EP2376674A1 - Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation - Google Patents

Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation

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Publication number
EP2376674A1
EP2376674A1 EP09771552A EP09771552A EP2376674A1 EP 2376674 A1 EP2376674 A1 EP 2376674A1 EP 09771552 A EP09771552 A EP 09771552A EP 09771552 A EP09771552 A EP 09771552A EP 2376674 A1 EP2376674 A1 EP 2376674A1
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EP
European Patent Office
Prior art keywords
activating agent
phosphate
aqueous
water
agent
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Application number
EP09771552A
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German (de)
English (en)
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EP2376674B1 (fr
Inventor
Thomas Kolberg
Eckart SCHÖNFELDER
Olaf Dahlenburg
Manfred Walter
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Chemetall GmbH
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Chemetall GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102—Pretreatment of 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/10—Scrim [e.g., open net or mesh, gauze, loose or open weave or knit, etc.]

Definitions

  • the invention relates to a process for phosphating metallic surfaces, in which the metallic surfaces are treated before phosphating with an aqueous colloidal activator based on titanium phosphate before phosphating, and corresponding activating agents.
  • phosphating has been a pretreatment process used for metallic surfaces for temporary or prolonged corrosion protection and often also for improving the adhesion of a subsequent primer or lacquer layer.
  • the zinc-containing phosphating processes which are referred to as so-called layer-forming (i.e., highly visible crystalline layers) phosphating processes, are of excellent quality and to date are only to a limited extent replaced by pretreatment processes with equivalent layer properties.
  • layer-forming (i.e., highly visible crystalline layers) phosphating processes are of excellent quality and to date are only to a limited extent replaced by pretreatment processes with equivalent layer properties.
  • zinc-nickel or zinc-manganese nickel-phosphates are of outstanding quality and usually on aluminum, iron or zinc rich metallic surfaces under an organic coating for reasons of corrosion protection and paint adhesion is absolutely necessary.
  • the zinc-containing phosphating require a prior activation for the formation of a high-quality coating, in which the clean or cleaned metallic surface with nuclei on the basis of phosphate colloid and / or phosphate particles and optionally with other substances is occupied.
  • the layer of the crystalline zinc-containing phosphate can be formed largely to completely closed.
  • the crystalline layer is formed comparatively fine-grained and / or substantially uniformly shaped crystals.
  • a coating of zinc manganese-nickel phosphate usually has a coating weight due to good activation. rich from 1, 0 to 3.5 g / m 2 and phosphate crystals of often less than 12 microns average crystal size viewed under the scanning electron microscope.
  • the resulting phosphate layer will typically have a coating weight in the range of 5 to 8 g / m 2 and phosphate crystals of often more than 30 ⁇ m mean crystal size under the scanning electron microscope.
  • the coat weight for the paint adhesion to the subsequent primer or lacquer layer is much too high, since if the phosphate layers are too thick, too little paint adhesion is to be expected.
  • the consequence of the too large phosphate crystals are a lower paint adhesion, a lower corrosion resistance, a lower mechanical strength of the phosphate layer, uneven paint surfaces and a significantly higher chemical consumption. The quality of these properties is often strictly proportional.
  • activating agents often have in series production only a period of use of about one day until they need to be enriched to a greater extent with a supplementary solution in order to remain well able to work or or until they are replaced by a new approach solution become.
  • activating agents on the market that have a working life of up to about four or five days by the addition of organic polymer in mass production, but which is then limited to working within five working days.
  • the limited duration of use manifests itself primarily in the fact that the formed during Zinkphosphatieren phosphate coatings due to the changing activating agent over the working week in their coating weight, for example, from about 1, 3 g / m 2 to a coating weight of, for example, 4.5 g / m 2 and thus increase in their layer thickness. This is also associated with a deterioration in corrosion resistance and paint adhesion.
  • coating weights of about 1.0 to about 3.5 g / m 2 are permissible in most automotive plants. With an even higher coating weight, however, a decrease in paint adhesion and a higher consumption of chemicals are also associated. It is therefore advantageous if the change in the bath composition of the activating agent as well as the layer weight and the further layer properties fluctuates less strongly over the production time.
  • bath here stands for the treatment bath.
  • values of the changes and fluctuations in the layer weight in the range of ⁇ 0.3 to a maximum of ⁇ 1.0 g / m 2 were determined over a week, depending on the laboratory test series or plant, the layer weights always being in the range between 1 , 0 and 3.5 g / m 2 remained. It is advantageous if an activating agent causes only slight property fluctuations and changes in the properties of the phosphate layer produced during the phosphating over the duration of use.
  • an activating agent can also be used for a prolonged period at a higher temperature, ie has a higher thermal stability, ie at temperatures in the range from 30 to 60 or possibly even in the range from 30 to 80 ° C. over time can be used. Due to such higher temperature stability, the entire process is less sensitive. Temperature fluctuations, especially in the higher temperature ranges, are then compensated and ensure a constant quality of the phosphate layer. Because if a less temperature-stable activating agent is used for a long time above its temperature stability limit, the agglomeration of the colloids is accelerated and thus degrades the activation effect much faster.
  • EP 0 454 211 B1 teaches methods for applying phosphate coatings to metal surfaces by activating with a titanium phosphate activating agent and then zinc phosphating activating the metal surfaces with an activating agent bath containing 0.001 to 0.060 g / L Ti, 0.02 to 1, 2 g / L orthophosphate calculated as P 2 O 5 , 0.001 to 0.1 g / L contains Cu and alkali compounds.
  • the object is achieved by a method for phosphating metallic surfaces, wherein the metallic surfaces are treated prior to phosphating with an aqueous colloidal activating agent based on phosphate and titanium, wherein the activating agent contains at least one water-soluble silicon compound having at least one organic group.
  • the aqueous colloidal activating agent according to the invention preferably comprises titanium phosphate, orthophosphate, alkali metal and optionally at least one stabilizing agent and / or at least one further additive. It preferably contains at least one hydrolyzed or / and condensed silane / silanol / siloxane / polysiloxane.
  • the activating agent may preferably be a colloidal solution or colloidal dispersion or a powdery activating agent, the latter being dissolved and dispersed for use in a coating process.
  • a powdered activating agent may in particular have a residual water content, optionally including water of crystallization, of between 0 and about 15% by weight.
  • at least one water-soluble silicon compound can already be present in a pulverulent activating agent and / or can only be added in water upon dissolution and dispersion of the pulverulent activating agent.
  • An aqueous and often colloidal activating agent such as the activating agent A may initially preferably contain a water content in the range from 5 to 90% by weight of water.
  • a powdered activating agent such as the activating agent B
  • an initial water content of 5 to 30% by weight is preferred
  • an aqueous activating agent such as the activating agent D for example from an activating agent A
  • an initial water content of 20 to 90 wt .-% preferred.
  • the aqueous and usually colloidal activating agent A is an aqueous mixture which is prepared and / or prepared, for example, by mixing the respective components and optionally also by kneading and optionally with partial drying. Therefore, the aqueous colloidal activating agent A may optionally be present as a powder at the end of the preparation.
  • At least one further substance also in the dissolved and / or pulverulent state, may be added, if required, e.g. Dipotassium phosphate, disodium phosphate, potassium pyrophosphate, sodium pyrophosphate, potassium tripolyphosphate, sodium tripolyphosphate, at least one other stabilizing agent or / and at least one agent, e.g. for pH adjustment, e.g. at least one carbonate or / and at least one borate.
  • Dipotassium phosphate disodium phosphate
  • potassium pyrophosphate sodium pyrophosphate
  • potassium tripolyphosphate sodium tripolyphosphate
  • at least one other stabilizing agent e.g. for pH adjustment, e.g. at least one carbonate or / and at least one borate.
  • the powdery activating agent B usually contains colloidal titanium phosphate in a dried state.
  • at least one substance such as in each case at least one biocide, surfactant, stabilizer or / and additive for pH adjustment, in particular during dissolution and dispersion, may be added.
  • an aqueous colloidal activating agent according to the invention e.g. the activating agent D
  • an aqueous activating agent e.g. the activating agent A
  • a particularly storable aqueous colloidal activator such as e.g.
  • the activating agent D can be diluted with water and can hereby become the aqueous colloidal activating agent E according to the invention, which can then be applied to the metallic surfaces.
  • the dilution is preferably carried out with stirring.
  • at least one substance e.g. in each case at least one biocide, surfactant, stabilizer or / and additive for pH adjustment, in particular during dilution, are added.
  • a pulverulent activating agent F can be prepared, for example by mixing the individual constituents, and in particular can be stored. It preferably has a water content between 0 and 8 wt .-%. From this, then, if required, an inventive aqueous colloidal activating agent such as the activating agent G can be prepared, for example, by dissolving and dispersing in water - in particular with stirring, which can then be applied to the metallic surfaces. It is preferred that the colloids are formed predominantly or entirely only in the dissolution and dispersion.
  • the aqueous colloidal activating agent according to the invention can be prepared from an aqueous colloidal activating agent (precursor A) via a pulverulent activating agent (precursor B) and then dissolved and dispersed in water before application to the metallic surfaces (activating agent C) or are prepared from an aqueous colloidal activating agent (precursor A) via an aqueous colloidal activating agent (precursor D) and then diluted in water before application to the metallic surfaces (activating agent E).
  • the aqueous colloidal activating agent according to the invention can be dissolved and dispersed in water from a powder-form activating agent (precursor F) on the metallic surfaces prior to application (activating agent G).
  • the activating agents may preferably contain at least one stabilizing agent.
  • a stabilizer stabilizes in particular the titanium phosphate colloids.
  • the titanium phosphate colloids may agglomerate more readily and / or more rapidly in some aqueous colloidal activating agents and / or in some situations of the activating bath, and in particular may impair the activation quality after a short time. The stability and duration of use are then limited.
  • the addition or content of stabilizer is advantageous or even necessary for longer stability of the activator bath. This is especially true sometimes for a lifetime and stability of Aktivianssmittelbades of more than 4 hours.
  • Table 1 Overview of the various activating agents, their precursors, their contents and their state:
  • the aqueous colloidal activating agents according to the invention comprise at least one water-soluble silicon compound having at least one organic group
  • an activating agent such as e.g. the activating agents A, B, D and F in some process variants contain at least one water-soluble silicon compound having at least one organic group.
  • the terms “colloid (s)” and “colloidal” designate only titanium phosphate colloids or corresponding contents, since only these colloids have a significant activating effect for a subsequent phosphating.
  • the activating agent F usually contains no titanium phosphate colloids, since the powder deformed activator contains too little water for this purpose to form colloids. Because the term “colloid (s)” usually requires the presence of a sufficient amount of at least one liquid phase such as water.
  • An aqueous activating agent e.g. the activating agent A, C, D, E or / and G typically contains dissolved and often colloidal components. Its particles are typically partially or wholly in the particle sizes of the otherwise conventionally used term "colloidal" (eg, finely divided particles having particle sizes of between about 1 and 100 nm or between 1 and 300 nm, for example), but may sometimes have a small fraction of particle sizes
  • the particle sizes of the activating agent were determined using a Zetasizer Nano ZS from Malvern Instruments Ltd.
  • the pH values and conditions of the activating agent to be measured were chosen to be 0.1 g / l
  • the particle size distribution of an activating agent is polydispersed, ie in a bimodal or multimodal particle size distribution.
  • the ready-for-use colloidal activating agents according to the invention are usually present in the concentration of the treatment bath of an activating agent bath, occasionally also in a slightly elevated concentration before the concentration of the activator bath is adjusted by dilution with water.
  • the activating agents C and G are commonly referred to in the art as “powder activation", while the activating agents E are commonly referred to as "liquid activating”.
  • An activating agent in a preliminary stage of the production process of an activating agent such as the activating agent A, B, D and F is usually present in a higher concentration than that of the treatment bath of an activating agent bath. Preferably, they are highly concentrated.
  • a powdered activating agent according to the invention such as the activating agent B
  • a powdered activating agent is present as a powder, optionally as a granulated powder. In principle, it can also be produced by spray drying. It is largely or completely dry.
  • a pulverulent activating agent preferably has a powder particle size distribution essentially in the range from 1 to 1000 ⁇ m, particularly preferably in the range from 10 to 500 ⁇ m, in substantially dry state determined by sieve analysis with sieves in the range of about 500 to about 25 ⁇ m mesh size.
  • the powdered activating agent is preferably present in a readily free-flowing form. In this case, it is advantageous to ensure that the moisture content of the powder is not too high. In addition, it is advantageous if it is well dispersed and dissolved well when stirred in water, during dissolution and / or during dispersion.
  • the colloids are preferably dried up. When dissolving a powdered activating agent such as the activating agent B, the colloids are in high quality and usually in sufficient quantity.
  • aqueous colloidal activating agents of the invention e.g. the activating agents C, E or / and G are typically present in a colloidal solution and / or colloidal suspension.
  • Their titanium phosphate particles are typically partially or completely colloidal.
  • An aqueous colloidal activating agent A differs from an aqueous colloidal activating agent C in the concentration or / and in the phase inventory and optionally also in the overall chemical composition.
  • the aqueous colloidal activating agent A also often does not contain a substantial content of stabilizing agent, but often substantially or even only at least one orthophosphate and titanium phosphate among the phosphates. It is often highly concentrated. It has surprisingly been found that the addition of at least one stabilizing agent to an aqueous and optionally colloidal activating agent such as the activating agent A, C, DE or / and G leads to a partially very marked increase in the stabilization and the longevity of the activating agent.
  • an aqueous colloidal activating agent according to the invention in particular an activating agent C, E or / and G, is unstable, then it is advantageous or even necessary to add stabilizing agents.
  • the stability is based on the low or high tendency of the colloids to agglomerate or to lack colloids. Agglomerated or missing colloids have a poor or no activation effect.
  • An aqueous colloidal activating agent of the present invention preferably differs from an activating agent of a precursor such as the activating agent A due to the dilution and is usually in a somewhat more stable state because the agglomeration of the colloids is lower.
  • An inventive aqueous colloidal activating agent such as the activating agent C with at least one stabilizing agent differs from an activating agent of a precursor such as the activating agent A in particular by a significantly increased stability and thus by overall significantly improved properties of the coating process and the phosphate coating.
  • the aqueous colloidal activator D is often a concentrate. It contains colloids in the aqueous phase. Its stability is usually ensured by at least one stabilizing agent.
  • An aqueous colloidal activating agent according to the invention such as the activating agent E, can be prepared from an aqueous more highly concentrated colloidal activating agent of a precursor such as the activating agent D by dilution with water and optionally by adding at least one substance such as z. B. in each case at least one biocide, surfactant, stabilizer or / and additive for pH adjustment can be produced.
  • a pulverulent activating agent F can be mixed together, for example in a mixer, from the individual substances and mixtures to be added in the dry or largely dry state (usually up to a maximum of 8 or even up to a maximum of 15% by weight of water content). In this case, mixing, kneading or / and granulation may preferably take place.
  • the water content is preferably only or almost exclusively contained as water of crystallization and / or as residual moisture. Colloids are usually hardly or not present here.
  • An aqueous colloidal activating agent according to the invention can be prepared from a powdery activating agent of a precursor, such as the activating agent F, by dissolving and dispersing in water, e.g. while stirring and optionally adding at least one substance, e.g. in each case at least one biocide, surfactant, stabilizer or / and additive for pH adjustment are produced.
  • the colloids are formed from the titanium phosphate-containing substances in contact with water.
  • the quality of activation of an aqueous activator G is somewhat less than that of the aqueous activators C and E.
  • the cost of creating the aqueous activator G is often lower, and for simple applications the activator quality of the activator G is usually sufficient.
  • the concentrates and baths of an aqueous colloidal activating agent according to the invention often have quite similar or identical properties to one another.
  • the properties of the phosphate layers upon previous activation with an aqueous colloidal activating agent of the invention such as the aqueous activating agent C, E or G are often quite similar or the same among themselves.
  • the suitability and quality of the activator bath can be assessed, in particular, by coating weight, visually discernible uniformity of the zinc phosphate layer, degree of coverage with zinc phosphate layer, corrosion test results or / and paint adhesion test results.
  • an activating agent such as the activating agent A, B, C, D, E, F and / or G contains as the main ingredient or as an essential ingredient at least one phosphate such as e.g. in each case at least one sodium, potassium or / and titanium-containing phosphate, in particular as the main constituents of sodium and / or potassium orthophosphate (s) and at least one titanium-containing phosphate.
  • phosphate such as e.g. in each case at least one sodium, potassium or / and titanium-containing phosphate, in particular as the main constituents of sodium and / or potassium orthophosphate (s) and at least one titanium-containing phosphate.
  • the phosphates are in an aqueous colloidal activating agent such as the activating agent A, C, D, E or / and G in the form of titanium phosphate, titanyl phosphate, disodium phosphate and / or dipotassium phosphate.
  • an aqueous colloidal activating agent such as in particular the activating agent A, C, D, E or / and G may optionally also have a content of at least one stabilizing agent such as, for example, pyrophosphate and / or tripolyphosphate.
  • the content of an aqueous activating agent such as the activating agent A, C, D, E or / and G of phosphate can be calculated as phosphate compounds preferably in the range of 0.05 to 400 g / L and more preferably in the range of 0.10 to 280 or from 0.20 to 200 g / L or with a powdered activating agent such as the activating agent B and / or F in the range of 0.5 to 98 wt .-% and in particular in the range of 3 to 90 or from 10 to 80% by weight (each for concentrates and baths).
  • the content of an aqueous activating agent such as the activating agent A, C, D, E or / and G of phosphate can be calculated as PO 4 preferably in the range of 0.005 to 300 g / L and in particular in the range of 0.010 to 200 or 0.020 to 100 g / L or in the case of a pulverulent activating agent such as the activating agent B and / or F in the range from 0.1 to 80 wt.% And in particular in the range from 1 to 65 or from 10 to 50 wt. (each for concentrates and baths). In the case of incorporating cleanser with a silicate content from one of the previous baths, this silicate content and this silicate do not belong to the term "silicon compound" in the context of this application.
  • the at least one silane / silanol / siloxane / polysiloxane is not included in an aqueous or powdered activator precursor such as the activating agent A, B, D or F and will not be used until the preparation of an aqueous colloidal activating agent of the invention such as Activating agent C, E or G added.
  • the total content of the water-soluble silicon compounds having at least one organic group in an activator precursor such as activator A, B, D or F may be either about zero or in an aqueous activator such as activator A, C, D, E or /.
  • G are preferably 0.0001 to 50 g / L and in particular 0.001 to 20 g / L, in particular for coating on the metallic surfaces 0.001 to 0.2 g / L, or in a powdered activating agent as in the activating agent B or / and F preferably about zero or 0.001 to 25 wt .-% and in particular 0.01 to 5 wt .-%, calculated in each case as silane and / or as a corresponding mainly present silicon-containing starting compound (respectively for concentrates and baths).
  • silanes / silanols / siloxanes / polysiloxanes in the context of this application is used here for silanes, silanols, siloxanes, polysiloxanes and their reaction products or derivatives, which are often "silane” mixtures
  • silanes silanols, siloxanes, polysiloxanes and their reaction products or derivatives
  • Particular preference is given to the addition of at least one silane having at least one organic group, it being customary to speak of "silane”, since it is often unknown whether the "commercially available silane" contains at least one silane, At least one silanol, at least one siloxane, at least one polysiloxane or any mixture of these substances
  • Even with self-modified "silanes it is often not possible or only with extremely great effort to determine which substances in a certain stage of manufacture or after storage or after addition to a solution or suspension. Due to the often complex chemical reactions that occur in this case, and complex analyzes and
  • the at least one organic group of the water-soluble silicon compound may, for example, each independently be at least one aliphatic, cycloaliphatic, heterocyclic or / and aromatic group, each independently saturated or unsaturated and each independently having at least one or no functional group.
  • the at least one functional group may, in particular, be selected from aldehyde groups, amido groups, amino groups, carbonyl groups, ester groups, ether groups, urea groups, hydroxide groups, imido groups, imino groups, Groups, nitro groups and / or oxirane groups.
  • the at least one water-soluble silicon compound may have one, two or more than two silicon atoms in the molecule. Their molecule may optionally be branched or / and assume a two-dimensional or three-dimensional form.
  • the silicon compound in an activating agent such as the activating agent A, B, D, E, F or / and G it is preferred to contain at least one hydrolyzable or / and at least one at least partially hydrolyzed silane. It may preferably contain at least one monosilosilane, at least one bis-silyl-silane or / and at least one tris-silyl-silane. In each case, at least one allylsilane, alkoxysilane, amino silane, succinic anhydride silane, cycloalkylsilane, cycloalkoxysilane, epoxysilane, phenylsilane or / and vinylsilane may preferably be present.
  • the activating agent according to the invention may comprise a mixture of at least two silanes, for example 1.) at least two amino-silanes such as at least one mono-amino-silane and at least one bis-amino-silane, for example 2.) at least one bis silyl-silane such as at least one bis-amino silane and at least one alkoxy silane such as at least one trialkoxy Silyl-propyl-tetrasulfan or as eg 3.) at least one vinylsilane and at least one bis-silyl-silane such as at least one bis-amino-silane.
  • the aqueous composition contains at least one silane selected from the group of
  • Aminoalkylaminoalkylalkyldialkoxysilane (epoxycycloalkyl) alkyltrialkoxysilane, alpha-aminoalkyliminoalkyltrialkoxysilane, bis (trialkoxysilylalkyl) amine, bis (trialkoxysilyl) ethane, (epoxyalkyl) trialkoxysilane,
  • aminoalkyl aminoalkyltrialkoxysilane N- (trialkoxysilylalkyl) dialkylenetriamine, poly (aminoalkyl) alkyldialkoxysilane, tris (trialkoxysilyl) alkyl isocyanurate, ureidoalkyltrialkoxysilane and acetoxysilane.
  • the aqueous composition contains at least one silane selected from the group of
  • silicon compounds are bis (3-trimethoxysilylpropyl) amine, bis (3-triethoxysilylpropyl) amine, 3-aminopropyltriethoxysilane, bis (triethoxysilyl) ethane, Phenylaminopropyltrinnethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydride, 3-glycidoxypropyltrinnethoxysilane and triaminofunctional silane.
  • the activating agent preferably contains at least one partially or completely hydrolyzed silane / silanol / siloxane or / and optionally also condensed silane / silanol / siloxane / polysiloxane as silicon compound.
  • the content of titanium in an aqueous activating agent such as the activating agent A, C, D, E or / and G may preferably be in the range of 0.0001 to 10 g / L, more preferably in the range of 0.001 to 5 or 0.005 to 1 g / L or in a powdered activating agent such as the activating agent B and / or F preferably be about zero or in the range of 0.001 to 10 wt .-% and in particular in the range of 0.005 to 2 or from 0.01 to 1 % By weight (each for concentrates and baths).
  • the total content of cobalt, copper or / and nickel in an aqueous activating agent such as the activating agent A, C, D, E or / and G may preferably be about zero or in the range of 0.00001 to 0.1 g / L and in particular in the range of 0.0005 to 0.05 or from 0.01 to 0.02 g / L or in a powdered activating agent such as the activating agent B and / or F preferably be about zero or in the range of 0, 0001 to 2 wt .-% and in particular in the range of 0.001 to 0.8 or from 0.01 to 0.4 wt .-% (in each case for concentrates and baths).
  • a content of cobalt, copper or / and nickel can contribute to the refinement of the phosphate layer and has a bactericidal effect.
  • a weight ratio of the contents of titanium to those of water-soluble silicon compounds having at least one organic group (calculated in each case as silane or / and as corresponding silicic starting compound) in the range of (0.3 - 2.6) : 1 proved to be good, in the range of (0.2 - 3.0): 1 as at least sufficient.
  • the total content of sodium and / or potassium in an aqueous activating agent such as the activating agent A, C, D, E or / and G preferably in the range of 0.005 to 300 g / L and in particular in the range of 0.01 to 200 or from 0.02 to 100 g / L or in a powdered activating agent such as the activating agent B and / or F preferably in the range of 0.1 to 70 wt .-% and in particular in the range of 1 to 60 or from 10 to 50% by weight (each for concentrates and baths).
  • an aqueous activating agent such as the activating agent A, C, D, E or / and G preferably in the range of 0.005 to 300 g / L and in particular in the range of 0.01 to 200 or from 0.02 to 100 g / L or in a powdered activating agent such as the activating agent B and / or F preferably in the range of 0.1 to 70 wt .-% and in particular in the range of 1
  • the activating agent may preferably also contain a content of at least one biocide, wetting agent, softening agent, complexing agent, sequestering agent, stabilizer or marker.
  • the total content of at least one labeling ion and / or on at least one labeling compound such. based on lithium, lanthanide (s), yttrium or / and tungsten, as a dye marker and / or fluorescent markers in an aqueous activating agent such as the activating agent A, C, D, E or / and G preferably be about zero or in the range of 0 , 0001 to 100 g / L and in particular in the range of 0.001 to 10 or from 0.01 to 1 g / L or in a powdered activating agent such as the activating agent B and / or F preferably be about zero or in the range of 0.001 to 20 wt .-% and in particular in the range of 0.01 to 10 or from 0.1 to 1 wt .-% (in each case for concentrates and baths).
  • an aqueous activating agent such as the activating agent A, C, D, E or / and G preferably be about zero or in the range of 0
  • at least one softening agent such as in each case at least one dicarboxylic acid, tricarboxylic acid, higher carboxylic acid, polycarboxylic acid, oxydicarboxylic acid, oxytricarboxylic acid, higher oxycarboxylic acid, poly
  • HEDP (i -Hydroxyethylidene) diphosphonic acid
  • Such compounds serve in particular as complexing agents and / or as sequestering agents.
  • the content of softening agents in an aqueous activating agent such as the activating agent A, C, D, E or / and G may preferably be zero or in the range of 0.0001 to 50 g / L and in particular 0.001 to 20 g / L preferably in a powdered activating agent such as the activating agent B and / or F be about zero or in the range of 0.001 to 25 wt .-% and in particular 0.01 to 5 wt .-% are (in each case for concentrates and baths).
  • an activating agent such as the activating agent A, B, C, D, E, F or / and G may optionally also contain in each case at least one addition of at least one stabilizing agent.
  • a stabilizer stabilizes the titanium phosphate colloids.
  • the stabilizing agent may comprise at least one substance, e.g. at least one based on at least one organic polymer, organic Copolvmer, pyrophosphate, tripolyphosphate and / or phosphonate or be.
  • the activating agent preferably contains as stabilizing agent in each case at least one / an anionically modified polysaccharide, water-soluble organic copolymer, such as e.g.
  • stabilizing agents in particular one based on acrylate, ethylene or / and polyelectrolyte, carboxylic acid, phosphonic acid, diphosphonic acid, triphosphonic acid, polyphosphonic acid, polyelectrolyte or / and derivatives thereof, such as e.g. Carboxylic acid esters, phosphonic acid esters or / and derivatives thereof.
  • the stabilization takes place via electrostatic and / or steric stabilization.
  • orthophosphates also often have a certain, but not a high stabilizing effect, they are not referred to as stabilizing agents for the purposes of this application.
  • the content of stabilizing agents in an aqueous activating agent such as the activating agent A, C, D, E or / and G may preferably be about zero or in the range from 0.0001 to 300 g / L and in particular from 1 to 200 g / L or in a powdered activating agent such as the activating agent B and / or F preferably be about zero or in the range from 0.001 to 80 wt .-% and in particular 1 to 60 wt .-% are (in each case for concentrates and baths).
  • an aqueous activating agent such as an activating agent A, C, D, E or / and G may preferably also have a content of a detergent mixture, of at least one surfactant or / and of at least one hydrotrope such as e.g. in each case at least one alkane sulfate, alkanesulfonate or / and glycol or added to the activating agent.
  • Suitable surfactants are in principle all amphoteric, nonionic, anionic and cationic surfactants.
  • the content of each at least one detergent mixture, surfactant or / and hydrotrope in an activating agent such as the activating agent A, C, D, E or / and G preferably be about zero or in the range of 0.001 to 100 g / L and in particular in the range of 0.005 to 50 or from 0.01 to 10 g / L or in a powdered activating agent such as the activating agent B and / or F preferably be about zero or in the range of 0.01 to 99 wt .-% and in particular in the range of 0.05 to 90 or from 0.1 to 80 wt .-% (in each case for concentrates, baths and activating detergents).
  • a wide variety of substances can be used to adjust the pH and / or to buffer the chemical system, preferably at least one borate or / and at least one carbonate.
  • Particularly preferred are alkali metal compounds such as e.g. at least one alkali borate or / and at least one alkali carbonate. The content of these compounds can vary within wide limits.
  • It is preferably either about zero or is often 0.1 to 200 g / L or preferably 1 to 100 g / L in an aqueous activating agent such as the activating agent A, C, D, E or / and G or is in a powdered activating agent such as the activating agent B and / or F preferably about zero or is 0.01 to 95 wt .-% and especially 0.1 to 90 or 1 to 80 wt .-% (each for concentrates, baths and for activating detergents).
  • an aqueous activating agent such as the activating agent A, C, D, E or / and G
  • a powdered activating agent such as the activating agent B and / or F preferably about zero or is 0.01 to 95 wt .-% and especially 0.1 to 90 or 1 to 80 wt .-% (each for concentrates, baths and for activating detergents).
  • the activating agent may preferably also contain a content of at least one biocide.
  • the content of biocide (s) in an activating agent such as the activating agent A, B, C, D, E, F or / and G is preferably about zero, or in the range of 0.0001 to 2 g / L and especially in the Range from 0.005 to 0.3 or from 0.01 to 0.05 g / L or in an activating agent such as the activating agent B preferably be about zero or in the range of 0.01 to 10 wt .-% and in particular in the range from 0.05 to 2 or from 0.1 to 1.5% by weight (each for concentrates and baths).
  • the pH in an aqueous activating agent such as the activating agent A, C, D, E or / and G is in the range of 7 to 13, more preferably in the range of 8 to 12 or 8.5 to 11.
  • the pH value may also be less than 7, if it does not come to disturbing precipitations in Aktivianssstoffbad, or be greater than 13, if this bath does not attack the system parts too much.
  • an aqueous colloidal activating agent according to the invention such as the activating agent C, E or / and G, can preferably be applied to the metallic surfaces at a temperature in the range from 10 to 80 ° C., more preferably in the range from 15 to 60 or 20 up to 50 ° C.
  • the activating agent according to the invention may preferably be applied to the metallic surfaces by flooding, swelling, spraying, dipping or / and rolling on and optionally squeezing. In most embodiments, the activating agent is applied by spraying or dipping.
  • the metallic surfaces may preferably be cleaned, degreased or / and pickled prior to activation and subsequently and / or optionally rinsed with water in between. In many embodiments it is necessary to subsequently rinse with water after cleaning, degreasing and / or pickling.
  • the metallic surfaces can preferably be rinsed with water after activation and before phosphating. In many embodiments, this rinse is optional.
  • the metallic surfaces may preferably be phosphated after rinsing, rinsed and / or with at least one organic coating such as e.g. at least one primer, at least one lacquer, at least one adhesive carrier and / or at least one adhesive are provided. This can be dried, rinsed or rinsed if necessary after the application of a coating and then dried.
  • at least one organic coating such as e.g. at least one primer, at least one lacquer, at least one adhesive carrier and / or at least one adhesive are provided.
  • the layer weight of the produced zinc phosphate layer has been found to be satisfactory in the experiments at values of 1.5- 3 g / m 2 , at values of> 3 - ⁇ 4 g / m 2 and at values between approximately 1 and 1.5 between 4 and 4.5 g / m 2 mostly proved to be satisfactory.
  • the coating weight is not the only criterion for evaluating the quality of an activating agent bath. Rather, the visually recognizable uniformity of the zinc phosphate layer, the degree of coverage with zinc phosphate layer, the corrosion test results and / or the paint adhesion test results can also be used here.
  • the activating agents according to the invention have usually proven to be good if their activating effect turned out to be good or very good over at least 120 h, which is measurable in particular on the coating weight. A good to satisfactory activating effect could even be achieved over more than 300 hours in the case of activating agent baths according to the invention. This is because when the activating gain decreases, the increase in the coating weight of the zinc phosphate layer to above 3.5 g / m 2 and at the macroscopically visible degree of coverage with zinc phosphate layer or on metallically shiny parts or at locations with rust attack is particularly evident.
  • metallic materials are basically Lich all types of metallic materials possible, in particular those of aluminum, iron, copper, titanium, zinc, tin and / or alloys containing aluminum, iron, steel, copper, magnesium, nickel, titanium, zinc and / or tin, wherein their use can also be adjacent or / and successively.
  • the material surfaces can also be precoated or / and be, for example, with zinc or an alloy containing aluminum or / and zinc.
  • the object is also achieved with an aqueous colloidal activating agent based on titanium phosphate and at least one further titanium-free phosphate for the treatment of metallic surfaces prior to phosphating, in which the activating agent contains at least one water-soluble SiI ciumharm having at least one organic group.
  • aqueous colloidal activating agent A which has been prepared essentially by mixing, kneading or / and granulating the components, or with an aqueous colloidal activating agent C, which was prepared from an aqueous colloidal activating agent A via a powdered activating agent B.
  • the activating agent may preferably have a composition according to one of the method claims, in particular at least one stabilizing agent.
  • aqueous or pulverulent activating agent according to the invention, to the knowledge of the Applicant, it is surprisingly possible for the first time to achieve bath life which can be used well without or without the addition of concentrates or / and of supplementing agents for more than 120 hours.
  • either no addition or at most the addition of concentrates and / or supplements is added up to the level of the bath volume discharged over the bath service time and a nearly constant low layer weight in the range of, for example, 1.0 to 3.5 g / m 2 is achieved ,
  • the activating agent according to the invention may also preferably be added to a cleaning agent and used in a cleaning agent. This makes it possible to clean and activate in one step and saves at least one bath. This is particularly advantageous for simple production runs without very high quality requirements.
  • the metallic articles activated and phosphated by the process according to the invention and optionally also further coated may be used in particular in the automotive industry, the automotive supplier industry and the steel industry, as well as in the construction industry and in apparatus construction.
  • the substrates coated by the process according to the invention can be used in particular as wire, wire mesh, tape, sheet metal, profile, cladding, part of a vehicle or missile, element for a household appliance, element in construction, frame, guard rail, radiator or fence element, Shaped part of complicated geometry or small part such as screw, nut, flange or spring.
  • the duration of use of the activating agent could be increased in part by about a factor of 5 to 10, even without supplementing the activating agent, owing to the addition of a very small amount of at least one silicon compound.
  • test panels consisted of cold-rolled steel (CRS) with a thickness of 1.2 mm or of galvanized steel on both sides with a coating of hot-dip galvanizing (HDG) or of an electrolytic galvanizing (EG) with a thickness of approx. 7 ⁇ m on each side.
  • the area of the substrates measured over both surfaces was about 400 cm 2 .
  • the activating agents are given in Table 2.
  • the activating agents A were prepared by mixing, adding water and optionally kneading at elevated temperature.
  • the activating agents B were prepared from the activating agent A with the addition of several additives in the solid state and by mixing.
  • the activating agents C were prepared from the activating agents B by addition of water, stabilizing agent (s), silane and optionally a pH adjusting additive and by stirring. This was followed by dispersing and dissolving in water.
  • the activating agents D were prepared from the increasingly water-containing activating agents A, which in addition already contained a first stabilizing agent, by adding water, stabilizing agent (s), optionally silane and at least one additive with stirring.
  • the activating agents E were prepared from the activating agents D by adding water, stabilizing agent and optionally silane and by stirring. There were no differences in the behavior of the activating agent E when silane was already added to the activating agent D or first to the activating agent E. d) Thereafter, the surfaces were zinc phosphated for 3 minutes at 55 0 C by immersion in a phosphating solution.
  • the phosphating solutions used are characterized below.
  • the coated substrates were dried in a drying oven at 100 ° C. for 10 minutes.
  • the dry test panels were provided with a cathodic dip paint and coated with the other layers of a customary in the automotive industry for bodies paint structure (layer structure and paints according to Daimler AG in lunar silver).
  • composition of the respective activating agents or the results of the tests are listed in Tables 2 and 3, respectively.
  • any silane added to the activator has previously been partially or fully hydrolyzed or / and condensed.
  • the pH of the aqueous solution was adjusted in this case.
  • Silane types each having at least one organic group:
  • AIs stabilizing agents have been used in the activating agents pyrophosphate (e), tripolyphosphate (s), thickening agent or / and at least one of the additives No. 9 to 11.
  • the temperature stability is indicated in the Tables so that the values of the layer weight of the zinc phosphate layer generated thereafter in the experiments at a Aktiv istsstoffbadtemperatur of, for example 40 0 C to the range of values from 1, 5 - did not exceed 3 g / m 2, wherein the respective bath life in the rating flowed.
  • the coating weight was measured with a Gardometer type ... ?? from Fa. ... ?? determined on the principle of determination of ... at ....
  • the average crystal size was roughly estimated when viewed under the Scanning Electron Microscope (SEM) or appropriately magnified SEM images.
  • the inventive examples B 1 to B 27 relate to so-called powder activations and B 28 to B 31 so-called liquid activations.
  • phosphating solutions I to V were used in diving. In addition to nitrate, they mainly contained nitrite, nitroguanidine or hydrogen peroxide as accelerators.
  • cations in addition to alkali metal ions, iron ions, and cations leached from metal surfaces, they essentially contained only zinc, manganese, and nickel as in typical low-zinc phosphating solutions.
  • As anions they partially contained silicon hexafluoride and small amounts of free fluoride.
  • the application of the phosphating I to V was carried out by dipping.
  • the zinc phosphate crystal sizes were in the inventive examples partially slightly smaller or even significantly smaller than in the comparative examples.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé de phosphatation de surfaces métalliques, les surfaces métalliques étant traitées avant la phosphatation au moyen d'un moyen activateur aqueux colloïdal à base de phosphate et de titane, le moyen activateur contenant au moins un composé de silicium soluble dans l'eau comprenant au moins un groupe organique. L'invention concerne en outre des moyens activateurs correspondants.
EP09771552.8A 2008-12-09 2009-12-09 Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation Active EP2376674B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008054407.8A DE102008054407B4 (de) 2008-12-09 2008-12-09 Verfahren zur Beschichtung von metallischen Oberflächen mit einem Aktivierungsmittel vor dem Phosphatieren, entsprechende Aktivierungsmittel sowie Verwendung der mit dem Verfahren beschichteten Substrate
PCT/EP2009/066680 WO2010066765A1 (fr) 2008-12-09 2009-12-09 Procédé de revêtement de surfaces métalliques au moyen d'un moyen activateur avant la phosphatation

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EP2376674A1 true EP2376674A1 (fr) 2011-10-19
EP2376674B1 EP2376674B1 (fr) 2018-03-14

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US (2) US9364855B2 (fr)
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JP (1) JP5595414B2 (fr)
CN (2) CN106947967B (fr)
BR (1) BRPI0922732B1 (fr)
CA (1) CA2746090C (fr)
DE (1) DE102008054407B4 (fr)
ES (1) ES2673644T3 (fr)
MX (1) MX2011006059A (fr)
WO (1) WO2010066765A1 (fr)

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DE102013202286B3 (de) * 2013-02-13 2014-01-30 Chemetall Gmbh Verwendung eines Silan-, Silanol- oder/und Siloxan-Zusatzes zur Vermeidung von Stippen auf Zink-haltigen Metalloberflächen und Verwendung der beschichteten Metallsubstrate
WO2015124322A1 (fr) * 2014-02-20 2015-08-27 Tata Steel Ijmuiden B.V. Traitement d'activation de substrats d'acier revêtus
DE102014105226A1 (de) 2014-04-11 2015-10-15 Thyssenkrupp Ag Verfahren zur Aktivierung von zu phosphatierenden Metalloberflächen, vorzugsweise verzinktem Stahlblech
JP6660116B2 (ja) * 2015-08-03 2020-03-04 東京応化工業株式会社 シランカップリング剤水溶液、単分子膜製造方法及びめっき造形方法
CN105063577A (zh) * 2015-08-25 2015-11-18 山东建筑大学 一种耐高温磷酸钙盐-磷灰石膜层的制备方法
CN105106022B (zh) * 2015-08-25 2018-05-01 福建省诺希科技园发展有限公司 一种抗菌牙齿生长修复材料的制备方法
CN105887064B (zh) * 2016-06-15 2018-01-23 武汉钢铁有限公司 一种汽车镀锌板磷化处理生产方法
CN107090206A (zh) * 2017-05-04 2017-08-25 明光市飞洲新材料有限公司 一种铸造涂料专用悬浮触变剂的制造方法
GB2561260B (en) 2017-06-21 2019-05-08 C Ling Ltd Pull-in head assembly
KR101968836B1 (ko) * 2017-09-26 2019-04-12 현대제철 주식회사 전기아연도금강판 및 이의 제조방법
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CA2746090C (fr) 2018-04-17
US20140051311A1 (en) 2014-02-20
DE102008054407B4 (de) 2018-03-29
US9358574B2 (en) 2016-06-07
MX2011006059A (es) 2011-08-03
EP2376674B1 (fr) 2018-03-14
ES2673644T3 (es) 2018-06-25
BRPI0922732A2 (pt) 2016-01-05
CN106947967A (zh) 2017-07-14
DE102008054407A1 (de) 2010-06-10
US9364855B2 (en) 2016-06-14
WO2010066765A1 (fr) 2010-06-17
US20110226159A1 (en) 2011-09-22
CN106947967B (zh) 2020-07-03
CN102308024A (zh) 2012-01-04
BRPI0922732B1 (pt) 2019-12-10
JP2012511631A (ja) 2012-05-24
CA2746090A1 (fr) 2010-06-17
JP5595414B2 (ja) 2014-09-24

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