, if no coat of varnish or other type of organic coating is applied to the phosphate coating, this is called "treatment" or "passivation", rather than "pretreatment". These coatings are also designated as conversion layers, when at least one cation of the metallic metal surface, that is, of the surface of partPetition 870190063443, of 07/08/2019, p. 10/65
    2/78 te metallic, is leached and used for the layered structure.
    In coating methods without subsequent washing, particularly after a conversion coating, so-called drying processes (“processes without washing”) are of considerable importance, especially for the rapid coating of continuously conveyed strips made of at least one metallic material . These strips can be sheets with narrow widths or very large. A phosphate coating is applied to these strips, usually directly after galvanizing, but optionally also by appropriate cleaning or degreasing and after washing with water or an aqueous medium, and optionally after activation of the metal surface by moisten with a phosphate solution, and the strips are dried. Strips can be damaged by washing after the phosphate coating has dried, particularly if the phosphate coating is non-crystalline or only partially crystalline.
    In the past, these problems were treated on a commercial scale by adding nickel to the phosphating solution, so that the phosphating solution had a nickel content ranging from 0.5 to 1.5 g / l. For zinc-manganese-nickel phosphating, the zinc content was normally selected to be in the range of 0.6 to 3.5 g / l, and the manganese content in the range of 0.4 to 2.5 g / l l.
    However, high quality phosphate solutions and phosphate layers have a significant content of zinc, manganese and nickel. Nickel, in particular, should be avoided, due to its toxicity and harmful effects. In addition, the inevitable heavy metal content has an adverse impact on wastewater, phosphate sludge and grinding powder. However, there is no process available for treating strips that ensures high protection against uncovered corrosion (protection against corrosion in the absence of layers of varnish / base paint), particularly for metallic surfaces rich in zinc.
    Despite the comparatively high phosphate content of the unmodified inorganic passivating agent in document DE102008000600 A1,
    3/78 the compositions are not phosphating solutions, and the coating process is not phosphating, since a phosphating solution:
    1. For high-quality phosphate layers, for example, for phosphating processes, rich in zinc and / or manganese, before activation, for example, based on titanium phosphate particles or zinc phosphate particles, it is necessary to enable the formation of a high quality phosphate layer;
    2. In general, only a pH range of 2 to 3.5 can be used in phosphating operations containing zinc;
    3. A total content of titanium and / or zirconium compounds greater than 0.05 g / l or greater than 0.1 g / l, is generally not tolerable, without adverse effects, since it is known that compounds of titanium and zirconium for phosphating are bath contaminants;
    4. In practice, there is never a significant content of silanes / silanois / siloxanes / polysiloxanes;
    5. A low content of a complexing agent is rarely present, since complexing agents are sometimes considered to be bath contaminants;
    6. A total content of cations in the range of 3.5 to 9.5 g / l, and compounds containing phosphorus, in the range of 5 to 20 g / l, calculated as PO 4 , are generally present in bath solutions;
    7. A high content of alkali and ammonium compounds is often present, with the pH generally being in the range of 2.0 to 3.5, even for comparatively high levels of ammonium compounds;
    8. For a content of at least one complex fluoride, normally only complex fluoride based compounds of boron and / or silicon are present;
    9. For phosphating parts using a phosphating solution rich in zinc and / or manganese, crystalline layers are typically formed with typical crystal shapes, at least for the treatment of individual parts, for example, by immersion and / or spraying; and
    10. For the protection of exposed corrosion, the surfaces
    4/78 zinc-phosphate crystals withstand a salt spray test on non-varnished, phosphated surfaces, typically only up to two hours without rust formation, due to pores and lack of cohesiveness, while coatings according to the invention normally resist in a salt spray test for at least two days, without any additional coating treatment, without the coatings according to the invention being thicker than comparable phosphate coatings.
    When, in very rare cases, a titanium and / or zinc compound is used in a phosphating solution for a phosphating process, the total content of these compounds is typically less than 0.2 g / l. This is due to the fact that it is known that higher levels of these compounds usually result in defective coatings, particularly on aluminum-rich surfaces. It is very unusual to add a complexing agent and / or an organic polymer / copolymer to a phosphate solution. When, in very rare cases, a silane is used in a phosphating solution for a phosphating process, the content is very low. But, a combination of these mentioned additives is never used in phosphating.
    DE 102008000600 A1 A1 and the properties of their coatings are constantly being observed that the behavior of aqueous inorganic, unmodified compositions (ie aqueous compositions, which do not contain polymers and / or organic copolymers and which remain stable for weeks) so different from the phosphating solutions and the phosphate layers therefrom, that the aqueous compositions according to the invention and their coating methods cannot be designated as phosphating. However, the method according to the invention can be a conversion coating method of the first type.
    Patent applications DE 102008000600.9 and PCT / EP2009 / 05267 relating to chemically similar passivating agents and passivation methods, as well as the corresponding foreign applications
    5/78 correspondingly, are hereby incorporated explicitly for reference, particularly with respect to aqueous compositions, additions to aqueous compositions, coating steps, bath characteristics, layer formation, layer properties and the determined effects , particularly, for the exemplified modalities and comparative examples. Similarly, patent applications on which the priority is based are explicitly incorporated by reference in subsequent applications.
    But for passivating agents without a high quality organic polymer / copolymer content, the dry film that is formed often does not have sufficient moisture resistance after application and drying. In particular, resistance to moisture immediately after drying is not suitable for a large number of uses of the treated substrate surfaces.
    This problem can be solved by selecting and adding an appropriate polymer system. In addition, in this way, the corrosion resistance of the treated substrate surfaces can be greatly increased, the additional processing for molded parts can be improved, without additional lubricants, such as greases and oils, and the ability to overcoat using various coating systems. can be vastly improved.
    It has been found that almost all organic polymers and copolymers, which can be mixed in the passivating agent of DE 102008000600 A1, result in precipitation, particularly of polymer particles, so that the modified passivating agent can no longer be used. This is due to the fact that the vast majority of polymers and copolymers currently in common use are not stable in dispersions, emulsions and / or strongly acidic solutions. This precipitation results in inhomogeneous dry files, which cannot be sufficiently formed for films or are not sufficiently formed for films. The properties of films are therefore different and not as satisfactory as films with appropriate film-forming characteristics. In addition, the films,
    6/78 therefore, they are often no longer transparent, although for many applications transparent films are required. It has been shown that all tested types of anionic organic polymers / copolymers, unmodified, are unstable in an acidic medium and therefore cannot be used according to the invention. In addition, many of the cationic organic polymers / copolymers have proven to be unstable in an acidic environment.
    Surprisingly, it has now been discovered that a stable composition, which is modified according to the invention, makes it possible for the surface appearance of the substrate to remain discernible with virtually no change. Thus, for example, the granular structure can be easily visible through the coating according to the invention.
    It has also been found that organic polymers and copolymers, which are mixed in the passivating agent of DE 102008000600 A1 and do not result in precipitation, significantly improve the properties of the coating formed in this way, compared to the properties of the polymer-free coating and organic copolymers. In addition, it has been found that individually selected organic polymers and copolymers enhance the properties and the spectrum of properties to such an extent that the application areas of substrates coated in this way are significantly expanded.
    Surprisingly, it has been found that a comparatively small addition of a polyurethane-rich cationic dispersion, with a polycarbonate content and / or an acid-tolerant dispersion, based on acrylate and / or styrene, which is / are present in stable form in the aqueous composition, it results in a different spectrum of properties, much better, than an unmodified passivation agent, only on the basis of components a) to d), as shown schematically in Figures 1 and 2. However, in these figures it is not the element and the content of compound that are selectively related to each other, but, in fact, the relationships of inorganic passivating agent to polymers / copolymers, together with their additives, such as, for example, wax. However, the trends indicated in the figures are a function of the specific composition and thickness
    7/78 layer.
    By adding a cationic polyurethane dispersion, results of particularly high quality are shown, when compared with an unmodified passivation agent, based only on components a) to d), in the salt spray test according to DIN EN ISO 9727, in the constant humidity test by condensation water according to DIN EN ISSO 6270-2 CH, in the anti-fingerprint properties, which are tested by immersing the treated substrate surfaces in a synthetic hand perspiration solution, with appropriate evaluation by colorimetry, compared to an untreated sample, in the ability to overcoat, in the sliding behavior, in the wet stacking test (one of the corrosion tests) and in the resistance to cleaning agents, refrigerants, ethanol and deionized water.
    Within the meaning of the present patent application, “passivation” means the coating of the substrate surface with specialized inorganic and / or organic compositions, which can be applied to dry films in quantities that are often less than 1 g / m 2 , which, in particular, prevent oxidation of the substrate surface. Often, but not always, no subsequent organic coating is applied for permanent anti-corrosion protection, since the corrosion resistance of the passivation coating, in many cases, is only temporary in nature, and is sufficient for storage, transport or processing of the component coated with the passivating agent. However, in some cases, passivation does not exclude the subsequent application of at least one organic coating, such as a base paint, for example, or even a system of varnish and / or an adhesive.
    The object, therefore, is to propose a coating method by means of which the corrosion protection layer produced using an aqueous composition, particularly also without subsequently coating with a base varnish / paint, has good corrosion protection (protection against exposed corrosion), particularly on a metal strip. The goal is for a roll (strip roll) to be processable, typically,
    8/78 by the steel producer during subsequent processing operations, without rust attack.
    In addition, for some embodiments, good molding ability and / or good alkali resistance during moderate alkaline cleaning and / or during molding, using alkaline and / or acidic cooling lubricants, is / are advantageous. Optionally, another objective is so that the coating also preferably has, after molding, good protection against corrosion and, preferably, also good adhesion of the varnish. Another objective is that the layer has so-called anti-fingerprint properties.
    The object is obtained by a method to coat metal surfaces, using an aqueous composition as a solution or as a dispersion, in which the composition contains:
    a) at least 1 g / l phosphate, calculated as PO 4 ,
    b) at least 0.1 g / l of at least one titanium and / or zirconium compound, calculated as Ti metal,
    c) at least 0.1 g / l of at least one complexing agent,
    d) at least 0.5 g / l of aluminum, chromium (lll) and / or zinc cations, and / or at least one compound containing aluminum, chromium (lll) and / or zinc, and
    e) 1a 500 g / l of at least one cationic or non-ionic organic polymer / copolymer, acid-tolerant, in relation to the content of solids and active substances in the additives to the organic polymer / copolymer.
    Organic, cationic and non-ionic polymers / copolymers are inherently acid tolerant. Anionic polymers / copolymers can be modified to become acid tolerant, for example by adding the salt of a strong acid. The organic polymer / copolymer, cationic or non-ionic, acid-tolerant, can be present as an individual additive or as a mixture of individual additives, or also present in the (total) mixture of e) and / or in the aqueous composition, in each case, as a dispersion, solution, or colloidal solution, emulsion and / or dispersion. The least
    9/78 an organic polymer / copolymer, cationic or non-ionic, tolerant to acids, is preferably stable in the aqueous composition within the scope of acidic and / or neutral pH for at least five days. All organic polymers / copolymers are advantageously stable in the range of strongly acidic pH, or optionally also in the range of weakly acidic and / or neutral pH, particularly at a pH in the range of 1 to 6, 2 to 5 or 3 to 4 Each additive can be cationic, non-ionic or acid-tolerant anionic.
    In this context, a wet film of the aqueous composition can be applied, preferably, to strips or metal sheets and dried.
    Within the meaning of the present patent application, "active substances" refers to the content of substances, including solvents and ions, that take part in chemical reactions in the aqueous composition, and in chemical reactions to form the dried coating and, optionally, also partially or completely hardened.
    An individual additive for e, a mixture of individual additives for e), and / or the (total) mixture of e) can have a) a minimum film-forming temperature, preferably within the range of -20 to + 100 ° C, within the range of 0 to + 80 ° C, or within the range of +20 to + 60 ° C, or the film formed in this way may have b) a transformation temperature T g preferably, within the range of -10 to + 120 ° C, within the range of +10 to + 100 ° C, or within the range of +30 to + 80 ° C, and / or c) a hardness using the Kõnig pendulum, preferably within the range of 10 to 140 s, within 30 to 120 s, or within 50 to 100 s. The organic polymer / copolymer e) preferably has a minimum MFT film forming temperature in the range of -20 to + 100 ° C, or the resulting film preferably has a transformation temperature T g in the range of - 10 to + 120 ° C and / or a Kõnig pendulum hardness within 10 to 140 s.
    Within the meaning of this patent application, the terms "additive" or add mean that that substance or mixture of substances is added, intentionally, at least once.
    The content of at least one organic polymer / copolymer, cationic or non-ionic, tolerant to acids e) in the aqueous composition, in relation to
    10/78 to the content of solids and active substances in these additives is preferably within the range of 8 to 400 g / L, 15 to 320 g / L, 25 to 280 g / L, 40 to 240 g / L, 60 to 200 g / L, 80 to 180 g / L, 100 to 160 g / L, or 120 to 140 g / L.
    The organic polymer / copolymer e) particularly preferably contains a cationic polyurethane resin and / or a modified anionic acrylate and is therefore acid tolerant. The aqueous composition according to the invention advantageously contains, in addition to at least one stable, cationic polyurethane resin, at least one acid-tolerant, organic, cationic or non-ionic polymer / copolymer, which is stable in the composition. The content of the aqueous composition of organic polymer / copolymer, based on and / or with a content of poly (meth) acrylate, polyacrylamide, polycarbonate, polyepoxide, polyester, polyether, polyethylene, polystyrene, polyurethane, polyvinyl. polyvinylpyrrolidone and / or modifications thereof, particularly in the range of 1 to 500 g / l, 8 to 400 g / l, 15 to 320 g / l, 25 to 280 g / l, 40 to 240 g / l, 60 to 200 g / l, 80 to 180 g / l, 100 to 160 g / l or 120 to 140 g / l, based on the content of solids and active substances.
    The films produced according to the invention are usually clear, dry or at least dried and oil-free inorganic organic coatings, with a layer thickness, preferably within the range of 0.1 to 20 µm. 1 to 10 μιτι, or rarely, 0.1 to 50 m. The films have excellent protection against corrosion, particularly during transport, taming and additional treatment. Typically, they form a dry film with sliding properties, whereby the substrate which is treated according to the invention can be processed and molded, for example, in molded components, without subsequent coating with additional lubricants. These films typically have good resistance to atmospheric action and are resistant to moderately alkaline cleaning processes. The films can be used as a pretreatment, before varnishing or additional coating with organic compositions, such as an adhesive. When drying is carried out at temperatures within the range of 60 to 120 ° C of peak metal temperature (PMT), for example, a separate heat treatment for hardening can be
    11/78 optionally dispensed for low temperature hardening resins, which are based, for example, on a catalytic polyurethane resin, and used according to the invention. In particular, the resistance of the dried film to various chemicals, for example, alcohols, ketones and acid or alkaline reaction media, can be improved by adding hardeners, crosslinkers, polymerization initiators etc., such as those based on aziridine, resin from melamine formaldehyde, and blocked isocyanate, for example. However, in most cases, the addition of melamine formaldehyde resin and / or blocked isocyanate requires additional drying and / or heating at PMT higher than 120LjC.
    The compositions according to the invention represent an organic-inorganic hybrid system. At the same time, they have the properties of an acid passivating agent and a base paint.
    In principle, the weight ratio of the inorganic passivating agent based on a) through d) to the organic polymer components e) can be varied over wide limits.
    Weight-based ratios [a) to d)]: [e) + f)] can preferably be adjusted within the range of 20: 1 to 1:30, particularly within the range of 10: 1 to 1:20, particularly preferably, in the range of 6: 1 to 1:10 or 4: 1 to 1: 8, and most preferably, in the range of 2: 1 to 1: 6, 1.5: 1 to 1: 54. or 1: 1 to 1: 3, most preferably, approximately 1: 2, for example, particularly, for aqueous compositions and for the dry films produced therefrom.
    The aqueous composition according to the invention preferably has a weight ratio of polymer / organic copolymers e) to the inorganic passivating agent based on a) to d) in the range of 8: 1 to 0.2: 1 or 6 : 1 to 0.8: 1. Particularly preferred for aqueous compositions and dry films produced therefrom are a weight ratio of organic, cationic or non-ionic, acid-tolerant polymers / copolymers e) to the inorganic passivating agent based on a) through d) within the scope from 5: 1 to 0.3: 1, particularly preferably, in the range of 3.5: 1 to 0.8: 1 or 2.5: 1 to 1.2: 1; Organic polymers / copolymers e) are preferably copolymers.
    Hydrophilic cationic groups are preferably incorporated into the main chain and / or the side chains of the cationic polyurethane resin by means of at least one amine, particularly by means of at least one alkanolamine, such as, for example, an N- alkyldialcanolamine. Quaternary ammonium groups are preferably incorporated into the main chain of cationic polyurethane resin. These groups may optionally have acidic groups such as anionic counterions and / or quaternizing agent groups, which are formed, for example, when acetic acid and / or phosphoric acid, for example, is / are used as acid, and / or dibutyl sulfate and / or benzyl chloride, for example, is / are used as a quaternizing agent. When acid and / or quaternizing agent is / are added to the aqueous composition, which contains cationic polyurethane resin, for example, anionic counterions are preferably incorporated in the quaternary ammonium groups, for example, in the main resin chain of cationic polyurethane. Structural units with at least one group containing silicon and / or at least one epoxy group, are preferably incorporated into the cationic polyurethane resin. The cationic polyurethane resin preferably contains additives, for example, at least one preservative, at least at least one emulsifier, at least one metal salt, such as a magnesium salt and / or at least one organic solvent, for example, at least one solvent based on pyrrolidone, for example, polyvinylpyrrolidone and / or N-methylpyrrolidone. The compatibility of cationic polyurethane resin, for example, with the unmodified inorganic passivating agent, may possibly be due to the presence of amino groups in the main chain, on the one hand, and the presence of counterions, such as PO 4 3 ', on the other hand.
    The selection of specific organic (co) polymer components also depends on the properties of the desired coating. If a given water solubility of the coating produced is adequate, organic (non) ionic (co) polymers may be sufficient for e). If particularly high quality properties are desired, organic, cationic (co) polymers are particularly recommended for e). Powder
    However, these (co) polymers are often also expensive, due to their complicated synthesis. On the other hand, the water solubility of the coating according to the invention can also be greatly reduced by adding a crosslinker, for example, based on aziridine or diimide, or by adding a silane, silanol, siloxane and / or polysiloxane and / or through the sol-gel bridge of organic polymers and inorganic particles.
    In many embodiments, a prerequisite for the use of, for example, a cationic polyurethane resin and / or acid-tolerant, organic, cationic or non-ionic polymers / polymers in the aqueous composition is its suitability for comparatively low pH levels , for example, at a pH in the range of 2 to 3, and preventing precipitation in the aqueous composition for at least five days, or four weeks, and preferably several months (long-term stability). Complexing agents are usually necessary to enable the use of the inorganic preparation as a stable solution. The pH of the aqueous compositions according to the invention is preferably in the range of 0.5 to 7, particularly preferably in the range of 1 to 5.5 or 1.5 to 4 or 2 to 3.5. In some embodiments, the pH can also be taken to a weakly acidic or neutral level, due to the content of complexing agent and, optionally, other components.
    The coating according to the invention, based on cationic polyurethane resin, for example, preferably offers a high water resistance and a high level of adhesion for the subsequent coating. In some variants of modality, these high quality properties result only after a latency period of approximately one hour, or approximately one day, after coating. In addition, it is preferable that this coating has a mechanical strength, which is comparatively high for these thin coatings, high transparency or turbidity, a readiness to accept white and / or colored pigments, and chemical resistance increases for organic solvents, alkaline chemicals and / or acidic, and / or water, for example. Adding carbon black proved to be particularly satisfactory for
    14/78 produce gray or black coatings.
    In addition, in many embodiments, the composition according to the invention may contain, in addition to or as an alternative to at least one cationic polyurethane resin, at least one other acid-tolerant, organic cationic or non-ionic polymer / copolymer , in this context "stability" means that there is no precipitation in the composition according to the invention for a very long period of time, particularly for at least 5 or 20 days, or even for at least 4 weeks. It is often preferable that the aqueous composition contains at least one acid-tolerant, organic, cationic or non-ionic polymer / copolymer, which is based on and / or has a (meth) acrylate, acrylamide, polycarbonate, epoxy resin content, ethylene oxide, polyester, polyether, styrene, urethane, vinyl, and / or vinylpyrrolidone, and that, alone and / or in a mixture e) of them is stable in acidic or, optionally, also in neutral medium. This means that precipitation does not occur during incorporation into the composition or even after a period of time, for example, after five days. The aqueous composition preferably contains at least one organic polymer / copolymer, which is based on and / or has a (meth) acrylate, acrylamide, polycarbonate content, epoxy resin, ethylene oxide, polyester, polyether, styrene, urethane , vinyl, and / or vinylpyrrolidone, and which is stable in an acidic and / or neutral medium and does not result in precipitation.
    The content of methacrylate, acrylamide, polycarbonate, epoxy resin, ethylene oxide, polyester, polyether, styrene, urethane, vinyl, and / or vinylpyrrolidone in the modified passivating agent can preferably be in the range of 1 to 500 g / l, particularly preferably, within the range of 8 to 420 g / l, 25 to 340 g / l, 30 to 280 g / l, 60 to 220 g / l, 80 to 180 g / l, or 100 to 140 g / l. The weight ratio of cationic polyurethane resin, which optionally can also be a copolymer and can comprise more than 50% by weight of polyurethane, for the sum of methacrylate, acrylamide, polycarbonate, epoxy resin, ethylene oxide, polyester, polyether , styrene, urethane, vinyl, and / or vinylpyrrolidone, which are not bonded to a cationic polyurethane resin
    15/78 onica during the addition, including cationic polyurethane resin, is preferably in the range of at least 30 °%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80 %, at least 90% or approximately, 100%. The weight ratio of polyurethane to the sum of methacrylate, acrylamide, polycarbonate, epoxy resin, ethylene oxide, polyester, polyether, styrene, urethane, vinyl, and / or vinylpyrrolidone is preferably within the scope of at least 30% at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90% or approximately 100%.
    Alternatively or additionally, the composition according to the invention may contain a water-soluble or water-dilutable, cationic, acid-tolerant epoxy resin with amino groups and, optionally, may also contain phosphate groups. In addition, contents of the acid-tolerant cationic copolymer, based on polyester-polyurethane, polyester-polyurethane-poly (meth) acrylate, polycarbonate-polyurethane, polyester-polyurethane-poly (meth) acrylate, polycarbonate-polyurethane, and / or polycarbonate- polyurethane-poly (meth) acrylate, particularly as dispersions, have been shown to be advantageous additives in the aqueous composition. Therefore, it is preferable that the composition contains acid-tolerant cationic copolymer, based on polyester polyurethane, polyester-polyurethane-poly (meth) acrylate, polycarbonate-polyurethane, polyester-polyurethane-poly- (meth) acrylate, polycarbonate-polyurethane, and / or polycarbonate-polyurethane-poly (meth) acrylate, and / or based on water-soluble, or water-dilutable, cationic, acid-tolerant epoxy resin. All of the above-mentioned organic polymers / copolymers are preferably the only additives added to the passivating agent. The methacrylate / and / or acrylate content, particularly as acid-tolerant (meth) acrylate containing copolymers, in the aqueous composition is preferably in the range of 2 to 300 g / l, particularly preferably in the range of 5 to 220 g / l, 30 to 180 g / l, 60 to 150 g / l or 90 to 120 g / l. The acrylate and / or methacrylate part of the copolymers can, in particular, be from 1 to 60% by weight, 5 to 50% by weight, or 10 to 35% by weight, of the copolymers. The acid-tolerant (meth) acrylate added preferably contains phosphonate and / or sulfonate groups.
    16/78
    The content of organic polymers and copolymers is taken into account as added compounds, including their additives, in a compound form, in which these compounds are often obtained commercially, or produced in a form that is not processable until added to the modified passivation, and the content of acid-tolerant organic polymers and copolymers in these products is preferably at least 95% by weight of the solids and active substances contained in these products.
    The aqueous composition according to the invention is usually a colloidal dispersion or solution. The proportion of cationic polyurethane resin and, optionally, other acid-tolerant dispersions, colloidal solutions and powders, may possibly be so low compared to the dissolved components that the character of the dispersion is difficult to discern.
    The composition according to the invention preferably contains at least one lubricant f). The composition according to the invention preferably contains at least one additive (g), such as, for example, in each case, a wetting agent, a demulsifier, an emulsifier, an anti-foaming agent, a film-forming agent, a corrosion inhibitor and / or a UV absorber. Additives that improve wetting, limit foaming and allow the formation of the coating film are selected and preferably added to the passivating agent. The coating is preferably made into a film after application, particularly during drying.
    In the method according to the invention, at least one wax selected from the group consisting of paraffins, polyethylenes and polypropylenes and added to the aqueous composition, particularly at least one oxidized wax and / or at least one microcrystalline wax, can be used as a lubricant f ), which can sometimes also be used as a molding agent. Lubricants are preferably completely or substantially free of halogens, such as, for example, fluoride. It is particularly advantageous to use the wax as an aqueous dispersion and / or as a
    17/78 dispersion stabilized cationically, anionically and / or sterically, since afterwards it can be easily maintained in a homogeneous distribution in the aqueous composition. The melting point of the wax used as a lubricant is preferably within the range of 40 to 165 ° C, particularly preferably within the range of 50 to 160 ° C, particularly within the range of 100 to 165 ° C or within the range of 120 to 150 ° C.
    The addition of an oxidized polyethylene, with a melting point in the range of 100 to 150 ° C, is particularly preferred. This lubricant can be present, for example, in a catholic stabilized form in water, but it can also contain emulsifiers.
    It is particularly advantageous to also add to a lubricant with a melting point in the range of 100 to 165 ° C a lubricant with a melting point in the range of 45 to 95 ° C, particularly in quantities of 2 to 30% by weight, De preferably 5 to 20% by weight of the total solids content, that is, in relation to solids that include active substances, for example, at least one polyethylene wax and at least one paraffin. The latter can also be advantageously used alone as an independent lubricant. The weight ratio of the lubricant with the highest melting point to the lubricant with the lowest melting point is preferably 2: 1 to 1: 2, particularly preferably 3: 2 to 2: 3, 4 : 3 to 3: 4 or, practically or exactly, 1: 1.
    The at least one lubricant, which at the same time can also optionally be a molding agent, is preferably present in a content of approximately zero or in the range of 0.5 to 80 g / l, 0.8 to 65 g / l, or 1 to 50 g / l, for solids that include active substances, and, particularly preferably, in a range of 1.5 to 40 g / l, 2 to 0 g / l, 2 , 5 to 24 g / l, 3 to 18 g / l, or 6 to 12 g / l in the aqueous composition. Even for a high wax content, in many embodiments a coating can have a configuration with good overcoating ability. A lubricant and / or molding agent can be added to reduce the friction coefficient of the coating, particularly during molding. Paraffin, polyethylene and / or oxidized polyethylene, among others, are recommended18 / 78 for this purpose.
    The weight ratio of the content of the organic, acid-tolerant polymers / copolymers e) to the lubricant content f) in the aqueous composition, particularly in the bath, and in the dry film can vary over a wide range. This ratio is preferably in the range of 100: 12 to 100: 0.1, 100: 9 to 100: 0.3, or 100: 7 to 100: 0.5, particularly preferably in the range of 100: 6 to 100: 1 , 100: 5 to 100: 2, or 100: 4 to 100: 3.
    A wax content is particularly advantageous when the coating according to the invention must not be overcoated. Lubricant can also be added to reduce the friction coefficient of the coating, particularly for molding and / or as protection against scratches. Paraffin, polyethylene, polypropylene, oxidized polyethylene and / or oxidized polypropylene, among others, is / are recommended for this purpose. Individual waxes can be present in amorphous and / or crystalline form.
    The aqueous composition preferably contains multiple lubricants, particularly two or three lubricants, for which the properties of at least two of the lubricants are very different from each other. To mold substrates that are coated with the preparation, at least one lubricant, particularly at least one wax, or a combination of at least two lubricants, particularly, at least one is a wax, with melting points or scopes of very different fusion. Accordingly, the melting point or the melting range between two lubricants can differ by at least 15 ° C. For simplification, only melting points are described below. The friction coefficient of the coating can thus be adjusted in such a way that an optimized sliding of the coated substrates in the molding tools is ensured. This means that the sliding ability of the treated substrate surfaces is such that an optimum adjustment of the molded part to be produced is possible by means of a tool holding pressure. If the surface of the coated substrate does not have sufficient sliding capacity, there is a risk of inadvertent thinning of the substrate, generally without significantly reducing the wall thickness during molding, as a result of
    19/78 that the substrate in the mold may involuntarily change to smaller dimensions present in the regions of the mold, which in the worst case may result in the substrate cracking. If the surface of the coated substrate has an excessive sliding capacity, there may be a risk that the tape that is coated according to the invention cannot be wound onto a roll with sufficient stability. Furthermore, for the production of individual sheet there is a risk that during punching, particularly of small parts, and / or during lamination molding and / or cutting of molded parts, the tape feed cannot be obtained with a precise adjustment, resulting in inadequate dimensional stability of the molded pates to be produced. A combination and at least two different waxes can preferably be selected in such a way that a satisfactory, clear varnish adherence of the coating according to the invention can be ensured on the layer of powder varnish or wet varnish based on organic solvent and / or water applied subsequently.
    In addition, at least one film-forming agent, such as at least one long-chain alcohol, for example, can be added to the composition according to the invention. The at least one film forming agent, which is added and / or to be added in the form of at least one long chain alcohol, is used to improve film formation, particularly during drying. An organic film, substantially or completely homogeneous, is formed by the organic film forming agent, together with at least one long chain alcohol, by formation and film, particularly, during and / or after release and water and other volatile components. At least one long chain alcohol can be used to better film the polymer particles of the aqueous composition during drying, storage, as a temporary plasticizer for the polymer particles.
    The content of at least one film-forming agent in the aqueous composition, particularly in the bath, can preferably be 0.01 to 60 g / l, relative to solids, including active substances, particularly preferably 0.08 to 48 g / l or 0.12 to 35 g / l, especially so
    Injured 20/78, 0.2 to 25 g / l, 0.3 to 20 g / l, or 0.5 to 16 g / l, particularly 1 to 12 g / l, 2 to 10 g / l, 3 to 8 g / l, or 4 to 6 g / l. The weight ratio of the content of organic film-forming agent (polymers / organic copolymers) to the content of film-forming agents in the bath can vary over wide limits. This ratio is preferably in the range of 100: 10 to 100: 0.1, 100: 6 to 100: 0.4, or 100: 5 to 100: 0.8, particularly preferably in the range of 100: 4 to 100: 1.2 or 100: 3 to 100: 1.5.
    It is understood that film formation means the formation of a film of a material with a high organic fraction, such as a polymer dispersion in which, mainly, polymer particles are transformed into a uniform film at room temperature or at a temperature slightly higher. This is often referred to as melting and / or coalescing the polymer particles. Film formation occurs from an aqueous medium during drying, optionally with plasticization of the polymer particles by the remaining film forming agents. Film formation can be made possible and / or improved using soft synthetic resin (hardness using the Kõnig pendulum of less than 30s, measured at room temperature according to DIN EN ISSO 1522) and / or adding substances that work as temporary plasticizers (film-forming agents, Kl). Film-forming agents act as specific solvents, which plasticize the surfaces of the polymer particles and, thus, allow a change in their geometry, due to the interference of organic particles, but, in particular, they are not highly volatile, and particularly they evaporate in largely after the water has evaporated, and preferably does not remain permanently on the film. The resulting film is often free or essentially free of pores and is unable to incorporate dissolved and / or non-dissolvable particles, such as, for example, inorganic particles. In this context, it is advantageous for this plasticizer, on the one hand, to remain in the aqueous composition for long enough to be able to act on the polymer particles for a long period of time, and, on the other hand, to subsequently evaporate and thus escape from movie. In an appropriate film formation, a film is formed
    21/78 transparent, but not a milky white or even a powdery film, which is a sign of a defective film formation. For absolutely perfect film and formation, the temperature of the wet film applied to a surface must be above the minimum film-forming temperature (MFT). Only then are the polymer particles sufficiently plastic to coalesce. In this context, it is particularly advantageous when film-forming agents, such as temporary plasticizers, cause little or no change in the pH of the aqueous composition.
    The selection of film-forming agents is not simple; a mixture of at least two film-forming agents is often beneficial. The film-forming agents preferably have a boiling point at 760 mm Hg nm in the range of 140 to 400 ° C, particularly in the range of 250 to 340 ° C, 160 to 310 ° C, or 170 to 280 ° C, and / or an evaporation number for ether = 1 in the range of 100 to 5000, particularly in the range of 120 to 4000, 135 to 2800, or 150 to 1600. The so-called long-chain alcohols, preferably those which containing 6 to 14 or 8 to 12 C atoms, are particularly advantageous as film forming agents. These alcohols can also be alkoxylated. The alcohols are preferably at least one glycol and / or derivatives thereof, for example, on the basis of butandiol; for example, on the basis of ethylene glycol, such as ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethyl glycol propyl ether, ethylene glycol hexyl ether, ethylene glycol, diethylene glycol, ethylene glycol, diethylene glycol, diethylene glycol, diethylene glycol, diethylene glycol , tripropylene glycol ethyl ether; and / or, for example, on the basis of propylene glycol, such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monobutyl glycol, monpropylene glycol monobutyl glycol, monpropylene glycol, monpropylene glycol, tripropylene glycol, monpropylene glycol, tripropylene glycol , and / or propylene glycol phenyl ether.
    Contrary to film formation, which can occur at comparatively low temperatures, for example, in the range from 5 ° C, for chemical-thermal crosslinking of organic coatings, it is necessary to
    22/78 various temperatures of at least 50 ° C for crosslinking. Film-forming agents are preferably selected and added in such an amount that the composition preferably turns into film at temperatures above 5 ° C, particularly preferably above 10 ° C, above 20 ° C , or above 40 ° C, particularly above 60 ° C, above 80 ° C, above 100 ° C, or above 120 ° C. Similarly, it is preferable when the minimum film forming temperature for synthetic resins, which include film forming agents, results in film formation at temperatures above 5 ° C, particularly preferred above 10 ° C, above 20 ° C, or above 40 ° C, particularly above 60 ° C, above 80 ° C, above 100 ° C, or above 120 ° C. Subsequent drying preferably takes place at slightly higher temperatures (at least 10 °, 15 ° or 20 ° C) or at much higher temperatures (at least 30 °, 50 °, 70 °, 90 ° or 100 °) than the minimum film-forming temperature for synthetic resins, which include film-forming agents. Water and organic solvents, optionally present, escape during drying. Film formation normally starts then, in which organic substances, optionally in the form of particles, are able to clump together more intimately, become softer due to the higher temperature, and form a closed film. It is particularly preferred when a significant part of the film formation has already occurred at room temperature.
    In individual embodiments, the coalescence of the polymer particles can also occur without the addition of a film-forming agent, for example, when the hardness using the Kõnig pendulum of organic polymer additives is less than 10 s.
    In addition, in individual embodiments, at least one crosslinker can also be added to the composition according to the invention. This crosslinker can assist in the realization of a film-like coating, which is only physically dried and homogenized, stronger, due to chemical reactions, and more resistant. The resistance of film-like coatings to water and chemicals is usually further improved in this way. To that end, it is advantageous when
    23/78 the organic polymer / copolymer contains COOH groups and / or other groups that are suitable for crosslinking.
    Suitable crosslinkers can be selected as a function of drying and / or crosslinking temperatures. Organic crosslinkers based on melamine formaldehyde are normally used in a temperature range of approximately 120 ° to approximately 250 ° C, preferably in the range of 140 ° to approximately 200 ° C, while the other organic crosslinkers are normally or usually used in a temperature range of approximately 50 ° to approximately 120 ° C, preferably within the range of approximately 60 ° to approximately 110 ° to approximately 100 ° C. These latter crosslinkers are now referred to as organic low temperature crosslinkers. For example, at least one aziridine, preferably polyfunctional (active in the range 40 to 250 ° C, for example), at least one carbodiimide, such as at least one polycarbodiimide (active in the range 80c to 250 ° C , for example), at least one isocyanate, preferably blocked (active in the range of 80 ° to 250 ° C, for example), at least one melamine formaldehyde (active in the range of 120 ° to 250 ° C, for example) , at least one triazine (active in the range of 1000 ° to 250 ° C, for example), and / or at least one diamine, (active in the range of 60 ° to 250 ° C, for example), can be used as a crosslinker . However, a blocked isocyanate can be disadvantageous if it causes the reaction to proceed extremely slowly, making it unsuitable for drying at low temperatures of conducted treatments. In comparison with a melamine based crosslinker, a triazine based crosslinker has the advantage that formaldehyde is not separated during the thermal reaction (drying, crosslinking).
    The following can preferably be used as the at least one crosslinker: organic crosslinkers, such as adipine dihydrazide, organic crosslinkers based on aziridine, for example polyfucnioal polyaziridine, based on an azo compound, based on diamine, based on in diimide, for example, multifunctional plicarbodiimides, based on formaldehyde, for example, urea formaldehyde and / or mela formaldehyde
    Mine, for example, hexamethoxymethyl melamine, based on peroxide, based on trizine, for example, tris- (alkoxyfrbonylamino) triazine, and / or based on triazole. A crosslinker based on zirconium carbonate, which is stable and / or stabilized in an acid or neutral medium, can also optionally be used as a crosslinker.
    The crosslinker may be suitable, in particular, to crosslink at least partially, at least one of the synthetic resins contained in the coating composition, and / or to react chemically with at least one of the synthetic resins contained. Crosslinking, including the chemical reaction, can preferably take place by chemical and / or chemothermal means. The crosslinker can also often function as a reaction catalyst and / or sometimes as a corrosion inhibitor. The crosslinker can assist in improving resistance against corrosive media, such as chemical substances or effects of atmospheric action and against mechanical loads, improving or ensuring the stability of the discernible color of the substrate, particularly for zinc and zinc-containing surfaces, under high humidity and / or exposure to humid environments, avoid or extensively reduce the darkening of a transparent coating. In some embodiments, the crosslinker may be present in a stable form in the aqueous composition, in order to remain homogeneously distributed and dispersed in it for a long term, and / or remain with little or no reactivity at temperatures below approximately 40 or 45 ° C, for example example, and thus be stable in storage, but above about 45 or 50 ° C, for example, to enable the desired reaction with synthetic resins, after the coating is applied.
    The weight ratio of the content of organic film-forming agent to the content of crosslinkers in the aqueous composition, particularly in the bath, can vary over wide limits. This ratio is preferably in the range of 100: 10 to 100: 0.1, 100: 5 to 100: 0.2, or 100: 2.5 to 100: 0.3, particularly preferably in the range of 100: 2 to 100: 0.5 , 100: 1.6 to 100: 0.8, or 100: 1.4 to 100: 1.
    In this respect, the content of at least one crosslinker may vary
    25/78 extensively, depending on the type of crosslinker, the synthetic resins involved and / or the desired coating properties, and / or also the combination of various crosslinkers in the aqueous composition. The at least one crosslinker is preferably selected in such a way that crosslinking reactions in the aqueous composition do not occur, or essentially do not occur, before the coating is applied. The optional addition of at least one blocker and / or reaction stabilizer, which in each case helps to suppress crosslinking reactions in the aqueous composition, before the coating is applied, is advantageous.
    The content of at least one crosslinker in the aqueous composition is preferably in the range of 0.2 to 80 g / l, relative to solids, including active substances, or 0.5 to 50 g / l, particularly preferably , within the range of 1.5 to 35 g / lm, 3 to 20 g / l, or 6 to 10 g / l.
    In addition, it is advantageous to add at least one wetting agent, to enable the application of the wet film, which is uniform in the flat extent and thickness of the layer, and also in an airtight and flawless manner. In principle, many wetting agents are suitable for this purpose, preferably acrylates, silanes, polysiloxanes, silicone surfactants and / or other alcohols, which reduce the surface tension of the aqueous composition and help to moisten the entire metal surface. The wetting agent can be added in a total amount ranging from 0.1 to 10 g / l, particularly 1 to 4 g / l.
    In addition, at least one defoaming agent can also be added to the composition according to the invention, preferably in a total amount ranging from 0.1 to 10 g / l, particularly 1 to 4 g / l. In some cases, the addition of a defoaming agent is necessary to limit foaming. This is because, with very strong foaming, bubbles can possibly remain on the coating and form pores. In principle, useful additives, including the varnish additives often used for varnishes, are basically known to someone skilled in the art.
    The aqueous composition according to the invention contains
    26/78 preferably, cations of aluminum, chromium (lll) and / or zinc, and / or at least one compound containing aluminum, chromium (lll) and / or zinc, and some modalities, also cations of aluminum, chromium (IIIO iron , manganese and / or zinc, and / or at least one compound containing chromium (lll), iron, manganese and / or zinc The basic composition according to the invention, i.e., and particularly the fresh center and / or the composition d fresh bath, and often also, the replacement solution, which is added to the bath as needed during use, particularly to keep the bath ready for operation, in a very large number of modes, preferably has a significant content of cations and / or at least one compound of aluminum, chromium (ll), iron, manganese and / or zinc.The composition preferably has a total content of cations of iron and / or manganese, and / or at least one compound with an iron and / or manganese content, within the range of 0.1 to 20 g / l, 0.5 to 12 g / l, 1 to 8 g / l or 2 to 5 g / l, calculated as metal . In many modalities, in addition to cations and / or compounds of aluminum, chromium, iron, manganese, titanium, zinc and / or zirconium, the composition has little or no significant cation content of other heavy metals and / or heavy metal compounds, in addition to those mentioned now. The composition also frequently does not contain corm. However, the composition can often absorb additional cations and / or compounds, when in contact with the facilities or with the metal surfaces to be coated and / or as a result of the inclusion of impurities. Therefore, the original chromium-free composition can also contain traces, or, in isolated cases, even small amounts of corm, chromium compounds and / or cations / compounds, for example, from other steel refiners. The composition preferably has a total content of aluminum, chromium (lll) and / or zinc cations within the range of 0.5 to 80 g / l, 1 to 50 g / kl, or 2 to 30 g / l, calculated as metal, or, particularly preferably, it has a total content of aluminum chromium (lll), iron, manganese and / or zinc cations and / or at least one compound with an aluminum, chromium (lll), iron content, manganese and / or zinc, within the range of 0.5 to 80 g / l, 1 to 50 g / l, or 2 to 30 g / l, calculated as metal. The cation content of aluminum, chromium (lll) and / or zinc and / or at least one compound containing aluminum, chromium (lll) and / or zin
    27/78 co, or Otero of aluminum, chromium (lll), iron, manganese and / or zinc cations, or at least one compound containing aluminum, cormo (lll), iron, manganese and / or zinc, are especially preferred, in the range of 3 to 25, 4 to 20, 5 to 15, 6 to 12 or 8 to 10 g / l, calculated as metal. A chromium (lll) content such as cations and / or compounds, is particularly preferably approximately zero or is in the range of 0.01 to 30, 0.1 to 20, 0.3 to 12, 0.5 to 8, 0.8 to 6 or 1 to 3 g / l, calculated as metal. With respect to cations and / or metal-containing compounds, the composition according to the invention is composed only, or only essentially, of cations of aluminum, chromium (lll) and / or zinc, or at least one compound containing aluminum, chromium (lll) and / or zinc, particularly when alkali metals, titanium, hafnium, zirconium, and compounds thereof are excluded. The chromium (VI) content as cations and / or compounds can, in particular, be zero, approximately zero, or be in the range of 0.01 to 8, 0.05 to 5, 0.1 to 3, or 0.3 at 1 g / l, calculated as metal. Preferably, at least 60%, at least 80%, at least 90% or even at least 95% of these cations and compounds are based on aluminum and / or zinc, when alkali metals, titanium, hafnium, zirconium and compounds thereof are excluded. The content of these cations and compounds can be varied within a wide range and can optionally be present in a complex state. It can also be taken into account that, due to the stripping action of the main component of the metal surface, for example, zinc for galvanized surfaces, iron for steel surfaces, and aluminum for aluminum surfaces, the addition is carried out in smaller quantities along a very long production time, because the main component is replaced only due to the stripping action. It is particularly preferred when the composition according to the invention essentially contains only alkali metal (s), aluminum, titanium, zinc and / or zirconium cations, or that only those cations are added to the composition. With respect to cations and / or compounds containing metal, it is particularly preferred when only cations and / or compounds of alkali metal (s), aluminum, chromium (lll), titanium, zinc and / or zirconium are added to the composition of a28 / 78 according to the invention. It is especially preferred when only or essentially only alkali metal (s), titanium and zinc, or alkali metal (s), titanium and aluminum, are contained in the composition according to the invention, or are added thereto. With respect to cations and / or metal-containing compounds, it is particularly preferred when only cations and / or compounds of alkali metal (s), aluminum, chromium (lll), titanium, zinc and / or zirconium are added to the composition of according to the invention. In this regard, optionally, other types of cations, trace impurities, introduced impurities and / or pickled impurities from devices and / or substrates may appear.
    In most embodiments, the content of cations and / or at least one alkaline earth metal compound is approximately zero or ranges from 0.001 to 1.5 g / l, 0.003 to 1 g / l, 0.01 to 0, 5 g / l, or 0.03 to 0.1 g / l, calculated as the respective metal. When the content of these cations / compounds is very low, no negative effects are expected. When the content of these cations / compounds is too high, the stability of the solution is put at risk and losses in corrosion protection can occur. The content of alkaline earth metals has a disruptive effect, when it results in precipitation. Precipitation with alkaline earth metals can easily occur due to the fluoride content (including complex fluoride). In most embodiments, the content of cations and / or at least one compound of at least one alkali metal is approximately zero or is within the range of 0.001 to 5 g / l, 0.01 to 2 g I, 0.1 to 1 g / l or 0.02 to 0.2 g / l, calculated as the respective metal. However, small amounts of alkali metals and alkaline earth metals are often not disruptive when they are present in the same range as in tap water.
    The aqueous composition according to the invention preferably has a phosphate content in the range of 1 to 250 g / l, calculated as PO 4 . The phosphate content of the composition is preferably in the range of 2 to 200 g / l, 3 to 120 g / l, 4 to 100 g / l, 5 to 80 g / l, 6 to 65 g / l, 7 at 50 g / l, 8 to 40 g / l, 9 to 30 g / l, 10 to 22 g / l, or 12 to 18 g / l, calculated as PO 4 . In particular, the phosphate content of the composition is in the range of 0.75 to 185 g / l, 1.5 to 150 g / l, 2.2
    29/78 to 90 g / l, 3 to 75 g / l, 4 to 60 g / l, 5 to 50 g / l, 6 to 40 g / l, 7 to 30 g / l, 8 to 22 g / l , or 10 to 16 g / l, calculated as P2O5. Corrosion protection is low when the phosphate content is excessively low. A phosphate addition is preferably high enough to achieve a clear improvement in corrosion protection and surface appearance. When the phosphate content is too high, matte coatings can form. The ratio of Al to PO 4 for compositions, whose content of cations and / or inorganic compounds is selected from those based on aluminum, chromium, iron, manganese and / or zinc, predominantly those based on aluminum, is preferably within the scope from 1:10 to 1:25, particularly within the scope of 1:12 to 1: 18. The ratio of Zn to PO 4 for compositions, whose content of cations and inorganic compounds is selected from those based on aluminum, chromium, iron, manganese and / or zinc, or based on aluminum, chromium and / or zinc, predominantly those based on zinc, is preferably in the range of 1: 4 to 1:20, particularly in the range of 1: 6 at 1:15. Phosphate is preferably added as at least one compound selected from monophosphates (orthophosphates based on PO4 3 ', monohydrogen phosphates based on HPO4 2 ·, dihydrogen phosphates based on H 2 PO4 -)> diphosphates, triphosphates, phosphorous pentoxide and / or phosphoric acid (orthophosphoric acid, H3PO4). A phosphate addition can be an addition of monometallic phosphate, an addition of phosphoric acid and metal, phosphoric acid and metal salt / metal oxide, diphosphate, triphosphate, polyphosphate and / or phosphorous pentoxide to water or to a mixture watery.
    When at least one orthophosphate, at least one triphosphate and / or phosphoric acid, for example, is / are added, a corresponding chemical balance is established, particularly depending on the pH and concentrations of those additives. The more acidic the aqueous composition, the greater the shift in chemical equilibrium towards orthophosphoric acid (H3PO4), and at higher pH values, the equilibrium shifts towards tertiary phosphates based on PO 4 3 '. Within the meaning of the present patent application, in principle, a large number of different orthophosphates can be added. Aluminum, chrome and / or zin orthophosphates
    30/78 co, proved to be particularly appropriate. Preferably, at least one orthophosphate is added to the aqueous composition, with a total addition, in the range of 1 to 250 g / l, calculated as PO 4 , particularly preferably, in the range of 2 to 200, 3 to 120, 4 at 90, 5 at 75, 6 at 60, 8 at 50 or 10 at 30 g / l. The total addition corresponds to the overall content.
    The aqueous composition can be prepared using phosphoric acid anhydride P2O5, an acid containing phosphorus, at least one salt and / or ester of orthophosphoric acid, and / or at least one salt and / or ester of a condensed phosphoric acid, optionally, together with at least one metal, carbonate, oxide, hydroxide and / or salt, such as nitrate, for example, together with phosphoric acid.
    The addition of at least one complexing agent may be advantageous and / or necessary, when the pH must be increased, to absorb quantities of ions and / or compounds, particularly other types of ions and / or additional compounds, and / or stabilize the composition, particularly to avoid and / or activate precipitation. The complexing agent helps to bring inorganic components to solution and keep them stable in solution. The complexing agent is used to maintain a high content of compounds, particularly cations, such as aluminum, chromium, iron, manganese or zinc, and / or cations that are introduced or pickled from the installation and / or metal surfaces dissolved in the composition . This is because the precipitation of, for example, fluorides, hydroxide oxides and / or phosphates, particularly aluminum, iron, manganese and / or zinc, can be disruptive, due to the increased formation of iodines and / or due to the fact that precipitation impairs or even prevents the use of the coating composition. When precipitation occurs, in some situations the complexing agent can be added, if necessary, to end the precipitation. The at least one complexing agent is used, in particular, to complex cations, such as aluminum, chromium, iron, magnesium, manganese, titanium, zinc and / or zirconium, and thus to stabilize the solution or suspension, approximately at low acidity. In addition, in many modalities, adding at least one complexing agent has been shown to have
    31/78 a more or less protective effect against corrosion. When the complexing agent (s) is (are) added again, and / or when there is a high content of complexing agent (s) in the aqueous composition, in some cases, it may be advantageous to add also at least one compound to the composition, which is approximately neutral or basic, in order to adjust a higher pH. Within the meaning of this patent application, the term "complexing agent" also includes chelating agents (See definition of "complexing agent" in Rõmpp)
    As a complexing agent, at least one compound based on complexing alkoxide, based on carboxylic acid, based on phosphonic acid and / or based on an organic compound, such as a phytic acid, and / or based on a compound of phenol, such as tannic acid, is particularly preferably at least one compound selected from compounds comprising phosphonic acids, complexing carboxylic acids, phytic acid, polyphenol-based acids and derivatives thereof. This also includes, in particular, at least one compound selected from compounds comprising phosphonic acids, diphosphonic acids, alkylene phosphonic acids, phytic acid, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, aminocarboxylic acids, hydroxycarboxylic acids, polyphenol based acids and derivatives of the same. In some embodiments, it has proved to be particularly advantageous to add two or three distinctly different complexing agents, for example, those based on phosphonic acid and hydroxycarboxylic acid.
    The higher the content of at least one complexing agent, in some embodiments, the higher the pH of the composition can be adjusted, as a function of the quantity of cations. The content of the complexing agent (s) can be varied over a wide range. The composition according to the invention preferably has a total content of at least one complexing agent in the range of 0.1 to 60 g / l. The total content of at least one complexing agent is preferably in the range of 0.3 to 50 g / l, 1 to 40 g / l, 1.5 to 30 g / l, 2 to 24 g / l, 2 , 5 to 18 g / l, 3 to 14 g / l, 4 to 10 g / l, or 6 to 8 g / l.
    32/78
    The content of complexing agent is preferably high enough that the composition is a stable solution, and that stable solutions are also optionally obtained when diluted with water. If the content of the complexing agent is too low, depending on the amount of cations, an increase in pH and / or an increase in the content of cations and / or compounds can lead to precipitation, thus possibly resulting in deposits and also in sludge formation. If the content of the complexing agent is too high, corrosion protection and / or moldability may be impaired.
    In the method according to the invention, at least one phosphonic acid, at least one phosphonic acid salt and / or at least one phosphonic acid ester can be added, preferably, to the aqueous composition. The aqueous composition preferably has a content of at least one phosphonic acid-based compound in the range of 0.1 to 60 g / l, particularly preferably in the range of 0.3 to 50 g / l, 1 to 40 g / l, 1.5 to 26 g / l, or 2 to 18 g / l. At least one phosphonic acid-based compound, for example, a diphosphonic acid and / or a diphosphonic acid containing an alkyl chain and, optionally, other groups, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), amino-tris (methylphenphosphonic acid) (ATMP), ethylendiamine-tetra (methylphenphosphonic acid) (EDTMP), diethylentriamine-penta (methylphenphosphonic acid) ( DTPMP), dieylentriamine-penta- (methylenphosphonic acid) (DTPMP), hexamethylendiamine-tetrameylenphosphonic acid (HDTMP), hydroxyeyylamino-di (methylenphosphonic acid) (HEMPA), and / or phosphonobutane-1,2,4-tricarboxylic acid is / are particularly preferred.
    In the method according to the invention, the composition preferably contains, in each case, at least one complexing carboxylic acid and / or a derivative thereof: for example, at least one compound based on formic acid, succinic acid, acid citric, maleic acid, malonic acid, lactic acid, oxalic acid or tartaric acid, including derivatives thereof. The at least one carboxylic acid can have a complexing and / or corrosion protection effect. In some embodiments, the aqueous composition preferably has a content of at least one with
    33/78 post based on complexing carboxylic acid in the range of 0.1 to 60 g / l, particularly preferably in the range of 0.3 to 50 g / l, 1 to 40 g / l,
    1.5 to 26 g / l, or 2 to 18 g / l.
    The composition according to the invention preferably contains at least one compound based on polyphenol acids, for example, a gallic acid, a tannic acid, and derivatives thereof, for example, salts and esters thereof and their derivatives.
    The aqueous composition preferably contains at least one complexing compound based on phytin and / or polyphenol, with a total content of these compounds ranging from 0.05 to 30 g / l, particularly preferably within the range of 0.3 at 25 g / l or 1 to 20 g / l, especially preferably within the range of 1.5 to 15 g / l or 2 to 10 g / l.
    In the method according to the invention, the aqueous composition preferably has a total content of at least one titanium and / or zirconium compound of at least 0.1 g / l, calculated as Ti metal. total is in the range of 0.1 to 50 g / l, 0.5 to 30 g / l, or 1 to 15 g / l, calculated as Ti metal. The titanium and / or zirconium compound can optionally be added to the whole or in part as at least one complex fluoride, and / or it can be present in the aqueous composition in whole or in part as at least one complex fluoride. The composition has, particularly preferably, a total content of at least one titanium and / or zirconium compound in the range of 1 to 250 g / l, 2 to 180 g / l, 3 to 130 g / l, 4 to 100 g / l, 5 to 80 g / l, 6 to 60 g / l, 8 to 50 g / l, 10 to 40 g / l, 15 to 30 g / l, or 20 to 25 g / l, calculated as Ti metal. The composition has, particularly preferably, a total content of at least one compound of titanium and / or zirconium, based on complex fluoride, in the range of 1 to 200 g / l, calculated as the respective compound. When a zirconium compound is used, its content is converted to the content of the corresponding titanium compound on a molar basis and expressed as Ti metal content. In individual cases, at least one compound can also be added as a titanium compound and / or zirconium, which is normally stable only in basic media, but which is also stable in acidic media, when at least one
    34/78 plexation, for example, a phosphonate, and / or at least one protective compound, for example, a surfactant, is also added, after which this compound is present in a complex and / or protected form in the aqueous composition. It is particularly preferred when only at least one compound of titanium and / or zirconium, based on complex fluoride, is added as a compound containing fluoride. In many embodiments, the composition, in each case, contains at least one complex fluoride and / or its aluminum, titanium, zinc and / or zirconium salt, which is present, for example, as a MeF 4 and / or MeFe complex . Particularly for metal surfaces that contain aluminum, it is important that complex fluoride is added in an amount that is not too low in order to produce an increased stripping action. The addition and content of at least one compound of titanium and / or zirconium are preferably high enough to provide protection against uncovered corrosion and, if necessary, also good varnish adhesion, for the varnish / paint coating. subsequent basis. If the content of at least one compound of titanium and / or zirconium is preferably high enough to provide good protection against uncovered corrosion and, if necessary, also good varnish adhesion, for the varnish / paint coating of subsequent basis. If the content of at least one titanium and / or zirconium compound is too high, and insufficiently complexing agent (s) is present, it can easily result in bath instability and therefore precipitation. This is because a complex fluoride or fluoride can also function as a complexing agent. But, within the meaning of the present patent application, fluoride and complex fluoride are not considered to be complexing agents. The addition and content of a titanium compound has proven to be advantageous, particularly for improving corrosion protection. The addition and content of a zirconium compound proved to be advantageous, particularly for hot-dip galvanized surfaces to improve the varnish adhesion, in many embodiments, the titanium and / or zirconium compound according to the invention can be at least appropriate complex fluoride, and / or at least one
    35/78 complexed substance, for example, at least one titanium chelate, particularly at least one titanium alkoxide, with less reactive titanium and / or zirconium compounds being preferred. The weight ratio of silane / silanol, siloxane / polysiloxane to complex fluoride based on titanium and / or zirconium, calculated as added silane and / or polysiloxane or, optionally, converted to H 2 TiF 6 on a molar basis, is preferably , less than 2: 1, less than 1.5: 1, less than 1: 1, or less than 0.5: 1.
    In individual embodiments, the composition according to the invention contains at least one fluoride-free compound, which contains titanium and / or zirconium such as, for example, a chelate. This compound can be used to bring titanium and / or zirconium to the composition in a different form and is therefore an option for a source of this compound. This compound can extend corrosion protection extensively and keep the aqueous composition stable in solution. The composition according to the invention preferably has a content of titanium chelates and / or zirconium chelates in the range of 0.1 to 200 g / l, particularly preferably in the range of 1 to 150 g / l , 3 to 110 g / l, 5 to 90 g / l, 7 to 70 g / l, 10 to 50 g / l or 15 to 30 g / i
    In particular, the content of titanium and / or zirconium compounds is selected in such a way that a content of titanium and / or zirconium remains in the range of 3 to 60 mg / m 2 , 5 to 45 mg / m 2 , or 10 to 35 mg / m 2 , calculated as Ti metal and determined by X-ray fluorescence analysis on the metal surface. That compound is added, particularly, when no other compound containing titanium and / or zirconium is / are present in the composition according to the invention. It is particularly advantageous when at least one compound containing titanium and / or zirconium is / are present in the composition according to the invention with the invention. Dihydroxy-bis- (ammonium lactate) titanate, in particular, can be used as that compound.
    In the method according to the invention, the aqueous composition preferably has, for example, no fluoride content or a free fluoride content Fii Vre within the range of 0.01 to 5 g / l, and / or a total content of fluoride F t0
    36/78 tai in the range of 0.5 to 80 g / l. The composition has, in particular, a free fluoride content F | free in the range of 0.1 to 3.5 g / l, 0.3 to 2 g / L, or 0.5 to 1 g / L, and / or a total fluoride content F to tai in the range of 1 to 50 g / l, 1.5 to 40 g / l, 2 to 30 g / l, 2.5 to 25 g, 3 to 20 g / l, 4 g / l, or 7 to 10 g / l. In many embodiments, no hydrofluoric acid, monofluoride and / or bifluoride is / are added to the composition according to the invention. In that case, a content of hydrofluoric acid, monofluoride and / or bifluoride in the composition according to the invention can result in at least one complex fluoride and / or derivative thereof in small amounts, based only on equilibrium conditions. In individual modalities, hydrofluoric acid, monofluoride and / or bifluoride, with a total content of 0.01 to 8 g / l, calculated as free fluoride Fiivre, particularly 0.1 to 5 g / l or 0.5 to 3 g / l, is / are added to the composition according to the invention.
    Within the context of the present invention, the term "silane" is also intended to include hydrolysis, condensation, polymerization and reaction products thereof, that is, particularly, silanois, siloxanes and, optionally, polysiloxanes. The term "polysiloxane" is also intended to include condensation, polymerization and polysiloxane reaction products.
    In the method according to the invention, in individual embodiments the composition has a content of at least one silane / silanol / siloxane / polysiloxane or at least one silane / silnol, siloxane, preferably with a content of at least one silane / silanol / siloxane / polysiloxane of approximately zero or within the range of 0.1 to 50 g / l, 0.5 to 30 g / l, 1 to 20 g / l, 2 to 10 g / l, or 3 to 6 g / l , calculated as Si metal. When the silane / silanol / siloxane / polysiloxane content is too low, in some embodiments the corrosion protection of the coating may be impaired, particularly for hot dip galvanized surfaces. When the content of silane / silanol / siloxane / polysiloxane is too high, this can result in instability of the solution and, thus, precipitation and / or incomplete wetting of the metal surface. An addition and content of at least one surfactant (wetting agent) can avoid problems when a high content of silane / silanol / siloxane / polysiloxane is present, but it can also harm the
    37/78 protection of the coating produced. It has been found that a content of at least one surfactant can sometimes have a major influence on the properties of the coating according to the invention, particularly for corrosion protection. Corrosion protection can be greatly improved, particularly for lower quality levels of hot dip galvanized substrates (HDG). For this purpose, at least one nonionic surfactant is preferably added and, alternatively or additionally, optionally also at least one cationic surfactant. A second surfactant can optionally function as a solubilizer. A silane / silanol / siloxane and / or polysiloxane often improves corrosion protection extensively.
    The composition preferably contains, in each case, at least one silane / silanol / siloxane / polysiloxane, particularly based on alkoxysilanol, alkylsilane, amidosilane, aminosilane, bis-silylsilane, epoxylsilane, fluorsilane, imidosilane, iminosilane, isocyanatosilane, (meth) silane acrylate and / or vinyl silane. Among these silanes / silanois, siloxanes / polysiloxanes, those based on aminosilanes have proved to be particularly suitable in several modalities, although the other silanes, silanois, siloxanes mentioned here may also be important, depending on the modality. Such silanes / silanois / siloxanes contribute to an increased pH when silanes and / or their derivatives, which may be present after further condensation, particularly at a slightly increased pH, for example, based on silanes / silanois / silxoanes with at least one nitrogen-containing groups, such as at least one amino group (amiosilane), starch group, imino group and / or imido group, in each case, and / or with at least one proton-accepting ammonium group, are added. The pH can also be increased in this way, for example, from original values in the range of 1 to 2 or 1.5 to 3 to values in the range of 1.5 to 4. A content of silanes / silanois / siloxanes with at least one nitrogen-containing group, such as at least one amino group (aminosilane), starch group, imino group, and / or imido group, in each case, is particularly preferred. Alkylsilanes can be, particularly, di-, tri- and / or tetrafunctional. The
    38/78 alkylsilanes may contain, in particular, no organically functional side chain, or, particularly, may contain a group containing terminal nitrogen. Alkylsilanes may contain no side chains, but they may also contain at least one side chain with a chain length of up to ten C atoms. In some embodiments, the aqueous composition preferably contains, in each case, an addition and hair content. at least one compound based on at least one silane / silanol / siloxane / polysiloxane a) containing at least one nitrogen-containing group, for example, at least one amino group or ammonium groups, b) based on bis-silane (s), c ) based on expoxysilane (s), d) based on fluorsilane (s), e) based on isocyanatosilane (s), f) based on (meth) acrylatosilane # ( s )> 9) based on vinyl silane (s), h) based on alkoxysilanes, and / or i) based on alkylsilane, in each case, within the range of 0.5 to 160 g / l, particularly preferably, within the range of 1 to 120, 2 to 80, 3 to 50 , 5 to 35, or 8 to 20 g / l, calculated as Si metal. Particularly preferred Siianos are
    3-aminopropyltriethoxysilane and / or 3-aminopropyltrimethoxysilane (APS), N- [2 (aminoethyl)] - 3-aminopropyltrimethoxysilane (AEAPS), methylsilane, butylsilane, epoxysilane, and / or tetraepoxysilane (TEOS). In some silanes / silanois / siloxanes / polysiloxanes, higher fluoride levels may result in the formation of HF gas. Siloxanes and / or polysiloxanes can also be formed, depending on the type and degree of polymerization, for example, a condensation. Alternatively, it has been shown that the addition and content of at least one polysiloxane or the addition of a combination based on silane and polysiloxane can also be advantageous.
    In the method according to the invention, the composition preferably contains at least one monomer / oligomer / polymer / organic copolymer. Within the meaning of the present patent application, the term "copolymer" also includes block copolymers and / or graft copolymers. The addition and content of at least one acid-tolerant organic compound of this type, preferably based at least partially on (meth) acrylate, carbonate, epoxy, ethylene, polyester, and / or acid-tolerant urethane, is important in some modalities, in order to improve the protection against corrosion,
    39/78 varnish adherence, moldability, friction, and / or absorption of impurities containing oil, of the metal surface covered with oil and / or dirt. The latter is often used to avoid cleaning metal surfaces covered with oil and / or dirt. In doing so, a small amount of finish laminating pass agent from a finish laminate pass operation, a small amount of lubrication grease for temporary corrosion protection, and / or a small amount of molding oil from a The molding operation can possibly be absorbed onto a metal surface, which is coated according to the invention. The aqueous composition preferably has an acid tolerant content of at least one monomer / oligomer / polymer / copolymer in the range of 1 to 500 g / l, particularly preferably in the range of 5 to 450 g / l 1.15 to 400 g / l, 25 to 300 g / l, 40 to 280 g / l, 60 to 260 g / l, 80 to 240 g / r, 100 to 220 g / l, 120 to 20 g / l , 140 to 180 g / l or 150 to 160 g / l. The acid tolerant monomer / oligomer / polymer / copolymer content is. preferably, high enough for moldability to be improved, particularly, with friction during molding being significantly reduced. The acid tolerant monomer / oligomer / polymer / copolymer content is preferably in such a range that the stability of the aqueous composition is maintained, and a good appearance of the coating surface is ensured, so that, particularly, no matte and / or striped coatings result. Coatings that are transparent and / or with little or no color are particularly preferred.
    The composition preferably contains at least one acid-tolerant organic monomer / oligomer / polymer / copolymer, based on and / or with a (meth) acrylate, carbonate, epoxy, ethylene, polyester and / or urethane content. Each of these cited components can also be at least one component of a copolymer or copolymers. The aqueous composition preferably has an acid tolerant content of at least one monomer / oligomer / polymer / copolymer, based on a) (meth) acrylate, b) carbonate, c) epoxy, d) ethylene, e) polyester, and / or f) urethane,
    40/78 in each case, in the range of 0.5 to 300 g / l, particularly preferably in the range of 2 to 250 g / l, 5 to 200 g / l, 8 to 140 g / l, 12 to 100 g / l, or 16 to 60 g / i
    It is particularly preferred to add at least one cationic polyurethane resin, which is a polymer and / or copolymer and which preferably contains a part of a polyethylene and / or at least one other polymer.
    It is particularly preferred to add modified anionic polyacrylate, which is a polymer and / or copolymer and which preferably contains a part of polystyrene and / or at least one other polymer.
    However, the organic polymers and / or copolymers to be added must allow stability in the aqueous composition for at least five days.
    In the method according to the invention, the composition preferably contains, in each case, at least one inorganic and / or organic compound in the form of particles. Organic particles can be present, particularly, as a component of an organic polymer / copolymer. The particles often have particle sizes ranging from 10 to 300 nm. In some embodiments, the aqueous composition preferably has a content of inorganic and / or organic particles in the range of 0.05 to 120 g / l, particularly preferably in the range of 0.1 to 80 g / l, 0.3 to 50 g / l, 1 to 30 g / l, 1.5 to 15 g / l, or 2 to 10 g / l.
    The composition according to the invention preferably contains at least one inorganic compound in the form of particles, based on AI2O3, SiO 2 , TiO 2 , ZnO, ZrO 2 , mica, clay mineral, carbon black, and / or corrosion protection particles, which have a particle diameter less than 300 nm, as measured by a scanning electron microscope. Particles are used, in particular, as white pigment (s), colored pigment (s) and / or as corrosion protection pigment (s). Inorganic particles, such as those based on AI 2 O 3 , SiO 2 , THIO 2 , zro 2 , mica and / or clay mineral, often function as particles with a barrier effect, optionally with bonding to the metal surface. They can be used as white pigments, for example, the
    41/78 in order to cover the metal surface and produce a clear film. But, if necessary, colored pigments can also be added. For example, ZnO particles can have a corrosion protection effect, until they are possibly dissolved. Corrosion protection particles can be based, in particular, on silicate, mainly alkaline silicate and / or alkaline earth silicate, or also based on phosphates, phosphosilicates, molybdates etc. Particularly, due to their barrier function and / or the release of ions, corrosion protection particles can assist with a corrosion protection effect. The content of inorganic particles is preferably low enough that interference friction does not occur during modulation. The content of inorganic particles is preferably high enough that the particles have the barrier function and a higher corrosion protection is obtained.
    In individual embodiments, the composition according to the invention contains at least one accelerator, for example, at least one accelerator, selected from the group consisting of accelerators based on chlorate, nitrite, nitrobenzene sulfonate, nitroguanidine, perborfate and at least one other nitro-organic compound with oxidizing properties, which are known from phosphating. These compounds can also help to reduce or prevent the formation and hydrogen gas at the interface with the metal surface. In some embodiments, the aqueous composition contains at least one such accelerator in the range of 0.05 to 30 g / l, particularly preferably in the range of 0.3 to 20, 1 to 12, 1.5 to 8 or 2 to 5 g / l.
    The composition according to the invention preferably contains at least one additive, for example, in each case, at least one wetting agent, a demulsifier, an emulsifier, a defoaming agent, a corrosion inhibitor and / or an absorber of UV. If necessary, at least one other additive can be added, as is usual and known, in principle, for conversion coatings, passivations and base varnishes / paints. The aqueous composition preferably contains at least one additive with a total content of the additives in the range of 0.001 to 50 g / l, particularly preferably in the range of 0.01 to 30, 0.1 to 10, 0, 5 to 6,
    42/78 or 1 to 3 g / l.
    The object is achieved using a composition corresponding to the main claim.
    The object is further achieved using a coating, which is prepared using the method according to the invention and / or using an aqueous composition according to the invention.
    The aqueous composition can vary within wide limits and preferably contains
    (a) 1a 250 g / l phosphate, calculated as PO 4 , or 0.75 to 185 g / l phosphate, calculated as P2O5,
    b) 0.1 to 50 g / l of at least one titanium and / or zirconium compound, calculated as Ti metal,
    c) 0.1 to 60 g / l of at least one complexing agent,
    d) 0.5 to 80 g / l of aluminum, chromium (lll) and / or zinc cations and / or at least one compound containing aluminum, chromium (ll) and / or zinc, and
    e) 1a 500g / l of at least one organic polymer / copolymer, cationic or non-ionic, acid-tolerant, with respect to the content of solids and active substances.
    The composition according to the invention preferably contains:
    to 400 g / l of organic polymers / copolymers e), to 50 g / l or 0 gl / l of lubricant f), to 50 g / l of Al, Cr (lll), and / or Zn d) combined, 200 g / l phosphate, such as PO 4 , to 150 g / l phosphate, as P2O5, 40 g / l complexing agent c),
    0.5 to 30 g / l Ti and / or Zr b) together, calculated as Ti metal, and optionally at 50 or approximately 0 g / l F of at least one fluoride compound (F to tai), and /or
    0.5 to 30 or approximately 0 g / l of silicon compound (s), calculated as Si metal, and optionally, silicon compound (s), calcu43 / 78 sides as Si metal, and optionally, also at least one of the other compounds cited in the present patent application.
    The aqueous composition preferably contains:
    to 300 g / l organic polymers / copolymers e), to 30 g / l or 0 g / l of lubricant f), to 30 g / l of Al, Cr (lll), and / or Zn d) combined, at 120 g / l phosphate, such as PO 4 ,
    2.2 to 90 g / l of phosphate, such as P2O 51 to 18 g / l of complexing agent c), to 15 g / l of Ti and / or Zr b) combined, calculated as Ti metal, and optionally , at 25 or approximately 0 g / l of F of at least one fluoride compound (F to tai)> θ / or at 5 or approximately 0 g / l of silicon compound (s), calculated as Si metal, and optionally , silicon compound (s), calculated as Si metal, and optionally also at least one of the other compounds cited in the present patent application.
    These levels mentioned apply to concentrate as well as to baths. For baths, all the above information regarding scopes can, in each case, for example, be divided by a dilution factor of, for example, 1, 2 or 4.
    The weight ratio of (Al, Cr 3+ , Fe, Mn, and Zn) :( Ti and Zr) and / or (Al, Cr 3+ , and Zn) :( Ti and Zr) is preferably within the range of 0.1: 1 to 3: 1. These weight ratios are particularly preferably in the range of 0.5: 1 to 2.5: 1 or 1: 1 to 2: 1.
    In addition to the added contents, particularly aluminum, chromium (lll), iron, manganese, titanium, zinc and / or zirconium, these and, optionally, other cations can be contained in the composition according to the invention, on the one hand, by incorporation, for example, of previous baths, impurities and / or leaching of materials from the tank and tubes and surfaces to
    44/78 be coated and, on the other hand, by the addition of other cations, compounds, which contain metal, for example, at least one alkali metal, molybdenum and / or vanadium.
    In many embodiments, the aqueous composition according to the invention is preferably free or essentially free of compounds based on epoxy, phenol, starch, chromium (VI), and / or based on other heavy metals, for example, those based on chromium, molybdenum, nickel, vanadium and / or tungsten. In many embodiments, the aqueous composition according to the invention is preferably free or essentially free of compounds, which are used as accelerators in phosphating, particularly compounds based on chlorate, nitrite, nitroguanidine, peroxide and / or other accelerators containing N.
    The compositions according to the invention are preferably free or essentially free of chromium (VI). But, for some of the compositions according to the invention, they can also be optionally free or essentially free of chromium (II), particularly, optionally, free or essentially free of cations and / or chromium compounds.
    The aqueous composition preferably does not contain calcium and / or magnesium, or only a content of not more than 0.5 g / l, particularly preferably not more than 0.15 g / l, of calcium and / or magnesium, and / or no toxic or environmentally harmful heavy metals, or only a content of no more than 0.5 g / l, particularly preferably not more than 0.15 g / l, of at least one heavy metal toxic or harmful to the environment, for example, chromium. In fluoride free compositions, a determined or higher content of calcium and / or magnesium may also be present.
    The composition according to the invention preferably has a pH in the range of approximately 0 to 10. The pH is particularly within the range of 8.1.5 to 6, 2 to 5, 2.5 to 4, or 3 to 3.5. In this respect, a low pH is preferred in many modalities, in order to produce a somewhat pickling effect and transfer a high proportion of the pickled cations upside down.
    45/78 and / or in a coating under or inside a polymer coating, so that the conversion effect is clearly maintained, despite a high proportion of organic polymers / copolymers in the composition. On the other hand, it needs to be ensured that the content of pickled cations does not have a major negative effect on corrosion protection.
    In principle, in some embodiments with an increased content of at least one complexing agent, a pH of the composition can also be adjusted within the range of 4 to approximately 10, in which case, an increased amount of at least one approximately neutral and / or compound basic added in each case. Particularly ammonia, at least one other basic compound, which optionally contains nitrogen, for example, at least one amine, at least one basic compound, which contains carbonate, hydroxide and / or oxide, at least one organic polymer / copolymer, and / or at least one silane / silnol.solxoane / polysioloxane can be added to influence the pH. For example, zinc oxide, manganese carbonate and / or essentially neutral or basic polymers and / or copolymers can also be added. The content of approximately neutral and / or basic media, which assist in adjusting the pH and which are added mainly or exclusively to adjust the pH, can preferably be zero, or be in the range of 0.05 to 100 g / l, particularly preferably within the range of 0.2 to 60 g / l, 1 to 40 g / l, 2 to 25 g / l, 3 to 18 g / l, or 4 to 12 g / l. Due to the content of fluoride and / or silane, polysiloxane, it may be advantageous not to take measurements with a glass electrode, but instead to use pH indicator paper.
    All or most of the compounds, which are also present in corresponding constituents in the solution, are preferably added as additives to the aqueous concentrate, to prepare an aqueous composition. The bath composition is prepared, preferably from the aqueous concentrate by diluting the aqueous concentrate, together with 10 to 1000% of the content of solids and active substances in the concentrate with water. However, in some embodiments, a highly concentrated and / or undiluted suspension or emulsion can also be advantageously used.
    46/78
    Surfaces of all metallic materials can be coated according to the invention. Metal surfaces made of aluminum, iron, copper, magnesium, titanium, zinc, tin and / or their alloys are coated, preferably, particularly, surfaces of zinc, steel and hot dip galvanized (HDG), electrolytically galvanized, Galvalume®, Galfan® and / or Alusi®. The composition according to the invention proved to be superior, particularly for metallic surfaces rich in zinc and / or rich in aluminum. The metal components, which are coated using the method according to the invention, can be used, particularly, in automotive manufacturing, as architectural elements under construction, or for the manufacture of equipment and machines for example, electrical equipment or household appliances. Mounting parts, strips, plates, molded parts, injected parts and small parts, such as screws and profiles, are particularly suitable as metallic objects to be coated.
    In particular, a temperature of the aqueous composition of 10 to 40 ° C is appropriate during coating. A substrate temperature of 10 to 40 ° C is particularly appropriate during coating. The coating, which is produced according to the invention can have a coating composition that varies over a wide range. In particular, the coating can be characterized by the fact that it contains: organic polymer / copolymer 50 to 15,000 mg / m 2 lubricant 0, or 3 to 2000 mg / m 2
    Al, Cr, and / or Zn, calculated as metal 1 at 400 mg / m 2 sum of Ti and / or Zr, calculated as Ti metal 1a 300 mg / m 2 phosphate, calculated as PO 4 4 at 1600 mg / m 2 phosphate, calculated as P 2 O 5 3 at 1200 mg / m 2 Si compound (s), calculated as Si metal approx. 0, or 0.5 to 150 mg / m 2 .
    The coating according to the invention preferably contains:
    organic polymer / copolymer 250 to 8,000 mg / m 2 lubricant 0, or 10 to 1000 mg / m 2
    47/78
    Al, Cr, and / or Zn, calculated as metal 10 to 250 mg / m 2 sum of Ti and / or Zr, calculated as metal Ti 10 to 180 mg / m 2 phosphate, calculated as PO 4 40 to 1100 mg / m 2 phosphate, calculated as P 2 O 5 30 to 800 mg / m 2 Si compound (s), calculated as Si metal approx. 0, or 5 to 100 mg / m 2 .
    These levels can be determined using an analytical method of X-ray fluorescence on a coated, cut-out plate. In this regard, the weight ratio of (Al, Cr 3+ , and Zn): (Ti and Zr) of the coating composition can preferably be in the range of 0.5: 1 to 1.8: 1, from particularly preferred, in the range of 0.9: 1 to 1.4: 1.
    The weight of the layer of the layer that is formed according to the invention can vary over wide limits. The weight of the layer can range from 0.01 to 50 g / m 2 , 0.05 to 30 g / m 2 , 0.1 to 20 g / m 2 , 0.3 to 12 g / m 2 , 0.5 to 10 g / m 2 , 0.8 to 8 g / m 2 , 1 to 6 g / m 2 , 1.2 to 5 g / m 2 , 1.5 to 4 g / m 2 , 1.8 to 3 g / m 2 , or 2 to 2.5 g / m 2 . For coating in pickling installations, the weight of the layer can be, in particular, in the range of 10 to 50,000 mg / m 2 , preferably in the range of 500 to 20,000, particularly preferably, in the range of 700 to 12,000 or 900 to 6,000, especially preferably, within the range of 1000 to 2000 mg / m 2 . For coating in pickling installations, the total content of titanium and / or zirconium in the dry film is preferably in the range of 1 to 100 mg / m 2 , particularly preferably in the range of 10 to 60 to 40 mg / m 2 , Ti and / or Zr, calculated as Ti metal. The total titanium and / or zirconium content can be measured by X-ray fluorescence. For coating in pickling facilities, the total silicon content in the dry film is preferably in the range of 1 to 80mg / m 2 , particularly preferably, in the range of 3 to 40 mg / m 2 , of Si, calculated as metal. For coating in pickling installations, the total content of P2O5 in the dry film is preferably within the range of 30 to 400 mg / m 2 , particularly preferably within the range of 60 to 300 mg / m 2 of P2O 5 .
    For coating in pickling installations, the thickness of the coatings according to the invention is often within the scope
    48/78 from 0.01 to 40 m, 0.1 to 20 m, 0.3 to 15 m, 0.5 to 10 m, or 3 to 10 m, particularly, within the range of 0.5 to 6.5 m, 0.8 to 4.5 m, or 1 to 3 m. For coating in installations other than pickling installations, such as for coating parts, the thickness of the coating is often in the range of 0.1 to 50 m, 0.2 to 20 m, or 0.3 to 15 m, particularly within the range of 0.5 to 2 m, 0.8 to 1.8 m, or 1 to 1.5 m.
    The aqueous compositions according to the invention often have a concentration of solids and active substances (total concentration) in the range of 10 to 800 g / l. A concentrate can often have a total concentration in the range of 200 to 800 g / l, particularly 400 to 750 g / l. If necessary, a dilution can be made. A concentrate is preferably diluted by a factor in the range of 1.1 to 25, particularly preferably in the range of 1.5 to 16, 2 to 10 or 3 to 6. The content of solids and active substances at being adjusted in the aqueous composition is mainly a function of the type of substrate to be coated, the specific installation and the wet film thickness required for the installation.
    In many embodiments, the composition according to the invention is used in a metal strip (roll) in a strip coating process. Many of the pickling facilities have a conveyor speed ranging from 10 to 200 m / min. The faster the strip is moved, the faster the reactions between the composition according to the invention and the metal surface need to occur, in order to avoid the need for excessively long installation sections. The reaction time between application of the composition and the complete drying of the composition can last from a fraction of a second to approximately 60 seconds. As a result, particularly for fast pickling installations, the aqueous composition may have insufficient reactivity and must therefore have higher acidity and greater pickling power. The pH of the aqueous composition is preferably in the range of 1.5 to 3.5 for strip coating processes. For coating in pickling facilities, the concentration of all solids and active substances in the aqueous composition is often in the range of 200 to 800 g / l or 300 to 650 g / l. The content of the component or
    49/78 individual additives are adjusted accordingly to the total content. The aqueous composition is usually applied to the cleaned or cleaned metal strip, by spraying and compression, or by immersion and compression, in the form of a wet film, which often has a wet film thickness within the range of 1 to 12 pm. For that purpose, instead, for application, a chemical applicator or laminating applicator can be used.
    In many variations of the modality, the wet film is applied to metal sheets or strips and dried (drying method or without rinsing). Drying can take place, preferably in a temperature range of approximately room temperature to approximately peak metal temperature (PMT) of 120 ° C, preferably in a temperature range of 50 to 100 ° C or 70 to 100 ° Ç. The composition according to the invention can be specifically adjusted for slow or fast treatment in a pickling plant, for example, by means of an appropriate concentration and appropriate pH. Thus, neither the wet film nor the dry film is rinsed with water, so that the cations and compounds that are stripped from the metal surface are not removed, but are instead incorporated into the coating.
    In the coating according to the invention of metal parts, for example, sections of sheet metal, injected parts, moldings, and parts with complicated shapes, the reaction time of the first contact of the composition until its complete drying (process without rinsing) or for washing components that are removable by rinsing with water (rinsing process), it is preferably from 0.5 to 10 minutes. Longer times are, in principle, possible. The concentration of all solids and active substances in the aqueous composition is often in the range of 10 to 500 g / l or 30 to 300 g / l. Particularly for rinsed coatings, it may sometimes be advisable to treat the coatings with a subsequent rinse solution, as much is often removed when rinsing with water. Instead of layer formation, as a result of contact with the composition according to the invention, it is possible in some compositions that essentially only one effect occurs
    50/78 pickling and / or just a very thin coating, so that for hot dip galvanized surfaces, for example, the pattern of crystallization of zinc is discernible at the limits of zinc grains.
    Finding more than one individual polymer / copolymer that does not precipitate in the compositions according to the invention, when mixed, and that is stable for a very long period, i.e., an acid-tolerant polymer / copolymer, has been a complicated process . Therefore, it was surprising that one of these acid-tolerant polymers / copolymers changed so broadly the spectrum of properties of the coatings produced (See Figures 1 and 2).
    In DE 102008000600 A1 it was already surprising that the unmodified passivation coating, in contrast to a phosphate layer, provides an unusually high level of protection against exposed corrosion, even when the coating is even thinner than a phosphate layer. , and even when it is chromium free. In comparison, uncovered corrosion protection for unmodified passivation coatings was often better than comparable zinc phosphate coatings for a time factor of at least 20 or 30.
    It was surprising that the high quality properties of DE 102008000600 A1 compositions and coatings could now be dramatically increased, as shown by Figures 1 and 2 and the examples, and that the properties and the spectrum of properties could be improved so widely that application areas for substrates coated in this way have been significantly expanded.
    It was surprising that the aqueous composition according to the invention is stable for such a long period of time that it can be sold as a single component product, which is a great advantage over the unmodified passivations of DE 102008000600 A1 . This is because it has been shown that in the composition according to the invention it is not necessary to store an additive separately so that it is able to keep the product stable for a long time. Therefore, the composition according to the invention is much easier to maintain.
    51/78 sear than a two-component product, in which at least one additive needs to be stored separately and mixed immediately before the start of unmodified passivation.
    It was surprising that adding a cationic polyurethane resin to the composition according to the invention resulted in these exceptional properties of the coatings produced in this way.
    It was surprising that the composition according to the invention is unusually stable, even with a medium content of complexing agent and even with a very high content of solids and active substances.
    It was surprising that a stable composition, which is modified according to the invention, allows the appearance of the substrate surface to remain discernible, with virtually no change. Thus, for example, the granular structure can be easily visible through the coating according to the invention.
    The composition according to the invention and the method according to the invention can be used, particularly:
    - as a passivation agent for passivation of metal surfaces, with passivation coatings often having layer thicknesses ranging from 0.03 to 8 μιτι or 0.3 to 5 μιτι,
    - as a pre-treatment agent, for pre-treatment, before a subsequent coating, for example, before an organic coating, such as a varnish, the pre-treatment often having layer thicknesses ranging from 0.1 to 8 μιτι or 0.3 to 3 μπι,
    - as a subsequent rinse composition, for subsequent rinsing, for example, to seal, protect and / or to improve the properties of a pre-coat, for example, a conversion coating or an anodizing coating, the rinse coatings being subsequent layers often have a thickness of 0.03 to 5 μπι or 0.3 to 2 μιτι,
    - to produce thin film coatings, which often have a layer thickness ranging from 0.1 to 5 μιτι or 0.6 to2.5 μιτι, for example coatings for permanent coating and / or for paint
    52/78 base,
    - to produce thick film coatings, which often have a layer thickness within the range of 5 to 60 pm, or 12 to 25 pm for example, coatings for base paints,
    - as a pre-treated base paint to produce pre-pretreated coatings, with a conversion coating (pretreated base paint coatings), which often have layer thicknesses ranging from 0.1 to 30 pm, 1 to 20 pm or 3 to 12 pm,
    - to produce coatings on metal coatings, obtained by electroplating and / or non-current media, which often have a layer thickness ranging from 0.1 to 20 pm or 0.5 to 12 pm, and
    - to coat metallic and / or non-metallic surfaces, particularly for the simultaneous coating of metallic and non-metallic surfaces, and / or to protect metallic and / or non-metallic surfaces.
    The aqueous composition according to the invention can be used, in particular, as a passivating agent, as a pretreatment agent, as a subsequent rinse composition, to produce thin film coatings, to produce thick film coatings, such as base paint, as pre-treated base paint, and / or to coat metallic and / or non-metallic surfaces.
    The coating according to the invention can be used, in particular, passivation coating, as a pretreatment coating, as a subsequent rinse coating, as a thin film coating, with thick film coating, as a pretreatment base paint coating , and / or to protect metallic and / or non-metallic surfaces.
    EXAMPLES AND COMPARATIVE EXAMPLES
    Examples (B) and comparative examples (VB) described below are provided to explain the object of the invention in more detail.
    Aqueous compositions were mixed, whose compositions are shown as concentrated in Table 1. The dilution factor explains the
    53/78 dilution of the concentrate to the bath concentration used, that is, from a concentrate to a bath, so that for a concentrate, for example, 200 g and diluted with water to 1000 g, using a dilution factor of 5. The dilution factor means that the indicated composition was used without further dilution with water, as indicated in the table for its content for this example. In other examples, dilution was performed by a factor of up to 2, using deionized water. In contrast, the bath composition is shown in Table 2.
    Manganese was added as manganese carbonate and / or manganese oxide, and zinc was added as mono zinc phosphate and / or zinc oxide. 3-Aminopropyltrieoxysilane (APS) was added as silane
    1. 1-hydroxyethane-1,1-disphosphonic acid (HEDP) was used as a complexing agent 1 and L - (+) - tartaric acid was used as a complexing agent 2. The homogeneity and suitability of the application liquid were essentially influenced by the addition of the complexing agent 2. An ammonium molybdate salt was added to the inorganic mixture 2 as a corrosion inhibitor. Hexafluortitanic acid, hexafluorziconic acid and / or dihydroxobis (ammonium lactate) titanate were added as a compound of titanium and / or zirconium.
    Starting with the aqueous inorganic composition of the comparative example VBO in Table 1, which is very well suited as a passivating agent, various amounts and types of acid-tolerant polymers / copolymers were added, along with wax and associated additives. These polymers / copolymers are very well suited for this purpose, since they are stable even at pH values in the range of 1.5 to 3, due to the fact that there was no precipitation in the aqueous composition, when these substances were located and the dispersions produced in this way have been stable for at least 4 weeks, usually for up to more than 4 months. Non-ionic and / or cationic acid-tolerant resins were used as polymers / copolymers. A cationic polyurethane resin containing polycarbonate polyol as a dispersion (minimum MFT film formation temperature, approximately -5 ° C, 100% elasticity,
    54/78 approximately, 13 Mpa, elongation 230) and a modified anionic acrylic resin (T g approximately, 35 C, MFT approximately, 30 C, relatively hard, due to a Kõnig pendulum hardness of 70-120 s) used for testing.
    A wax emulsion based on oxidized polyethylene, cationically stabilized, and with a melting point of approximately 125 ° C, was used as a lubricant.
    A polysiloxane was used as a wetting agent to improve the wetting of the substrate during the application of wet film. A mixture of aliphatic hydrocarbons and SiO 2 was used as a defoaming agent. At least one glycol, particularly a polyethylene glycol ether containing 10 C atoms, has been added to further reduce the friction coefficient of the coating according to the invention. The pH was adjusted, as needed, using aqueous ammonia solution. The pH values in Table 1 apply to concentrates as well as bath concentrations. When the concentrates were diluted to prepare bath solutions, it was ensured that no precipitation occurred. The concentrates and bath solutions were stored at room temperature for up to 24 hours before use.
    Examples B1 - B18 according to the invention and comparative example VB0:
    In each chaos, multiple hot-dip galvanized steel sheets (HDG) and, in unexplained examples, cold rolled steel sheets (CRS), Galvalume® (AZ), Galfan® (ZA) and Alusi® ( AS) have also been used and tested.
    The plates were previously cleaned with a cloth, to remove a large part of oil to protect against corrosion and to obtain an even distribution of the oil or other impurities. The plates were then cleaned by spraying with a powder cleaning agent, free of silicate, moderately alkaline, until complete wetting with water was obtained. This generally took 20 to 30 seconds. This was followed by rinsing with tap water for 6 s for the immersion process, rinsing with
    55/78 tap for 6 s for the spraying process and rinse with demineralized water (DM) for 6 s. Most of the adherent water was then removed from the sheets by compression between two rubber rollers. The plates were then blow dried using oil-free compressed air.
    The dried plates were brought into contact with the aqueous composition, at a temperature of approximately 25 ° C, using a laboratory roller applicator. A wet film with a thickness of approximately 9 to 10 μπΊ was applied. A dry film with a thickness of 0.2 to 0.6 μιτι was produced by drying this wet film at 70 ° C of PMT. To that end, the sheets treated in this manner were dried at approximately 40 or 65 ° C PMT. Commercially available adhesive tape was then attached to the edges of the coated sheets in order to exclude edge effects during the corrosion test.
    The coated sheets were then tested for uncovered corrosion protection in the condensation water constant humidity test (KK test, currently referred to as the CH (constant humidity) test according to DIN EN ISSO 6270-2 and in the neutral salt spray test (NSS) according to DIN EN ISO9227. The evaluation was carried out visually. The values indicated for corrosion refer to the percentage of the surface area corresponding to the total surface area (100%), that is accessible for chemical exposure.
    The friction coefficient was determined according to a company-specific method, in which the application of the force required to move two overlapping coated sheets sideways is measured.
    The resistance to cleaning agents, refrigerants, ethanol and deionized water was determined by saturating a cloth with the medium and performing a defined rubbing under pressure and, in practical use, it is important for the estimated useful life, based on chemical resistance . In this regard, organic coatings can suffer a loss of quality, compared to inorganic coatings.
    The anti-fingerprint properties were determined by immersion in a synthetic hand sweat test solution according to the
    56/78 with BSH Test Standard LV 02 C, Chapter 6.2.2.2, March 1, 2007. The results indicate that the chemicals left by the fingerprints do not result in visible changes, such as discoloration or signs of corrosion.
    57/78
    Table 1: Compositions of concentrates, their dilution and properties of dry films produced

    58/78
    in CXI 320 co St CXI 2.6 the o 00 25 126 LO 2.6 320 the X - 50 CXI 2, 5 the o 00 33 169 IO 2.5 320 CO X - CD IOX ~ 2.31 1200 CD 393 CXI 2.3 the the co 50 253 io 2.3 320 20 The the X - CD X - 400 34 the X - Dilution factor X Q_ Layer weight, mg / m 2 2 Ti support, mg / m m oCM Q_0) ΌΦ tThe Q.D ω
    B8 HDG LO 30 30 50 the co 30 m HDG The The m mx— 30 in B6 HDG The The 30 09 the co 20 B5 HDG The The in 20 40 in B4 HDG The The 30 50 80 20 B3 HDG The The The 20 60 in B2 HDG The The in 30 80 in m HDG m 50 30 09 100 40 VB0 HDG The The TheV " 09 100 20 Dry film properties Substrate % of surface corrosion after 120 h of CH test % of surface corrosion after 480 h of CH test % of surface corrosion after 72 h of salt spray test % of surface corrosion after 120 h of salt spray test % of surface corrosion after 240 h of salt spray test % of surface corrosion after 2 weeks of stacking test
    59/78
    0.16 0.16 + Ο 0.16 ο0.21 +0.21 ο0.25 ο0.25 ο0.25 > 0.4 Friction coefficient Anti-fingerprint behavior Resistance to cleaning agents at pH 10.5
    B8a ZE The 40 20 100 20 The'Λ B7a LU N The The LO 30 tn 0.16 + Ο B6aI LU N The The 30 The00 20 0.16 οB5a LU N The TheThe m 0.21 +B4a LU N The The 30 80 20 0.21 οB3a LU N The The The 09 in 0.25 οB2a LU N The The m 80 in 0.25 οB1a ZE TheT— 30 30 100 40 0.25 VBOa ZE The The The 100 20 > 0.4 Dry film properties Substrate % of surface corrosion after 120 h of CH test % of surface corrosion after 240 h of CH test % of surface corrosion after 48 h of salt spray test % of surface corrosion after 120 h of salt spray test % of surface corrosion after 2 weeks of stacking test Friction coefficient Anti-fingerprint behavior Resistance to cleaning agents at pH 10.5
    60/78
    B17 B18 2.17: 1 2.17: 1 95 85 THE00The 13.2 13.2 4.8 4.8 | ------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- ------------------------------------------! 1.5 1.5 1.8 1.8 I ------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- --------------------------------------------5.7 5.7 I24.9 24.9 18.5 18.5 16.3 16.3 4.7 4.7 11.2 11.2 00CO 00oo 4.5 4.5 the o B16 X—cm THEx ~ 55 13.2 CO LOx ~ 00x— m 24.9 18.5 16.3CM X - 00 00 tn The B15 x ~cm 130 35 13.2 00 LOx ~ 00x— LO 24.9 18.5 16.3 THE CMX— 00 00 4.5 The B14 5.56: 1 25020 CM 2.3 cm 3.4 CDx— 11.1 9.8 oo cm co cm The B13 2.94: 1 19015.2 5.5 1.7 04 4.8 21.2 tn X - 13.9 4.0 9.5 6.6 6.6 3.8 The B12 X - cm 16513.2 4.8 IO X - 00 X - m 24.9 18.5 16.3 4.7 CMx ~ 00 CO 4.5 The V m x - cm 16513.2 4.8 m X - 00 X - LO 24.9 18.5 16.3CM X - 00 oo 4.5 LO X - B10 x - cm 16513.2 4.8 LO X - 00 X - it 24.9 18.5 16.3CMX " 00 00 4.5 CM B9 1.45: 1 13510.8 3.9 CM X - IO X - The 30.4 22.6 19.9 LO co X - 9.5 9.5 5.5 CM Content in g / l Organic weight: inorganic ratio Poimero A (cationic PU) Polymer B (acid tolerant acrylate) Wax Long chain alcohol Wetting agent Defoaming agent Zn THE0. tf)THE04 CL I <DT Ti fraction, calculated as metal Ftotal Complexing agent Silane 1 cnT z Dilution factor
    61/78
    2.8 2.8 1600 1600 32 32 150 150 CO cxT 1600 32 150 23 I I I1600 32 -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -----------------------1150 2.8 1600 CDV ‘ 89 2.8 1600 cxi 126 2.8 1600 32 150 2.8 1200 24 112.5 2.8 the the co CD T - in CXI the the co CO 103 ί: Q_ Layer weight, mg / m 2 Ti support, mg / m 2 m oCMQ_0) ΌΦ ex ex D CO
    COCO HDG The The The the V 20 m 0.16 T co HDG The The The CXI m The CDTHE B16 HDG The The The CXI in The 0.16 B15 HDG The The The CXJ in The 0.16 B14 HDG The 20 20 30 50 TheT— 0.16 B13 HDG The The LO 20 30 The 0.16 B12 HDGI The The The CXI m The 0.16 V "co HDG The The The m m The 0.16 B10 HDG The The The The 20 m 0.16 B9 HDG The 20 m 20 40 20 0.16 Dry film properties Substrate % of surface corrosion after 120 h of CH test % of surface corrosion after 480 h of CH test % of surface corrosion after 72 h of salt spray test % of surface corrosion after 120 h of salt spray test % of surface corrosion after 240 h of salt spray test % of surface corrosion after 2 weeks of stacking test Friction coefficient
    62/78
    Anti-fingerprint behavior
    B17a B18a ZE ZE THE LO LO 30 the X - 00The + + The THE The 20 m 0.16 + + B15a B16a ZE ZE The THE LO LO LO 0.16 + + + The THE The THEx— The 0.16 + + + B14a LU N The THE The 50 20 CO o ' + + B13a LU N The THE The The5— The 0.21 + + + B10a B11a B12a ZE ZE ZE The THE The the X - The 0 ^ 21 + + + + The LO LO 30 The 0.25 + + + m 20 The 09 m 0.25 The + + B9a ZE m 20 The 09 the X - 0.25 TheDry film properties Substrate % of surface corrosion after 120 h of CH test I% surface corrosion after 240 h CH test % of surface corrosion after 48 h of salt spray test % of surface corrosion after 120 h of salt spray test % of surface corrosion after 2 weeks of stacking test Friction coefficient Anti-fingerprint behavior Resistance to cleaning agents at pH 10.5
    63/78
    With reference to the examples and comparative example in Table 1:
    In Examples B2 to B4 according to the invention, a concentrate was undiluted or diluted with water by a factor of 1.5 to 2 and then brought into contact with hot dip galvanized steel sheets (HDG). Different layer weights and other layer properties indicate that corrosion resistance and other properties are a function of the layer thickness.
    In Examples B5 to B7 according to the invention, the cationic polyurethane resin content was continuously increased at a low rate. For cationic polyurethane resin additives with a low content, compared to inorganic components, the results showed significant differences in layer properties, as also indicated in Figures 1 and 2.
    Starting from Examples B5 to B7 according to the invention, the cationic polyurethane resin content was further increased for Examples B11e B12 according to the invention. In Examples B8 to B10 according to the invention, the concentration of the bath was varied by appropriate dilution. In Examples B9, B10, B11, B13 and B14 according to the invention, all stringent customer requirements have been met.
    Examples B13 to B16 according to the invention additionally have a varied content of acid-tolerant acrylate with a low styrene fraction, which as a modified anionic dispersion is latently cationic, which has been replaced by a smaller fraction of polyurethane dispersion cationic. The properties of the coating showed a slight deterioration, only after this acrylate was added in larger quantities.
    In tests that are not described in the present, it was also determined that the inorganic ’’ fraction, as well as the “organic” fraction can be varied chemically by process conditions over wide limits, in order to produce superior coatings.
    With reference to the examples in Table 2:
    Unless otherwise indicated, they
    64/78 ments were adopted for the examples and comparative examples for Table 2 as well as for Table 1.
    Non-ionic and / or cationic resins, tolerant to acids, were used as polymers / copolymers. A cationic polyurethane resin, containing polycarbonate polyol (MTF approximately-5 ° C, elasticity at approximately 100, 13 Mpa, elongation 230%) as well as a modified anionic acrylic resin (T g approximately, 35 ° C, approximately MFT, 30 ° C, relatively hard due to the Kõnig pendulum hardness of 70-10 s) were used for the tests. Its weight ratio is indicated as "urethane: acrylate polymer ratio". L - (+) - tartaric acid (hydroxycarboxylic acid) was used as a complexing agent 2, particularly, to optimize the homogeneity and stability of the preparation for a very long storage period and subsequent application. The stability of the compositions was insufficient without the addition of hydroxycarboxylic acid, since phase separation and agglomerate formation easily occurred. These compositions were not usable (comparative examples VB39-VB41).
    An "inorganic" fraction is understood to mean the inorganic composition based on patent application DE 102008000600 A1 (inorganic mixture 1) or based on a very similar composition. Therefore, a distinction is made between inorganic mixture 1 and inorganic mixture 2. Inorganic mixture 1 is specifically optimized for use on hot dip galvanized metal surfaces and contains compounds based on monozinc phosphate, hexafluortitanic acid, complexing agent 1, molybdate , aluminum, manganese, nitrate and ammonium in similar quantities as for the inorganic mixture 1. In the inorganic mixture 3, the hexafluortitanic acid in the inorganic composition of the inorganic mixture 1 was replaced by hexafluorzironic acid.
    An "organic" fraction is understood to mean the organic composition, which contains at least one polymer / copolymer, wax and associated additives.
    In the comparative examples VB20 / 1 and VB20 / 2, passive agent
    65/78 inorganic acid was incorporated in an unmodified form as an inorganic fraction, and an organic additive was not mixed.
    Hot dip galvanized sheets (HDG) and electrolytically galvanized sheets (ZE) were used as substrates for Examples B21 - B47 according to the invention for the associated comparative examples.
    The plates were first cleaned with the alkaline cleaning agent Gardoclean® 5080 from Chemetall GmbH, at a concentration of 25 g / l, at pH 10 and 60 ° C, sprayed at 1 bar for a period of 20 s.
    The cleaned plates were rinsed, first with tap water and then with completely demineralized water. The adherent water was dried at 100 ° C for a period of approximately 2 minutes, until the water was completely evaporated.
    The composition according to the invention was applied to the cleaned plates using a No. 3 spiral applicator forming a wet film with a layer weight, often approximately 5 g / m 2 . The mixture of inorganic and organic fractions according to the invention was used to simultaneously form a conversion layer and a predominantly organic layer, which apparently was coordinated only gradually with the conversion layer.
    The dry layer thickness was adjusted by adjusting the concentration of the liquid composition and therefore adjusting the dry residue. The dry layer thickness was adjusted, for example, by 20% hair to approximately 1000 mg / m 2 dry film for Examples B21 - B41, and to 10% by weight for approximately 500 mg / m + 2 dry film for Examples B42 - B43.
    Corrosion protection was tested without a coat of varnish, on the one hand, in the salt spray test according to DIN EN ISO 2997, and, on the other hand, in the constant humidity test by condensation water (referred to as the test CH or previously KK test) according to DIN EN ISO 6270-2 CH. In the salt spray test, the percentage
    66/78 The surface corrosion rate was determined after 72 h, 120 h and 240 h. In the CH test, the percentage of corrosion and surface was determined after 120 h, 240 h and 480 h in the constant humidity test by condensation water according to DIN EN ISO 6270-2 CH.
    The moldability of coated bodies according to the invention, such as sheets, for example, is of great importance for many applications. During molding, cracks cannot appear and corrosion cannot occur in extremely thin dry films, often with a thickness of 0.4 to 2 m. The moldability of coated molded parts has been tested in three variants:
    1. Deep stamping using the Erichsen tester, Erichsen Model 142-20, with a compression pressure of 2500 kp.
    2. Deep drawing test under these conditions, followed by a 24 h salt spray test according to DIN EN ISO 927.
    3. Deep drawing test under these conditions, followed by a constant humidity test with condensation water and 120 h in accordance with DIN EN ISO 6270-2 CH.
    4. Examples B21 to B30 showed excellent moldability. None of the other examples have been tested extensively, since the properties of the dry film were less satisfactory.
    Varnish adhesion was tested in the cross-section test according to DIN EN ISO 2409 at a cutting distance of 1 mm, and in the conical mandrel curvature test according to DIN EN ISO 6860. In the coin test, one coin it was pulled with uniform pressure across the direction and movement and approximately perpendicularly to the coated substrate, in order to result in a uniform convex curvature, without chipping. This is not a standardized test, but in practice, it is very significant.
    The ability to overcoat bodies according to the invention, such as sheets, for example, is also very important for
    67/78 many applications. Unmolded bodies as well as molded coated bodies can be overcoated. For a composition rich in urethane, the ability to overcoat proved to be very good, while for a composition rich in acrylate, the ability to overcoat was often deficient. Examples B21 to B30 showed excellent aptitude for overcoating. None of the other examples have been tested extensively, since the properties of the dry film were less satisfactory.
    The thickness of the dry film resulting in the examples, applied to electrolytically galvanized substrate surfaces, under the same 10 conditions, was slightly greater than for hot-dip galvanized steel, due to the higher surface roughness of the metal-plated substrates.
    The resistance to cleaning agents was determined using the alkaline, liquid cleaning agent, Gardoclean S 5102 from Chemetall GmbH ,, at 15 a concentration and 25 g / l, at pH 10 and 65 ° C, for a period of 20 s, and determining the weight difference before, compared to after, cleaning.
    68/78
    Table 2: Bath compositions and properties of dry films produced
    B28 T 2.19 00 6'09 609 CD Ii 2.8 8'0 - 1.7 62.72.0-2.5 Homogeneous, B27 !The o o CO 53.4 53.3 THE) 00CM 00THEΓ-- CO2.0-2.5 Homogeneous, B26 CO 2.70 800.0 32.9 97.5 0'6 2.8 0.8 - B- X2.0-2.5 Homogeneous, B25 2.19 O o 00 30.3 91.5 0'6 2.8 CO o 'r-_ 62.72.0-2.5 Homogeneous, B24 ! n o o o 00 26.8 79.9 9.0 CO cm ' 8'0B- CO2.0-2.5 Homogeneous, B23 100% acrylate 2.70 800.0130.5 0'6 2.8 8'0I T- ' r- n2.0-2.5 Homogeneous, B22 2.19 O o 'o 00121.8 0'6 2.8 8'0 T- · B- 62.72.0-2.5 Homogeneous, B21 ! n 800.0106.8 9.0 2.8 00 o 'B- CO2.0-2.5 Homogeneous, VB20 / 2 • • 944.0 56.0 2.0-2.5 Homogeneous, VB20 / 1 • - 944.0 56.02.0-2.5 homogeneous, Content in g / l urethane: acrylate polymer ratio organic: inorganic rate DM water polymer A (cationic PU) polymer B (acid tolerant AC) oxidized polyethylene long chain alcohol wetting agent defoamer complexing agent 2 inorganic mixture inorganic mixture 2 T Q. application liquid
    B28 Cxj § B27 -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- ----------130 1080 B26 The CM 1040 B25 s CO o B24 CO The00 o B23 The CM 1040 B22 s 1080 B21 30 CO o VB20 / 2TJ c VB20 / 1d c HDG substrate Ti support, mg / m 2 dry film holder, mg / m 2
    69/78
    LO B28a cd CXI 1305 ID B28B28aThe The THETheTheCD CO B27a 36 1296 36 B27B27aThe The TheTheThe52 B26a CXI ID 1300 CXI ID B26B26aThe CM IDThemin B25a CD CXI 1305 <D B25B25aThe CXI IOThemCD CO B24a CD CO 1296 36 B24B24aThe CXI THEThem52 B23a CM ID 1300 CXI m I ------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- ------------B23B23aThe IO 20Thethe CXIID B22a O) CXI 1305 45 B22B22aCXI ID 20The20CD CO CM m 36 1296 36 B21B21aCXI ID TheThethe CMCD VB20 / 2aç CD IVB20 / 2VB20 / 2aLD 80 100o (XIThe12.5 VB20 / 1a CDCXI The'ç 12.5 the CM m>VB20 / 1aCXI ID Theinthe CDTi: dry substance rate aptitude for overcoatingZE substrate Ti support, mg / m 2 dry film holder, mg / m 2 Ti: dry substance rate Dry film propertiesHDG substrate corrosion in the salt spray test: % of surface corrosion after 48 h % of surface corrosion after 96 h % of surface corrosion after 168 h corrosion in the CH test: surface corrosion after 504 h Cleaning agent resistance, 65 ° C,120 s: % by weight of dry film removal moldability in stamping test
    70/78
    OKThe OK The The OK The The OK The The OK The The OK The The OK The The OK The The not possible, 100 The not possible, The10 09 deep, 2.5 t: deep drawing test salt spray test above + 24 h: % of surface corrosion after 24 h CH test above + 120 h: % of surface corrosion after 120 h
    B28a HDG Varnish adhesion without cleaning the dry film coated with epoxy-polyester powder varnish: CNF—0i Varnish adhesion after cleaning the dry film and subsequently coating with epoxy-polyester powder varnish: CXJH-0 > 20 B27a HDG GT2 S Λ i GT2 > 20IB26a IHDG IGT2 i ------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- --------------> 20 • GT2 The CMΛB25a HDG GT2 > 20 ! GT2 > 20 B24a HDG CXIΙ-Ο > 20GT2 > 20 ! B23a HDG ΙΟ > 20GT4 > 20B22a HDG 0 OJΛ0 > 20 B21a HDG 0 > 20 ! GT4 > 20 i VB20 / 2a HDG VB20 / 1a HDG Ι-Ο V + + GT1 V + Dry film properties substrate cross section according to DIN ENISO 2409 1 mm bending test by conical mandrel according to DIN EN ISO 6860 [mm] coin test cross section according to DIN ENISO 2409 1 mm bending test by conical mandrel according to DIN EN ISO 6860 [mm] coin test
    71/78
    B28a LU NCM IT) 20 πCM (D ZEThe CM <n (V<0 CM CD LU NlCM THE the co coin LU THE The CM CD N CO ΦCM CD ZETHE m The (Uco LU The The CM ffi N CM (D <0CM LU The THE CM CD N CD «B21 ZEThe CM THE coCMδCM OD ZEThe00 100 100 >(VThe LUThe The The CM NcoCD m>x: co _ç CM The coCM φ<D a>Φ THE<0 KO (ΛCO THE TheTHE dry filmspray jperficie dep 8ΦTHEΦ2 jperficie dep Φd) </) (Λ <0 The 0) φ Φ <0 Φ<0 Φ Ό O Ό O * o o Ό (0 Ό THE the no tCQ 10 2 »Aj co o t KQ (0 g φ ro ten (Λ 8 8 8 CL (/> The 0) Φ Φ THE -Q Ό2 ω the o X © 0 s The' xP o '
    B38The 0'009 35.2 35.2 CD 2.8 COr- CM B37 Id the CO 53.4 53.3 CD' 2.8 co -38.9 B36 100% AC 2.70 o o o co130.5 0'6 2.8 co1.7B35 I2.19 o o 'o 00coCM 0'6 2.8 8'0r-B34 ¢) 800.0co (D * O 9.0 2.8 8'0 B33 T 2.70 o o 'o co 65.2 65.2 0'6i 2.8 CO or-.B32 2.19 800.0 60.9 60.9 0'6 2.8 0.8 -. r-B31 In o o 'o co 53.4 53.3 9.0 2.8 0.8 V- ' r-B30 100% PU the cm o o 'o co 130.40'6 2.8 8'0 -. r- J B29TheCM o o 'o co 65.2 65.2 0'6 2.8 CO o 'K-. 3 Content in g / l urethane: acrylate polymer ratio organic: inorganic rate DM water polymer A (cationic PU) polymer B (acid tolerant AC) oxidized polyethylene long chain alcohol wetting agent defoamer complexing agent 2 inorganic mixture
    72/78
    Ο 2.0-2.5 Homogeneous,B38‘040 CM tf) B38aTHE 52B38a HDGTHE CM 38.9 2.0-2.5 Homogeneous,B37 30 O 00 OT— 36 B37a <o 1080 CD COB37a HDGThe CM 5 2.0-2.5 Homogeneous,B36 20 1040 CM tf) B36a the CM 1040 CM tf)B36a HDGtf) CO 62.7 2.0-2.5 Homogeneous,B35 s CO o tf) B35a CM CO o tf)B35a HDGtf) 09 ° 0 2.0-2.5 Homogeneous,B34 the CO o CO o 36 B34a CO o CO o 36B34a HDGtf) 80 J 2.0-2.5 Homogeneous,B33 the CM 1040 CM m B33a tf) CM 1300 CM tf)B33a HDGtf) THEV ” 62.7 2.0-2.5 Homogeneous,B321080 tf) B32a σ> CM 1305 tf)B32a HDGtf) The CO 2.0-2.5 Homogeneous,B31 the co CO o to CO B31a <D co 1296 <0 COB31a HDGtf) 202.0-2.5 Homogeneous,B30 the CM 1040 CM tf) B30a tf) CM 1300 CM tf)B30a HDGThe THE2.0-2.5 Homogeneous,B29 the CM 1040 CM tf) B29a 25 1300 CM tf)B29a HDGCM tf) inorganic mixture 2 τ Q. application liquidHDG substrate Ti support, mg / m 2 dry film holder, mg / m 2 Ti: dry substance rate aptitude for overcoatingZE substrate Ti support, mg / m 2 dry film holder, mg / m 2 Ti: dry substance rateDry film properties Substrate corrosion in the salt spray test: % of surface corrosion after 48 h % of surface corrosion after 96 h
    73/78
    tf>THE Varnish adhesion without cleaning the dry film coated with epoxy-polyester powder varnish: tf) The The00 tf) 100 tf) the o tf> the co CM The CM 08 CM THE THE THE OK THE THE GT1 V + + The THE 09 OK The The IGT2 > 20 • % of surface corrosion after 168 h corrosion in the CH test: surface corrosion after 504 h Cleaning agent resistance, 65 ° C, 120 s: % by weight of dry film removal moldability in stamping testdeep, 2.5 t: deep drawing test salt spray test over + 24 h % of surface corrosion after 24 h CH test above + 120 h % of surface corrosion after 120 h cross section according toDIN EN ISO 2409, 1 mm bending test by conical mandrel according to DIN EN ISO 6860 [mm] coin test
    Varnish adhesion after cleaning the dry film and subsequently coating with epoxy-polyester powder varnish:
    74/78
    B38a ZE The 40 09B37a IZE The 04 ms 100% PU 2.70 the the co 125.4 - the in CD B36a LU N m CO 100 B46 100% AC 2.70 800.0 • 125.5 in 0'6 B35a ZE m THE 100 B45 100% PU 2.70 o o CO 130.4 - - 9.0 B34a ZE IO CO the IO B44 100% AC 2.70 o o 'o co - 130.5 0'6 B33a ZE The04 The CD 100 B43 100% PU 2.70 900.0 62.3 • - m B32a ZE 25 CO The B42 100% AC 2.70 0'006 - 62.3 - 4.5 B31a ZE The THE The04 m> T7 2.19 o o 'o co 60.9 60.9 • 9.0 ο V + + B30a ZE The 04 CO VB40 100% PU 2.70 800.0 130.4 < • 0'6______ GT 2 > 20 > B29a ZE 04 m CO VB39 The <Xp o 'O O 2.19 o o 'o CO 121.8 • 9.0 cross section according to DIN ENISO 2409 1 mm bending test by conical mandrel according to DIN EN ISO 6860 [mm] coin test Dry film properties Substrate corrosion in the salt spray test: % of surface corrosion after 48 h % of surface corrosion after 72 h Content in g / l urethane: acrylate polymer ratio organic: inorganic rate DM water polymer A (cationic PU) polymer B (acid tolerant AC) crosslinker (polyfunctional aziridine) oxidized polyethylene
    75/78
    2.8 00Ο - r- η in CXÍI OCXI Homogeneous,m The CXI 1040 CXI in s The CXI - 2.8 0.8 in • - in (XIICXI Homogeneous, B46 8 • 1040 52 • B46 the CXI 2.8 0.8r- - in in CXII the CXI Homogeneous, B45 the CXI THE • CXI m B45 •2.8 00 Ο *r- - • in in cxiI the CXÍ Homogeneous, B44 the CXI 1040 • CXI m B44 - 20ο ' 9'0 8Ό • CN • inCXi ’I the CXJ * Homogeneous, B43 The • 520 (XI m B43 CXI •ο CD ο ' 0.8 • (XJ • in CxiI the Cxi Homogeneous, B42 The 520 CXJ m • B42 CXI • 2.8 0.8• s • in cxTI the Cxi not homogeneous, not applicable VB41 - • 1 - • VB41 • • 2.8 0.8• 55.8 • • in CXII the cxi VB40 • • • * - VB40 • • 2.8 80• 64.4 • • in cxiI the cxi VB39 - 1 - • VB39 • long chain alcohol wetting agent Defoaming agent complexing agent 2 inorganic mixture 1 inorganic mixture 2 inorganic mixture 3 * application liquid HDG substrate Ti support, mg / m 2 Zr support, mg / m 2 dry film holder, mg / m 2 Ti: dry substance ratio ratio of Zr: dry substance ZE substrate Ti support, mg / m 2 Zr support, mg / m 2
    76/78
    Ο CXI in m HDGThe The TheThem LU NJThe CM 30 1040 CXI ΙΌ •B46 HDGin the co the coTheB46 ZELT) The CM 09 104052B45 HDGThe The TheTheB45 ! ------------------------------------------------- -------------------------------------------------- -------------------------------------------------- -------------------------------------------------- ------------ZEThe CXJ the co 1040 • CM tf)B44 HDGThe io the CMthe CMB44 ZEm The CM the CD 624 CXI IO B43 HDGThe The ••B43 ZEthe CXI 100624 52 B42 HDG30 09 ••B42 ZE06 100< - -VB41 HDG • >-VB41 ZE - • •VB40 HDG• - •VB40 ZE• • • •VB39 HDG- • •-IVB39 ZEdry film holder, mg / m 2 Ti: dry substance ratio ratio of Zr: dry substanceDry film properties Substrate corrosion in the salt spray test: % of surface corrosion after 48 h % of surface corrosion after 96 h % of surface corrosion after 168 h Cleaning agent resistance, 65 ° C, 120 s % by weight of dry film removalDry film properties Substrate corrosion in the salt spray test: % of surface corrosion after 48 h % of surface corrosion after 72 h % of surface corrosion after 120 h
    77/78
    The compositions according to the invention proved to be very suitable as acidic preparations, with pH values, particularly, in the range of 1.5 to 3, for coating substrates made of pure zinc, zinc-titanium alloys, galvanized steel by immersion at hot, and electrolytically galvanized steel.
    If no complexing agent 2 has been added or complexing agent has been added, in total insufficient precipitation and heterogeneities can easily occur in these acidic compositions and, therefore, no suitable film could be applied (VB39 - VB41).
    Due to the stripping effect, during application and drying, a chemical reaction occurs between the treatment liquid and the substrate surface. Thus, excellent corrosion protection properties are obtained, while maintaining the optimum appearance of the substrate.
    A polymer / copolymer ratio e) + wax f) for inorganic fractions a) to d), approximately in the range of (2 to 2.5): 1 proved to be optimal for most of the properties of the coatings according to the invention.
    It was found that a certain content of Ti and / or Zr is necessary in all tests. This is because of the possible need to obtain a thin layer based on Ti and / or Zr on the metallic substrate. It has been shown that it is important that the support of Ti and / or Zr, calculated as metal, is in a range between 15 and 50 g / m 2 or between 20 and 40 g / m 2 , determined by fluorescence analysis by rays X. Corrosion protection can be impaired if the support is less. If support is greater, the stripping attack is often too great, or the consumption of chemicals is often unnecessarily high.
    It has proved advantageous and, sometimes, even necessary, that the composition according to the invention has a stripping effect on the metal surface. This is because if the stripping effect due to the composition is too low, the corrosion protection is often inadequate. If the stripping effect due to the composition is large more, an excessive amount of cations from the metal surface is absorbed
    78/78 due to the aqueous composition and the coating to be produced, with which the latter may have a lower corrosion protection.
    In many embodiments, the addition of a film-forming agent is useful for satisfactory, homogeneous coating formation. The film-forming agent is added, particularly for hard resins, in order to temporarily soften them. Adding at least one silane / silanol / siloxane was not shown to be necessary, either for the inorganic fraction or for the organic fraction, but it is useful in some compositions. This addition can be advantageous, particularly when aluminum-rich surfaces are coated.
    Adding at least one corrosion inhibitor, such as molybdate, can ensure additional corrosion protection.
    A high moisture resistance of the dry films was obtained for all samples according to the invention, when, after application, they were allowed to pass just a few hours until the films were used or until the moisture resistance test was carried out. In this case, the resistance to moisture resulted from another secondary reaction, after heating and / or drying.
    For good anti-fingerprint behavior of the coating according to the invention, a layer weight of at least 1000 mg / m 2 , or even at least 1200 mg / m 2 , is often required, and is often higher polymer / copolymer ratio is required. In particular, a higher content of acid-tolerant cationic polyurethane has proved useful for good anti-fingerprint behavior and good ability to overcoat the coating according to the invention.
    In comparison with coatings according to the invention in EZ and HDG [substrates], in zinc-aluminum alloys, such as Avalume® and Gafan®, for example, all necessary properties have been achieved, with the exception of a satisfactory aesthetic appearance of granular structure, since these alloys acquired a gray color in the absence of subsequent varnishing.
    权利要求:
    Claims (15)
    [1]
    1. Process for coating metallic surfaces, characterized by the fact that it has an aqueous composition having a pH value in the range of 1 to 4, containing:
    a) at least 1 g / L of phosphate, calculated as PO4,
    b) at least 0.1 g / L of at least one titanium and / or zirconium compound, calculated as Ti metal,
    c) at least 0.1 g / L of at least one complexing agent,
    d) at least 0.5 g / L of aluminum, chromium (III) and / or zinc cations and / or at least one compound containing aluminum, chromium (III) and / or zinc, and
    e) 1 to 500 g / L of a cationic dispersion rich in polyurethane containing polycarbonate and / or dispersion based on acrylate and / or styrene, where the composition has a weight ratio of organic polymers / copolymers e) to the inorganic passivation based on steps (a) to (d) in the range of 8: 1 to 0.2: 1, in which no instance of precipitation occurs in the aqueous composition and in which the coating is formed on film after application.
    [2]
    2. Process according to claim 1, characterized by the fact that the organic polymer / copolymer e) has a minimum temperature forming MFT film in the range of -20 to + 100 ° C, or the film thus formed has a temperature of transformation Tg in the range of -10 to + 120 ° C and / or a hardness using the pendulum of the Konig type in the range of 10 to 140 s.
    [3]
    3. Process according to claim 1 or 2, characterized by the fact that the composition has a weight ratio of organic polymers / copolymers e) to the inorganic passivating agent on the basis of a) to d), in the range of 6: 1 to 0.8: 1.
    [4]
    Process according to any one of claims 1 to 3, characterized in that the composition contains a total content of aluminum, chromium (III) and / or zinc cations and / or at least one compound with an aluminum content , chromium (III), and / or zinc, in the range of 0.5 to 80 g / L, calculated
    Petition 870190063443, of 07/08/2019, p. 11/65
    2/3 as metal.
    [5]
    Process according to any one of claims 1 to
    4, characterized by the fact that the composition contains a total content of iron and / or manganese cations, and / or at least one compound with an iron and / or manganese content, in the range of 0.1 to 20 g / L , calculated as metal.
    [6]
    Process according to any one of claims 1 to
    5, characterized by the fact that the composition contains a phosphate content in the range of 1 to 250 g / L, calculated as PO4.
    [7]
    Process according to any one of claims 1 to
    6, characterized by the fact that the composition contains a total content of at least one complexing agent, in the range of 0.1 to 60 g / L.
    [8]
    Process according to any one of claims 1 to
    7, characterized by the fact that the composition contains a total content of at least one compound of titanium and / or zirconium based on fluoride complex, in the range of 1 to 200 g / L, calculated as the respective compound.
    [9]
    Process according to any one of claims 1 to
    8, characterized by the fact that the composition contains a free fluoride content in the range of 0.01 to 5 g / L and / or a total fluoride content Ftotal in the range of 0.5 to 80 g / L.
    [10]
    Process according to any one of claims 1 to 9, characterized in that the composition contains a content of at least one silane / silanol / siloxane / polysiloxane in the range of 0.1 to 50 g / L, calculated on the basis of Si metal.
    [11]
    Process according to any one of claims 1 to 10, characterized in that the composition contains at least one inorganic compound in the form of particles, based on Al2O3, SiO2, TiO2, ZnO, ZrO2, soot and / or particles of corrosion protection, which have an average particle diameter less than 300 nm, measured in a scanning electron microscope.
    [12]
    Process according to any one of claims 1 to 11, characterized in that the metallic surfaces treated with the aqueous composition are based on aluminum, iron, magnesium, titanium, zinc
    Petition 870190063443, of 07/08/2019, p. 12/65
    3/3 and / or tin is treated with the aqueous composition, more particularly parts, tapes and / or plates.
    [13]
    13. Aqueous composition, characterized in that it is as defined in any one of claims 1 to 11.
    5
    [14]
    14. Coating, characterized by the fact that it is produced by the process, as defined in any one of claims 1 to 12.
    [15]
    15. Use of the coating as defined in claim 14, characterized by the fact that it is in the manufacture of vehicles, as architectural elements in the construction sector, or for the production of appliances and machines, such as, for example, electrical appliances or appliances. domestic use.
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    同族专利:
    公开号 | 公开日
    ZA201302578B|2014-06-25|
    JP5959521B2|2016-08-02|
    US20130177768A1|2013-07-11|
    CA2810747A1|2012-03-15|
    BR112013005656A2|2016-05-03|
    KR20140021511A|2014-02-20|
    CN103314136A|2013-09-18|
    AU2011298744B2|2015-01-22|
    JP2013542318A|2013-11-21|
    AU2011298744A1|2013-05-02|
    DE102011082312A1|2012-03-15|
    CA2810747C|2019-11-19|
    KR101895638B1|2018-09-05|
    WO2012032102A1|2012-03-15|
    MX2013002619A|2013-06-03|
    ES2664797T3|2018-04-23|
    CN103314136B|2016-03-16|
    EP2614175A1|2013-07-17|
    MX355473B|2018-04-19|
    EP2614175B1|2018-01-03|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-05-07| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-03-31| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-05-26| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/09/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102010040548|2010-09-10|
    DE102010040548.5|2010-09-10|
    PCT/EP2011/065506|WO2012032102A1|2010-09-10|2011-09-08|Method for coating metallic surfaces with a polymer-containing coating agent, the coating agent and use thereof|
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