Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
  • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
  • C09D5/084—Inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
  • C09D5/12—Wash primers
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
  • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1229—Composition of the substrate
  • C23C18/1241—Metallic substrates
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
  • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
  • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
  • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
  • C23C2222/20—Use of solutions containing silanes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T50/00—Aeronautics or air transport
  • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

• the invention relates to a method for coating metallic surfaces with an aqueous composition containing at least one silane and / or a compound related thereto and at least two further components. Furthermore, the invention relates to corresponding aqueous compositions and to the use of the substrates coated by the process according to the invention.
• Chromium (VI) compounds optionally together with various additives, or otherwise on phosphates, e.g. ZinkManganNickel-
• Phosphates optionally together with various additives.
• silanes / silanols in aqueous compositions for the preparation of siloxane / polysiloxane-rich anticorrosive coatings is basically known.
• silane / silanol / siloxane / polysiloxane is often referred to as silane in the following.
• These coatings have proven useful, but the methods of coating with a predominantly silane-containing aqueous solvent composition are sometimes difficult to apply. Not always, these coatings are formed with excellent properties.
• the corrosion protection and the paint adhesion of the formed siloxane or / and polysiloxane-rich coatings are often, but not always high and sometimes not sufficiently high for certain applications even with suitable application. It requires further processes using at least one silane, which have a high process safety and a high quality of the coatings produced herewith, in particular with regard to corrosion resistance and paint adhesion.
• silane-containing aqueous compositions moreover, a small amount of addition of at least one component has been selected from the group of organic monomers, Oligomers and polymers proven.
• the type and amount of silane addition is in part of critical importance for success.
• the addition amounts of silane for this purpose are comparatively low - usually only up to 5 wt .-% of all solids contents - and then act as a "coupling agent", the adhesion-promoting effect in particular between metallic substrate and paint and optionally between pigment and organic paint constituents In some cases, however, even a slight crosslinking effect may occur, with very little silane additions being added to thermally curable resin systems.
• composition of the aqueous bath even have better corrosion protection and better paint adhesion. This contradicts earlier experiences, according to which a rinse of a freshly applied and not even more dried coating based on
• Silane easily and often leads to a deterioration of the coating quality, if not even partial or occasionally leads to the complete removal of the coating.
• the object is achieved with a method for coating metallic surfaces with a silane / silanol / siloxane / polysiloxane-containing composition, the composition consisting essentially of a) at least one compound selected from silanes, silanols,
• an aqueous composition for coating metallic surfaces wherein the composition consists essentially of a) at least one compound selected from silanes, silanols, siloxanes and polysiloxanes and b) at least two titanium, hafnium, zirconium, aluminum or / and boron-containing compounds and optionally c) at least one kind of cation selected from cations of metals of the 1st to 3rd and 5th to 8th subgroups including Lanthanides and the second main group of the Periodic Table of the Elements or / and from at least one corresponding compound, d) at least one organic compound selected from monomers, oligomers, polymers, copolymers and block copolymers and / or e) from at least one influencing the pH Substance and also from f) water and g) optionally from at least one organic solvent.
• the composition consists essentially of a) at least one compound selected from silanes, silanols, siloxanes and polysilox
• silane is used here for silanes, silanols, siloxanes, polysiloxanes and their reaction products or derivatives, which are often also “silane” mixtures
• condensing in the context of this application refers to all forms of crosslinking, the Further crosslinking and the further chemical reactions of the silanes / silanols / siloxanes / polysiloxanes.
• coating in the context of this application relates onto the coating formed with the aqueous composition, including the wet film, the dried film, the throughdried film, the elevated temperature dried film, and the optionally further thermally and / or irradiated further crosslinked film.
• the aqueous composition according to the invention optionally comprises up to 15% by weight of the solids and active substances of substances a) to d) and f) of further substances which can help to improve the various properties of the aqueous composition and / or the coating and / or to adapt it to requirements
• additives such as biocide (s) and / or defoamer and / or at least one substance can be selected for these substances of silicon-free compounds having in each case at least one amino, urea or / and ureido group, hydroxide (s), carboxylate (s), nitrate (s) and phosphorus and oxygen-containing compounds such as phosphate (s) belong
• this term includes among the up to 15% by weight of the content of solids and active substances of the substances a) to d) and f) of further substances which are essentially only H ydroxide (e), acetate (s) and
• the aqueous composition is an aqueous solution, an aqueous dispersion or / and an emulsion.
• the pH of the aqueous composition is greater than 1, 5 and less than 9, more preferably in the range of 2 to 7, most preferably in the range of 2.5 to 6.5, in particular in the range of 3 to 6.
• the aqueous composition is at least one silane or / and at least one corresponding compound with at least one amino group, with at least one urea group or / and with at least one ureido group (imino) added, since the coatings produced hereby often have a higher paint adhesion and / or a higher affinity for the subsequent lacquer layer.
• silane or / and at least one corresponding compound having at least one such group it must be ensured that the condensation proceeds at very fast rates of pH below 2.
• the proportion of aminosilanes, ureidosilanes or / and silanes having at least one ureido group or / and corresponding silanols, siloxanes and polysiloxanes can be increased in the sum of all types of compounds selected from silanes, silanols, siloxanes and polysiloxanes, more preferably above 20 , over 30 or over 40 wt .-% are calculated as the corresponding silanols, most preferably above 50, above 60, above 70 or above 80 wt .-% are and optionally even up to 90, up to 95 or up to 100 Wt .-% amount.
• the aqueous composition has a content of silane / silanol / siloxane / polysiloxane a) in the range of 0.005 to 80 g / L, calculated on the basis of the corresponding silanols.
• This content is particularly preferably in the range from 0.01 to 30 g / l, very particularly preferably in the range from 0.02 to 12 g / l, to 8 g / l or to 5 g / l, in particular in the range from 0, 05 to 3 g / L or in the range of 0.08 to 2 g / L or to 1 g / L.
• These content ranges relate in particular to bath compositions.
• a concentrate is used to prepare a corresponding Bad ⁇ composition, in particular by dilution with water and optionally by adding at least one further substance, it is recommended, for example, a concentrate A with a content of silane / silanol / siloxane / polysiloxane a ) separately from a concentrate B containing all or almost all other constituents, and to merge these components in the bathroom.
• a concentrate A with a content of silane / silanol / siloxane / polysiloxane a separately from a concentrate B containing all or almost all other constituents, and to merge these components in the bathroom.
• at least one silane, silanol, siloxane and / or polysiloxane can also be partly or wholly in the solid state, be added in the solid state and / or be added as dispersion or solution.
• the content of silane / silanol / siloxane / polysiloxane a) in concentrate A is preferably in the range of 0.01 to 1000 g / L, calculated on the basis of the corresponding silanols. It is particularly preferably in the range from 0.02 to 200 g / l, very particularly preferably in the range from 0.05 to 120 g / l, in particular in the range from 0.1 to 60 g / l. Depending on the application, however, the concentration ranges of the concentrate A or of the bath may have different salary ranges.
• the composition particularly preferably contains a content of at least one silane, silanol, siloxane or / and polysiloxane a) each having at least one group selected from acrylate groups, alkylaminoalkyl groups, alkylamino groups, amino groups, aminoalkyl groups, succinic anhydride groups, carboxyl groups, epoxy groups, glycidoxy - Groups, hydroxy groups, urea groups, isocyanato groups, methacrylate groups and / or ureido groups (imino).
• the silanes, silanols, siloxanes and / or polysiloxanes in the aqueous composition, or at least their compounds added to the aqueous composition, or at least a portion of them are preferably water-soluble.
• the silanes are considered to be water-soluble if they have a solubility in water of at least 0.05 g / l, preferably of at least 0.1 g / l, at room temperature in the silane / silanol / siloxane / polysiloxane-containing composition. more preferably at least 0.2 g / L or at least 0.3 g / L.
• At least one silane / silanol / siloxane / polysiloxane is selected from fluorine-free silanes and the corresponding silanols / siloxanes / polysiloxanes each of at least one acyloxysilane, an alkoxysilane, a silane having at least one amino group such as an aminoalkylsilane Silane having at least one succinic acid group and / or succinic anhydride group, a bis-silyl silane, a silane having at least one epoxy group such as a glycidoxysilane, a (meth) acrylato-silane, a multi-silyl-silane, a ureidosilane, a vinylsilane or / and at least one silanol or / and at least one silane
• the at least one silane or the corresponding silanol / siloxane / polysiloxane particularly preferably has at least one amino group, urea group or / and ureido group.
• at least one silane or / and at least one corresponding silanol / siloxane / polysiloxane is selected from the group of or based on
• Aminoalkylaminoalkyltrialkoxysilan Aminoalkylaminoalkylalkyldialkoxysilan,
• aqueous composition at least one silane / silanol / siloxane / polysiloxane containing a fluorine-containing group.
• silane compound (s) the hydrophilicity / hydrophobicity can be set purposefully.
• At least one at least partially hydrolyzed or / and at least partially condensed silane / silanol / siloxane / polysiloxane is added to the aqueous composition.
• at least one pre-hydrolyzed, pre-condensed silane / silanol / siloxane / polysiloxane may optionally be added in each case. Such an additive is particularly preferred.
• At least one silane / silanol / siloxane / polysiloxane that is at least substantially or / and completely hydrolyzed and / or at least substantially or / and completely condensed can be added to the aqueous composition.
• an unhydrolyzed silane binds poorer to the metallic surface than an at least partially hydrolyzed silane / silanol.
• a largely hydrolyzed and not or only slightly condensed silane / silanol / siloxane binds much better in many variants to the metallic surface as an at least partially hydrolyzed and substantially condensed silane / silanol / siloxane / polysiloxane.
• a completely hydrolyzed and largely condensed silanol / siloxane / polysiloxane shows in many embodiments only a slight tendency to be chemically bound to the metallic surface.
• At least one siloxane or / and polysiloxane may be added to the aqueous composition containing little or no content, e.g. less than 20 or less than 40% by weight of the sum of silane / silanol / siloxane / polysiloxane - of silanes / silanols.
• the siloxane or polysiloxane is preferably short-chain and is preferably applied by rollcoater treatment. If necessary, this will then have an effect on the coating due to greater hydrophobicity and higher blank corrosion protection.
• the aqueous composition comprises at least two or even at least three compounds of titanium, hafnium, zirconium, aluminum and boron. These compounds may differ in their cations and / or in their anions.
• the aqueous composition, in particular the bath composition preferably has a content of at least one complex fluoride b), more preferably at least two complex fluorides selected from complex fluorides of titanium, hafnium, zirconium, aluminum and boron. Preferably, their difference is not only in the nature of the complex.
• the aqueous composition in particular the bath composition, has a content of compounds b) selected from compounds of titanium, hafnium, zirconium, aluminum and boron in the range from 0.01 to 50 g / L calculated as the sum of the corresponding metals.
• This content is particularly preferably in the range from 0.1 to 30 g / L, very particularly preferably in the range from 0.3 to 15 g / L, in particular in the range from 0.5 to 5 g / L.
• the content of compounds of titanium, hafnium, zirconium, Aluminum and boron in the concentrate for example in the silane / silanol / siloxane / polysiloxane-free concentrate B, preferably in the range from 1 to 300 g / l, are calculated as the sum of the corresponding metals. It is particularly preferably in the range from 2 to 250 g / L, very particularly preferably in the range from 3 to 200 g / L, in particular in the range from 5 to 150 g / L. It is preferred that it does not contain aluminum phosphate, titanium sulfate, zirconium nitrate or / and zirconium chloride.
• the composition preferably contains at least one complex fluoride, the content of complex fluoride (s) in particular being in the range from 0.01 to 100 g / l calculated as the sum of the corresponding metal complex fluorides as MeF 6 .
• This content is preferably in the range from 0.03 to 70 g / L, particularly preferably in the range from 0.06 to 40 g / L, very particularly preferably in the range from 1 to 10 g / L.
• the complex fluoride can be present in particular as MeF 4 or / and as MeF 6 , but also in other stages or intermediates. In many embodiments, at least one titanium and at least one zirconium complex fluoride are advantageously present simultaneously.
• the content of these compounds in the concentrate for example in the silane / silanol / siloxane / polysiloxane-free concentrate B, preferably in the range from 0.05 to 500 g / l, can be calculated as the sum of MeF 6 . It is particularly preferably in the range from 0.05 to 300 g / L, very particularly preferably in the range from 0.05 to 150 g / L, in particular in the range from 0.05 to 50 g / L.
• a different type of titanium, hafnium, zirconium, aluminum or / and boron compound may also be added, for example at least one hydroxycarbonate and / or at least one other water-soluble or slightly water-soluble compound, e.g. at least one nitrate and / or at least one carboxylate.
• only cations or corresponding compounds are selected as cations and / or corresponding compounds c) from the group of magnesium, calcium, yttrium, lanthanum, cerium, vanadium, niobium, tantalum, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, silver and zinc, particularly preferably from the group of magnesium, calcium, yttrium, Lanthanum, cerium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, copper and zinc, except when traced.
• the aqueous composition in particular the bath composition, has a content of cations and / or corresponding compounds c) in the range from 0.01 to 20 g / l, calculated as the sum of the metals. It is particularly preferably in the range from 0.03 to 15 g / L, very particularly preferably in the range from 0.06 to 10 g / L, in particular in the range from 0.1 to 6 g / L.
• the content of these compounds in the concentrate for example in the silane / silanol / siloxane / polysiloxane-free concentrate B, preferably in the range of 1 to 240 g / L are calculated as the sum of the metals. It is particularly preferably in the range from 2 to 180 g / L, very particularly preferably in the range from 3 to 140 g / L, in particular in the range from 5 to 100 g / L.
• the composition contains at least one kind of cations selected from cations of cerium, chromium, iron, calcium, cobalt, copper, magnesium, manganese, molybdenum, nickel, niobium, tantalum, yttrium, zinc, tin and other lanthanides or / and at least one corresponding thereto Connection.
• cations selected from cations of cerium, chromium, iron, calcium, cobalt, copper, magnesium, manganese, molybdenum, nickel, niobium, tantalum, yttrium, zinc, tin and other lanthanides or / and at least one corresponding thereto Connection.
• not all cations contained in the aqueous composition are not only dissolved out of the metallic surface by the aqueous composition but also at least partially or even substantially added to the aqueous composition Service. Therefore, a freshly prepared bath of certain cations or compounds may be free, which are released only from reactions with metallic materials or from reactions in the
• manganese ions or of at least one manganese compound has surprisingly been found to be particularly advantageous. Although apparently no or almost no manganese compound is deposited on the metallic surface, this additive apparently promotes the deposition of silane / silanol / siloxane / polysiloxane and thus significantly improves the properties of the coating.
• An addition of magnesium ions or at least one magnesium compound has unexpectedly been found to be advantageous since this addition promotes the deposition of Titan ⁇ and / or zirconium compounds, presumably as oxide and / or hydroxide, on the metallic surface and thus the properties the coating significantly improved.
• a combined addition of magnesium and manganese leads in part to even further improved coatings.
• the composition contains a content of at least one kind of cation or / and corresponding compounds selected from alkaline earth metal ions in the range of 0.01 to 50 g / L calculated as corresponding compounds, more preferably in the range of 0.03 to 35 g / L, completely more preferably in the range of 0.06 to 20 g / L, in particular in the range of 0.1 to 8 g / L.
• the alkaline earth metal ions or corresponding compounds may help to enhance the deposition of compounds based on titanium or / and zirconium, which is often advantageous in particular for increasing the corrosion resistance.
• the content of these compounds in the concentrate for example in the silane / silanol / siloxane / polysiloxane-free concentrate B, preferably in the range from 0.1 to 100 g / L are calculated as the sum of the corresponding compounds, more preferably in the range of 0.3 to 80 g / L, most preferably in the range of 0.6 to 60 g / L, in particular in the range of 0.5 to 30 g / L.
• the composition preferably contains at least one kind of cation selected from cations of iron, cobalt, magnesium, manganese, nickel, yttrium, zinc and lanthanides or / and from at least one corresponding compound c), in particular in the range from 0.01 to 20 g / L calculated as the sum of the metals. It is particularly preferably in the range from 0.03 to 15 g / L, very particularly preferably in the range from 0.06 to 10 g / L, in particular in the range from 0.1 to 6 g / L.
• the content of these compounds in the concentrate for example in the silane / silanol / siloxane / polysiloxane-free concentrate B, preferably in the range of 1 to 240 g / L are calculated as the sum of the metals. It is particularly preferably in the range from 2 to 180 g / L, very particularly preferably in the range from 3 to 140 g / L, in particular in the range from 5 to 100 g / L
• the composition contains a content of at least one organic compound d) selected from monomers, oligomers, polymers, copolymers and block copolymers, in particular at least one compound based on acrylic, epoxy or / and urethane.
• at least one organic compound having at least one silyl group can also be used.
• the composition contains a content of at least one organic compound d) selected from monomers, oligomers, polymers, copolymers and block copolymers in the range of 0.01 to 200 g / L calculated as solid addition.
• the content is particularly preferably in the range from 0.03 to 120 g / L, very particularly preferably in the range from 0.06 to 60 g / L, in particular in the range from 0.1 to 20 g / L.
• organic compounds may help in some embodiments to even out the formation of the coating.
• These compounds may contribute to the formation of a more compact, denser, more chemically resistant or / and more water resistant coating compared to silane / silanol / siloxane / polysiloxane-based coatings, etc., without these compounds.
• the hydrophilicity / hydrophobicity can be set purposefully.
• a highly hydrophobic coating is problematic in some applications because of the required attachment of particular water-based paints.
• a stronger hydrophobicity can be set.
• a combination with compounds having a certain functionality may prove to be particularly advantageous, for example compounds based on amines / diamines / polyamines / urea / imines / diimines / polyimines or derivatives thereof, compounds compounds based on, in particular, blocked isocyanates / isocyanuric / melamine compounds, compounds with carboxyl or / and hydroxyl groups, for example carboxylates, long-chain sugar-like compounds, for example (synthetic) starch, cellulose, saccharides, long-chain alcohols or / and their derivatives.
• long-chain alcohols in particular those having 4 to 20 carbon atoms are added, such as butanediol, butyl glycol, butyl diglycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethyl glycol propyl ether, ethylene glycol hexyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether or a propylene glycol ether such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol mono- propyl ether, dipropylene glycol monopropyl ether, tripropylene glyco
• the ratio by weight of compounds based on silane / silanol / siloxane / polysiloxane calculated on the basis of the corresponding silanols to compounds based on organic polymers calculated as a solids addition in the composition is preferably in the range from 1: 0.05 to 1: 3, especially preferably in the range from 1: 0.1 to 1: 2, very particularly preferably in the range from 1: 0.2 to 1: 1.
• this ratio is preferably in the range from 1: 0.05 to 1: 30, particularly preferably in the range from 1: 0.1 to 1: 2, very particularly preferably in the range from 1: 0.2 to 1:20, in particular in the range from 1: 0.25 to 1:12, in the range from 1: 0.3 to 1: 8 or in the range of 1: 0.35 to 1: 5.
• a catalyst for the hydrolysis of a silane e.g. Acetic acid are added.
• the blunting of the pH of the bath can be carried out, for example, with ammonia / ammonium hydroxide, an alkali hydroxide or / and an amine-based compound such as e.g. Monoethanolamine occur while the pH of the bath is preferably lowered with acetic acid, hydroxyacetic acid and / or nitric acid.
• Such contents are among the pH-affecting substances.
• the composition contains a content of silicon-free compounds having at least one amino, urea or / and ureido group, in particular compounds of amine / di- amine / polyamine / urea / imine / diimine / polyimine and their derivatives, preferably in the range of 0.01 to 10 g / L calculated as the sum of the corresponding compounds.
• the content is particularly preferably in the range from 0.03 to 7 g / L, very particularly preferably in the range from 0.06 to 4 g / L, in particular in the range from 0.1 to 1 g / L.
• At least one compound such as aminoguanidine, monoethanolamine, triethanolamine or / and a branched urea derivative having an alkyl radical is added.
• aminoguanidine significantly improves the properties of the coatings according to the invention.
• the composition may also have a content of nitroguanidine. It has now surprisingly been found that an addition, in particular of nitroguanidine, to the aqueous composition makes the appearance of the coatings according to the invention very uniform and noticeably increases the coating quality. This has a particularly positive effect on "sensitive" metallic surfaces such as on sandblasted iron or steel surfaces.An addition of nitroguanidine markedly improves the properties of the coatings according to the invention.A content of nitrite can markedly reduce the tendency to rust, in particular of steel surfaces unexpectedly found that addition of hydrogen peroxide to the aqueous composition of the invention improves the optical quality of the coated substrates.
• the composition also contains a content of phosphorus-containing compounds, in particular as oxyanions and / or as corresponding compounds, but preferably no aluminum phosphate.
• the content is particularly preferably in the range from 0.05 to 8 g / l, very particularly preferably in the range from 0.1 to 5 g / l, in particular in the range from 0.2 to 2 g / l.
• These compounds may each be at least one orthophosphate, an oligomeric and / or polymeric phosphate and / or a phosphonate.
• the at least one Orthophosphate and / or salts thereof and / or esters thereof may be, for example, in each case at least one alkali phosphate, iron, manganese or / and zinc-containing orthophosphate and / or at least one of their salts and / or esters.
• at least one metaphosphate, polyphosphate, pyrophosphate, triphosphate or / and their salts and / or their esters may also be added in each case.
• the phosphonate for example, at least one phosphonic acid such as at least one alkyl diphosphonic acid and / or its salts and / or its esters can be added in each case. It has now surprisingly been found that addition of orthophosphate to the aqueous composition according to the invention significantly improves the quality of the coatings, in particular on electrolytically galvanized substrates.
• the phosphorus-containing compounds of this substance group are not surfactants.
• the aqueous composition contains a content of at least one kind of anions selected from carboxylates, e.g. Acetate, butyrate, citrate, formate, fumarate, glycolate, hydroxyacetate, lactate, laurate, maleate, malonate, oxalate, propionate, stearate, tartrate or / and at least one corresponding, non-or / and only partially dissociated compound.
• carboxylates e.g. Acetate, butyrate, citrate, formate, fumarate, glycolate, hydroxyacetate, lactate, laurate, maleate, malonate, oxalate, propionate, stearate, tartrate or / and at least one corresponding, non-or / and only partially dissociated compound.
• the composition contains a content of carboxylate anions and / or carboxylate compounds in the range of 0.01 to 3 g / L calculated as the sum of the corresponding compounds.
• the content is particularly preferably in the range from 0.05 to 1.5 g / l, very particularly preferably in the range from 0.1 to 0.8 g / l, in particular in the range from 0.15 to 0.6 g / l ,
• At least one citrate, lactate, oxalate or / and tartrate can particularly preferably be added as carboxylate in each case.
• the addition of at least one carboxylate can help to complex a cation and make it easier to keep in solution, thus providing greater bath stability and stability
• the composition also contains a level of nitrate.
• nitrate in the range of 0.01 to 2 g / L calculated as the sum of the corresponding compounds.
• the content is particularly preferably in the range from 0.03 to 1.2 g / L, very particularly preferably in the range from 0.06 to 0.8 g / L, in particular in the range from 0.1 to 0.5 g / L , Nitrate can help to even out the formation of the coating, especially on steel.
• nitrite can convert, usually only partially, into nitrate.
• Nitrate may in particular be added as alkali metal nitrate, ammonium nitrate, heavy metal nitrate, as nitric acid and / or as corresponding organic compound.
• the nitrate can significantly reduce the tendency to rust, especially on surfaces of steel and iron.
• the nitrate may contribute to the formation of a defect-free coating or / and an exceptionally level coating which may be free of optically detectable marks.
• the composition contains a content of at least one kind of cations selected from alkali metal ions, ammonium ions and corresponding compounds, in particular potassium or / and sodium ions or at least one corresponding compound.
• the composition has a content of free fluoride ranging from 0.001 to 3 g / L, calculated as F ".
• the content in the range of 0.01 to 1 g / L, more preferably in the range from 0.02 to 0 , 5 g / L, most preferably in the range of up to 0.1 g / L.
• Such an additive is preferably added in the form of hydrofluoric acid and / or its salts.
• the composition contains a content of at least one fluoride-containing compound and / or fluoride anions, calculated as F " and without the inclusion of complex fluorides, in particular at least one fluoride of alkali fluoride (s), ammonium fluoride or / and hydrofluoric acid, more preferably in the range from 0.001 to 12 g / L, most preferably in the range of 0.005 to 8 g / L, in particular in the range of 0.01 to 3 g / L.
• s alkali fluoride
• hydrofluoric acid more preferably in the range from 0.001 to 12 g / L, most preferably in the range of 0.005 to 8 g / L, in particular in the range of 0.01 to 3 g / L.
• the fluoride ions or corresponding compounds can help the deposition of the metal ions on the metallic
• the content of these compounds in the concentrate for example in the silane / silanol / siloxane / polysiloxane-free concentrate B, can be controlled or reduced so that, for example, the deposition of the at least one zirconium compound can be increased or reduced , preferably in the range from 0.1 to 100 g / l, calculated as the sum of the corresponding compounds rich from 0.3 to 80 g / L, most preferably in the range of 0.6 to 60 g / L, in particular in the range of 1 to 30 g / L.
• the weight ratio of the sum of the complex fluorides is calculated as the sum of the associated metals to the sum of the free fluorides calculated as F " greater than 1: 1, more preferably greater than 3: 1, even more preferably greater than 5: 1, particularly preferably greater than 10 : 1.
• the aqueous composition may optionally have a content of at least one compound selected from alkoxides, carbonates, chelates, surfactants and additives such as biocides and / or defoamers.
• the abovementioned additives generally have a beneficial effect in the aqueous compositions according to the invention in that they further improve the good properties of the aqueous base composition according to the invention comprising components a), b) and solvent (s). These additives usually work in the same way if only one titanium or only one zirconium compound or a combination of these is used.
• the combination of at least one titanium and at least one zirconium compound, in particular as complex fluorides significantly improves the properties, in particular of the coatings produced therewith.
• the various additives thus surprisingly act as in a modular system and contribute to the optimization of the respective coating significantly.
• the aqueous composition of the invention has been very useful, since the composition with the various additives to the respective multimetal Mix and its specifics and requirements can be specifically optimized.
• the aqueous coating in the same bath a mix of different metallic materials such as in bodies or different small parts.
• substrates with metallic surfaces selected from cast iron, steel, aluminum, aluminum alloys, magnesium alloys, zinc and zinc alloys in any mix can be coated simultaneously and / or sequentially according to the invention, wherein the substrates can be at least partially metallically coated and / or at least partially can consist of at least one metallic material.
• the remainder to 1000 g / L of water or of water and at least one organic solvent such as ethanol, methanol, isopropanol or dimethylformamide (DMF).
• organic solvent such as ethanol, methanol, isopropanol or dimethylformamide (DMF).
• the content of organic solvents is particularly low or zero in most embodiments. Due to the hydrolysis of the at least one silane contained, a content can occur, in particular, of ethanol and / or methanol. It is particularly preferred to add no organic solvent.
• the composition is free of or substantially free of all types of particles or particles larger than 0.02 micron mean diameter, which could be optionally added, for example, based on oxides such as S1O 2 .
• the composition is poor, substantially free or free of higher levels or levels of water hardness builders such as e.g. Calcium contents above 1 g / L.
• the aqueous composition is free or low in lead, cadmium, chromate, cobalt, nickel or / and other toxic heavy metals.
• such substances are not deliberately added, but at least one heavy metal can be dissolved out of a metallic surface, for example, introduced from another bath or / and can occur as an impurity.
• the composition is poor in, substantially free of, or wholly free of bromide, chloride, and iodide, as they may possibly contribute to corrosion.
• the layer thickness of the coatings produced according to the invention is preferably in the range of 0.005 to 0.3 .mu.m, more preferably in the range of 0.01 to 0.25 .mu.m, most preferably in the range of 0.02 to 0.2 .mu.m, often at about 0.04 ⁇ m, about 0.06 ⁇ m, about 0.08 ⁇ m, about 0.1 ⁇ m, about 0.12 ⁇ m, about 0.14 ⁇ m, about 0.16 ⁇ m or about 0 , 18 ⁇ m.
• the organic monomer, oligomer, polymer, Copolymer or / and block copolymer-containing coatings are often somewhat thicker than those free or nearly free thereof.
• a coating is formed with the composition with a coating weight which, based on the content of titanium and / or zirconium, is in the range from 1 to 200 mg / m 2 calculated as elemental titanium.
• This layer weight is particularly preferably in the range from 5 to 150 mg / m 2 , very particularly preferably in the range from 8 to 120 mg / m 2 , in particular at about 10, about 20, about 30, about 40, about 50, about 60, about 70, about 80, about 90, about 100 or about 110 mg / m 2 .
• a coating is formed with the composition with a coating weight which, based on siloxanes / polysiloxanes, is in the range from 0.2 to 1000 mg / m 2 calculated as the corresponding largely condensed polysiloxane.
• This layer weight is particularly preferably in the range from 2 to 200 mg / m 2 , very particularly preferably in the range from 5 to 150 mg / m 2 , in particular at about 10, about 20, about 30, about 40, about 50, about 60, about 70, about 80, about 90, about 100, about 110, about 120, about 130 or about 140 mg / m 2 .
• the coating produced with the aqueous composition according to the invention can then be coated with at least one primer, lacquer, adhesive or / and with a lacquer-like organic composition, optionally curing at least one of these further coatings by heating and / or irradiation.
• the metallic substrates coated by the method according to the invention can be used in the automotive industry, for rail vehicles, in the aerospace industry, in apparatus engineering, in mechanical engineering, in the construction industry, in the furniture industry, for the production of crash barriers, lamps, profiles, cladding or small parts, for the manufacture of bodywork or bodywork parts, of individual components, preassembled or connected elements, preferably in the automotive or aviation industry, for the manufacture of devices or systems, in particular household appliances, control devices, test devices or construction elements.
• manganese has surprisingly been found to be particularly advantageous: Although apparently no or almost no manganese compound is deposited on the metallic surface, the additive strongly promotes the deposition of silane / silanol / siloxane / polysiloxane on the metallic surface. When nitroguanidine was added, it was surprisingly found that the appearance of the coated metal sheets is very uniform, especially on sensitive surfaces such as sandblasted iron or steel surfaces. Addition of nitrite has unexpectedly significantly reduced the potential for steel substrates.
• each additive having a significant positive effect which is mentioned in this application, has an additive effect for improving the coating according to the invention:
• the various properties, in particular of a multimetal system can be further optimized.
• the aqueous bath compositions are prepared as mixtures according to Table 1 using pre-hydrolyzed silanes. They each contain predominantly a silane and possibly also low contents of at least one similar further silane, which is also referred to simplifying silane and not silane / silanol / siloxane / polysiloxane and being usually this variety of compounds, sometimes in larger Number of similar compounds, even extends into the formation of the coating, so that there are often several similar compounds in the coating.
• prehydrolyzing may also take several days at room temperature with vigorous stirring, as far as the Silanes to be used are not already pre-hydrolyzed.
• the silane is added in excess to water and optionally catalysed with acetic acid.
• acetic acid was added only in some embodiments.
• acetic acid is already included as a catalyst for the hydrolysis. Ethanol is formed during hydrolysis but is not added. The finished mixture is used fresh.
• each per trial at least 3 previously cleaned with an aqueous alkaline cleaner and rinsed with hot water and then with deionized water panels were cold rolled steel (CRS), aluminum alloy AI6016 or from hot-dip galvanized or electrolytically galvanized steel or from Gaivaneal ® (ZnFe Layer on steel) with the corresponding pretreatment liquid of Table 1 on both sides at 25 0 C by spraying, dipping or Rollcoater treatment in contact. Then the sheets treated in this way were dried at 90 ° C. PMT and subsequently painted with a cathodic automotive dip paint (KTL).
• CRS cold rolled steel
• Al alloy AI6016 or from hot-dip galvanized or electrolytically galvanized steel or from Gaivaneal ® (ZnFe Layer on steel) with the corresponding pretreatment liquid of Table 1 on both sides at 25 0 C by spraying, dipping or Rollcoater treatment in contact.
• the sheets treated in this way were dried at 90 ° C. PMT and subsequently painted with
• the organofunctional silane A is an amino-functional trialkoxysilane and has one amino group per molecule. It is like all this used
• the organofunctional silane B has one terminal each
• the non-functional silane C is a bis-trialkoxysilane; the corresponding hydrolyzed molecule has up to 6 OH groups on two silicon atoms on.
• the polysiloxane D has a relatively short chain molecule with a terminal OH group. It has a hydrophobic effect on the coating.
• the complex fluorides of aluminum, silicon, titanium and zirconium are used largely on the basis of a MeF 6 complex, but the complex fluorides of boron largely based on a MeF 4 - complex.
• Manganese is added as metallic manganese to the respective complex fluoride solution and dissolved therein. This solution is mixed into the aqueous composition. If no complex fluoride is used, manganese nitrate is added. Copper is added as cupric nitrate and magnesium as magnesium nitrate. Iron and zinc are added as the corresponding nitrates. Nitrate alone is preferably added as sodium nitrate or nitric acid.
• the epoxy polymer A has a content of OH " and of isocyanate groups and is therefore subsequently chemically crosslinkable at temperatures above 100 ° C.
• the epoxy polymer B also has a content of OH " and of isocyanate groups and therefore also subsequently chemically crosslinkable at temperatures above 100 0 C.
• the polymer B is more stable in the bath in the selected compositions of the invention than the polymer A.
• the silylated epoxy polymer C has a low content of OH " - and isocyanate groups and is therefore subsequently chemically crosslinkable at temperatures above 100 0 C.
• the reactions take place above all in the solution, during drying or optionally also during hardening of the coating, in particular at temperatures above 70 ° C. All concentrates and baths proved to be stable for one week and without changes and without precipitations. It no ethanol was added. Levels of ethanol in the compositions resulted only from chemical reactions.
• the pH is adjusted in most examples and comparative examples, in the presence of at least one complex fluoride with ammonia, in other cases with an acid. All bathrooms show a good quality of the solution and almost always good bath stability. There are no precipitations in the baths. After coating with the silane-containing solution, rinse once with deionised water once. Thereafter, the coated sheets are dried at 120 0 C in a drying oven for 5 minutes. The visual inspection of the coatings can only be significantly carried out on the coatings on steel due to the interference colors and allows the uniformity of the coating to be assessed. The coatings without any complex fluoride content are quite uneven.
• a coating with titanium and with zirconium complex fluoride has surprisingly been found to be significantly more uniform than if only one of these complex fluorides had been applied. Addition of nitroguanidine, nitrate or nitrite also improves the uniformity of the coating. Partly the layer thickness increases with the concentration of these substances.
• Table 1 Compositions of baths in g / L based on solids contents, for silanes based on the weight of the hydrolyzed silanes; Residual content: water and usually a very small amount of ethanol; Process data and properties of the coatings
• the bath compositions are all stable and easy to apply in the short time of use. There are no precipitations and no color changes. There are no differences in behavior, visual impression and test results between the various examples and comparative examples that can be attributed to treatment conditions such as application by syringes, dipping or roller coater treatment.
• the resulting films are transparent and almost all are largely uniform. They show no coloring of the coating.
• the structure, the gloss and the color of the metallic surface appear only slightly changed by the coating.
• With a content of titanium or / and zirconium complex fluoride iridescent layers are formed, in particular, on steel surfaces.
• the combination of several silanes has not yet resulted in a significant improvement in corrosion protection, but can not be ruled out.
• a content of H 3 AIF 6 was determined on aluminum-rich metallic surfaces due to corresponding reactions in the aqueous composition.
• the combination of two or three complex fluorides in the aqueous composition has surprisingly been extremely successful.
• the layer thickness of the coatings produced in this way also depended on the type of application, which was initially varied in separate experiments, in the range from 0.01 to 0.16 ⁇ m, usually in the range from 0.02 to 0.12 ⁇ m at up to 0.08 microns, which was significantly larger with the addition of organic polymer.
• the corrosion protection grades are in the cross-cut test in accordance with DIN EN ISO 2409 after storage for 40 hours in 5% NaCl solution according to BMW specification GS 90011 from 0 to 5, where 0 represents the best values.
• the rockfall test in accordance with DIN 55996-1, the coated sheets undergo 10 cycles of steel scrap following the above-mentioned VDA change test Shot: The damage pattern is characterized by characteristic values from 0 to 5, where 0 represents the best results.
• the coated sheets are exposed to a corrosive sodium chloride solution by spraying for up to 1008 hours; then the infiltration in mm is measured from the scratch, the scratch is made with a standardized stylus to the metallic surface and wherein the infiltration should be as small as possible.
• the coated aluminum alloy sheets are exposed to a special corrosive atmosphere by spraying for over 504 hours; then the infiltration is measured in mm from the scratch, which should be as small as possible.

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• 2005
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