EP2376674A1

EP2376674A1 - Method for coating metal surfaces with an activating agent prior to phosphating

Info

Publication number: EP2376674A1
Application number: EP09771552A
Authority: EP
Inventors: Thomas Kolberg; Eckart SCHÖNFELDER; Olaf Dahlenburg; Manfred Walter
Original assignee: Chemetall GmbH
Current assignee: Chemetall GmbH
Priority date: 2008-12-09
Filing date: 2009-12-09
Publication date: 2011-10-19
Anticipated expiration: 2029-12-09
Also published as: MX2011006059A; CN106947967B; CN102308024A; US20110226159A1; DE102008054407A1; CA2746090C; BRPI0922732A2; JP2012511631A; DE102008054407B4; WO2010066765A1; US9364855B2; ES2673644T3; CA2746090A1; US20140051311A1; BRPI0922732B1; EP2376674B1; CN106947967A; US9358574B2; JP5595414B2

Abstract

The invention relates to a method for phosphating metal surfaces in which the metal surfaces are treated with an aqueous phosphate and titanium-based colloidal activating agent prior to phosphating, wherein the activating agent comprises at least one water-soluble silicon compound having at least one organic group. The invention also relates to a corresponding activating agent.

Description

Process for coating metallic surfaces with an activating agent before phosphating

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.

For many decades, 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. In particular, 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.

In particular, 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.

Due to a good activation, the layer of the crystalline zinc-containing phosphate can be formed largely to completely closed. In addition, in many embodiments, it is advantageous if the crystalline layer is formed comparatively fine-grained and / or substantially uniformly shaped crystals. For example, 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. However, if the activation is omitted prior to this type of phosphating, then 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 μm mean crystal size under the scanning electron microscope. In the latter case, 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.

The currently available in the market 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. There are a few single 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. In principle, 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. The term "bath" here stands for the treatment bath.

It is therefore desirable to develop and propose an activating agent that can be used for as many as five days (= 1 working week) and that shows only minor property fluctuations over this period (= long-term stability). If there is little variation in the coating weight of the phosphate layer produced and the average phosphate crystal size over the time of use, the quality of the activation is also considered to be good or even very good.

In the method according to the invention, 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.

Moreover, it is advantageous if 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.

It was therefore the object to propose an activating agent whose service life is better suited for mass production due to longer lasting stability and / or higher thermal stability.

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.

In the method of the present invention, 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. In this case, preferably 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. For the preparation of a powdered activating agent such as the activating agent B, for example from an activating agent A, an initial water content of 5 to 30% by weight is preferred, for the preparation of 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.

To an aqueous or powdered activating agent, such as in particular to the activating agent A and / or F, 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.

In principle, various processes are possible for the preparation of an aqueous colloidal activating agent. The most important procedures are listed here.

In the process according to the invention, in a process variant 1), an aqueous to moist (= "aqueous") activating agent such as the activating agent A may preferably be used to obtain first a powdered activating agent, in particular storable, such as the activating agent B, for example by further drying, mixing, kneading and / or granulating and then, if necessary, before dissolving an activating agent C on metallic surfaces, dissolving the pulverulent activating agent B in water and dispersing it. especially with stirring, which can then be applied to the metallic surfaces. The powdery activating agent B usually contains colloidal titanium phosphate in a dried state. In addition, if appropriate, 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.

In the process according to the invention, in a process variant 2) an aqueous colloidal activating agent according to the invention, e.g. the activating agent D, for example, from an aqueous activating agent, e.g. the activating agent A preferably by adding e.g. be prepared or prepared from at least one stabilizer. A particularly storable aqueous colloidal activator such as e.g. If desired, 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. In addition, optionally 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.

In the process according to the invention, in a process variant 3), 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. In addition, if appropriate, 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. In the process according to the invention, 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). Alternatively, 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. Such a stabilizer stabilizes in particular the titanium phosphate colloids. When the aqueous colloidal activating agent contains no or too little stabilizing agent, 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. In some aqueous colloidal activators or / and in some situations of the activator bath, 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 Aktivierungsmittelbades of more than 4 hours. Table 1: Overview of the various activating agents, their precursors, their contents and their state:

usually ⁺ instead of the usual bath concentration, it can also be a concentrate

Here, the aqueous colloidal activating agents according to the invention, such as the activating agents C, E and G, comprise at least one water-soluble silicon compound having at least one organic group, while 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.

For the purposes of this application, 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 In many embodiments, 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, such as the activating agents C, E and G, 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. They are usually precursors of the aqueous colloidal activating agents according to the invention, which are used in the concentration of the treatment bath of an activating agent bath. Preferably, a powdered activating agent according to the invention, such as the activating agent B, 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 μm, particularly preferably in the range from 10 to 500 μm, in substantially dry state determined by sieve analysis with sieves in the range of about 500 to about 25 μm mesh size. It preferably has an average powder particle size in the range from 25 to 150 μm, particularly preferably in the range from 40 to 80 μm. 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. In the case of a pulverulent activating agent, such as the activating agent B, 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.

The 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.

If 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, such as the activating agent C containing no stabilizing agent, 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, such as the activating agent G, 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. In part, the quality of activation of an aqueous activator G is somewhat less than that of the aqueous activators C and E. However, 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, such as the activating agents C, E and G, 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.

Preferably, 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.

Preferably, 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. In addition, 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.

In the process of the present invention, 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).

In the method according to the invention, 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.

Optionally, in some embodiments, 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.

In the process of the present invention, 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 /. and 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).

The term "SNan" or "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 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 work, the respective other silanes or other reaction products can usually not be specified.

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.

In the process according to the invention, as 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. Preference is given in particular to those silanes / silanols / siloxanes which have a chain length in the range from 2 to 5 C atoms and a functional group, the latter being suitable for the reaction with polymers. In particular, 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.

Preferably, the aqueous composition contains at least one silane selected from the group of

Glycidoxyalkyltrialkoxysilan,

methacryloxyalkyltrialkoxysilane,

(Trialkoxysilyl) alkylbernsteinsäuresilan,

Aminoalkylaminoalkylalkyldialkoxysilane, (epoxycycloalkyl) alkyltrialkoxysilane, alpha-aminoalkyliminoalkyltrialkoxysilane, bis (trialkoxysilylalkyl) amine, bis (trialkoxysilyl) ethane, (epoxyalkyl) trialkoxysilane,

aminoalkyl,

Ureidoalkylthalkoxysilan,

N- (trialkoxysilylalkyl) alkylenediamine,

N-

(aminoalkyl) aminoalkyltrialkoxysilane, N- (trialkoxysilylalkyl) dialkylenetriamine, poly (aminoalkyl) alkyldialkoxysilane, tris (trialkoxysilyl) alkyl isocyanurate, ureidoalkyltrialkoxysilane and acetoxysilane.

3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylthmethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (triethoxysilyl) propylbernsteinsäuresilan,

Alpha aminoethyliminopropyltrinnethoxysilan,

Aminoethylanninopropylnnethyldiethoxysilan,

Aminoethylanninopropylnnethyldinnethoxysilan,

ethyltriethoxysilane beta- (3,4-epoxycyclohexyl)

ethyltrimethoxysilane beta- (3,4-epoxycyclohexyl)

methyltriethoxysilane beta- (3,4-epoxycyclohexyl)

methyltrinnethoxysilan beta- (3,4-epoxycyclohexyl)

propyltriethoxysilane Gamnna- (3,4-epoxycyclohexyl)

propyltrinnethoxysilan Gamnna- (3,4-epoxycyclohexyl)

Bis (triethoxysilylpropyl) amine,

Bis (trimethoxysilylpropyl) Annin,

(3,4-epoxybutyl) triethoxysilane,

(3,4-epoxybutyl) trinnethoxysilan,

Gamma-aminopropyltriethoxysilane,

Gamma Aminopropyltrinnethoxysilan,

Gamma ureidopropyltrialkoxysilane,

N- (3- (trinnethoxysilyl) propyl) ethylendiannin,

N-beta- (aminoethyl) -gamma-aminopropyltriethoxysilane,

N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane,

N- (gamma-triethoxysilylpropyl) diethylenetriamine,

N- (gamma-trimethoxysilylpropyl) diethylenetriamine,

N- (gamma-triethoxysilylpropyl) dimethylenetriamine,

N- (gamma-trimethoxysilylpropyl) dimethylenetriamine,

Poly (aminoalkyl) ethyldialkoxysilan,

Poly (aminoalkyl) nnethyldialkoxysilan,

Tris (3- (triethoxysilyl) propyl) isocyanurate

Tris (3- (triethoxysilyl) propyl) isocyanurate and

Vinyltriacetoxysilane.

Particularly preferred 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.

In the process according to the invention, 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.

In the process of the present invention, 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).

In the process of the invention, 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.

In the process according to the invention, 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. In the method according to the invention, 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).

In the method according to the invention, 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.

In the method according to the invention, the total content of at least one labeling ion and / or on at least one labeling compound (marker due to their color, their fluorescence and / or their chemical and / or physical analyzability) 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).

In addition, 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 softening agent (= water-hardening bonding 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, polyoxycarboxylic acid, phosphonic acid, diphosphonic acid triphosphonic acid, polyphosphonic acid, phosphonic acid esters o- / / and their derivatives such as hydroxyphosphonic acid and / or derivatives thereof are added and / or contain. As phosphonic acid, for example, HEDP = (i -Hydroxyethylidene) diphosphonic acid is particularly preferred. Such compounds serve in particular as complexing agents and / or as sequestering agents. In the process of the invention, 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).

In addition, 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. Such 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. In particular, 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. 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. Although 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.

In the process according to the invention, 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).

In the process according to the invention, 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. In the method according to the invention, 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).

In addition, 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).

In the method according to the invention, the activating agent may preferably also contain a content of at least one biocide. In the inventive Preferably, 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).

Preferably, 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. In embodiments, may the pH value may also be less than 7, if it does not come to disturbing precipitations in Aktivierungsmittelbad, or be greater than 13, if this bath does not attack the system parts too much.

In the process according to the invention, 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.

In the method according to the invention, 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.

In the method according to the invention, 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. In the method according to the invention, the metallic surfaces can preferably be rinsed with water after activation and before phosphating. In many embodiments, this rinse is optional.

In the method according to the invention, 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.

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. However, 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. In addition, 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.

In principle, surfaces of all types of materials-if appropriate also of several different materials adjacent to one another and / or one after the other in the process-can be used as surfaces, in particular all types of metallic materials. Among the 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. If appropriate, 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 ciumverbindung having at least one organic group.

The object is also achieved with an 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. and in which the powdered activating agent B was then dissolved and dispersed for application in water, or with an aqueous colloidal activating agent E prepared from an aqueous colloidal activating agent A via an aqueous colloidal activating agent D and in which the aqueous activating agent E is diluted by dilution with Water was prepared, or with an aqueous colloidal activating agent G, which was prepared from a powdered activating agent F, wherein the powdered activating agent F substantially by mixing, kneading or and wherein the aqueous colloidal activating agent G was prepared therefrom by dissolving and dispersing in water, the term "colloidal" being based only on titanium phosphate colloids, the colloidal activating agent being titanium phosphate and at least one further being titanium contains non-containing phosphate and in the concentration for a treat- treatment bath of metallic surfaces before phosphating, wherein the colloidal activating agent also contains at least one water-soluble SiI i ciumverbindung having at least one organic group.

Incidentally, the activating agent may preferably have a composition according to one of the method claims, in particular at least one stabilizing agent.

With the 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. In this case, 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 ,

In addition, 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. With the method according to the invention, it was possible to further improve the bath life, bath stability, Khstall size, resistance at elevated operating temperature and corrosion protection.

It was surprising that 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.

It was also surprising that the thermal stability (= resistance at an operating temperature of the activating agent above 50 ^° C.) could be markedly improved.

Moreover, it was surprising that not only a stabilizing effect on the coating weight, but also an improving effect for the refining of the phosphate crystal sizes occurred in the long run, as the grain size level often looked at average crystal sizes in the range of 3 to 10 μm under the scanning electron microscope established.

Furthermore, it was surprising that the introduction of the measures according to the invention did not impair the quality of the deposited phosphate layer, but it was able to maintain uniform quality over the long term. Furthermore, the layer weight of the phosphate layer remained largely constant over the entire production period, because the coating weight fluctuations could even be in a laboratory experiment over 5 working days from originally +/- 0.1 to +/- 3.0 g / m ² in a conventional Aktivierungsmittelbad on + / - 0.1 to +/- 1, 0 g / m ² are lowered at a Aktivierungsmittelbad invention.

Examples and Comparative Examples:

The object of the invention will be explained in more detail with reference to embodiments. The examples were carried out using the following substrates, process steps, substances and mixtures: The 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 μm on each side. The area of the substrates measured over both surfaces was about 400 cm ² .

a) The substrate surfaces were cleaned in a 2.5% solution of an alkaline cleaner for 10 minutes at 60 ⁰ C and thereby degreased thoroughly.

b) Rinsing with tap water followed for 0.5 minutes at room temperature.

c) Then the surfaces were activated by immersion in a colloidal titanium phosphate-containing activator for 0.5 minutes at room temperature. 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.

e) It was then rinsed first with tap water and then with demineralized water.

f) Then the coated substrates were dried in a drying oven at 100 ^° C. for 10 minutes.

g) Finally, 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).

The 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. Optionally, the pH of the aqueous solution was adjusted in this case.

Silane types each having at least one organic group:

1 alkoxysilane A

2 alkoxysilane B

3 alkoxysilane C

4 alkoxysilane D

5 phenylsilane

6 succinic acid silane

7 Thaminofunctional silane

8 epoxysilane. 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.

Additive No .:

9 1 -Hydroxyethylene (1,1-diphosphonic acid)

10 amorphous silica

11 carboxylic acid copolymer.

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 Aktivierungsmittelbadtemperatur 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 ....

In addition, it was determined radiographically on a sample of a barely water-containing activating agent A that, as crystalline substances, primarily Na ₂ HPO ₄ , Na ₂ HPO ₄ -2H ₂ O and small amounts of TiOSO _{4 are} present. Titanium phosphate could not be detected by powder diffractometry.

The average crystal size was roughly estimated when viewed under the Scanning Electron Microscope (SEM) or appropriately magnified SEM images.

Tables 2: Activating agents used

significant increase in coating weight

The inventive examples B 1 to B 27 relate to so-called powder activations and B 28 to B 31 so-called liquid activations. For the phosphate coating experiments, phosphating solutions I to V were used in diving. In addition to nitrate, they mainly contained nitrite, nitroguanidine or hydrogen peroxide as accelerators. As 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. Their free acid FS values ranged from 1.4 to 1.7, their total acid GS values ranged from 22 to 28, their total acid Fischer GSF values ranged from 15 to 20, and their S Values as the ratio of FS to GSF were approximately in the range of 0.07 to 0.10. The coating weight was determined gravimetrically by weighing before and after the peeling of the phosphate layer, the peeling on aluminum alloys with nitric acid, on steel and zinc-rich surfaces with ammonium dichromate solution. The various phosphating agents all looked similar and similarly good, but the crystal forms and crystal sizes of the phosphate crystals varied significantly. There were always good or even very good phosphate coatings.

Table 3: Coatings and test results on coatings using the phosphating solutions on activating and phosphating for 5 days each

0

The smaller the values for the corrosion and paint adhesion tests, the better the results. It was found in these experiments that the corrosion results and the paint adhesion results were partly a little better, but never worse, if instead of activation according to the prior art, the activation according to the invention was used.

The zinc phosphate crystal sizes were in the inventive examples partially slightly smaller or even significantly smaller than in the comparative examples.

Claims

claims

A process for phosphating metallic surfaces, wherein the metallic surfaces are treated with an aqueous colloidal activating agent based on phosphate and titanium prior to phosphating, characterized in that the activating agent comprises at least one water-soluble silicon compound having at least one organic group contains.

2. The method according to claim 1, characterized in that the aqueous colloidal activating agent from an aqueous colloidal activating agent (precursor A) via a powdered activating agent

(Precursor B) and thereafter dissolved and dispersed on the metallic surfaces in water prior to application (activating agent C) or prepared from an aqueous colloidal activating agent (precursor A) via an aqueous colloidal activating agent (precursor D) and thereafter before Application on the metallic

Surfaces is diluted in water (activating agent E).

3. The method according to claim 1, characterized in that the aqueous colloidal activating agent before application to the metallic surfaces of a powdered activating agent (precursor F) is dissolved in water and dispersed (activating agent G).

A method according to claim 2 or 3, characterized in that at least one substance, e.g. in each case at least one biocide, surfactant, stabilizer or / and additive for pH adjustment, in particular during dissolution and dispersion or during dilution, are added.

5. The method according to any one of the preceding claims, characterized in that the activating agent contains at least one hydrolyzed o- / / and condensed silane / silanol / siloxane / polysiloxane.

6. Process according to any one of the preceding claims, characterized in that the total content of water-soluble silicon compounds having at least one organic group in an aqueous activating agent is in the range from 0.0001 to 50 g / L, calculated in each case as silane or / and as a corresponding mainly present silicium-containing starting compound.

7. The method according to any one of the preceding claims, characterized in that the aqueous colloidal activating agent contains titanium phosphate, orthophosphate, alkali metal and optionally at least one stabilizing agent and / or at least one further additive

8. The method according to any one of the preceding claims, characterized in that the content of the aqueous activating agent in titanium in the range of 0.0001 to 10 g / L.

9. The method according to any one of the preceding claims, characterized in that the content of the aqueous activating agent is calculated on phosphate as PO ₄ in the range of 0.005 to 300 g / L.

10.A method according to any one of the preceding claims, characterized in that the phosphate is present in the aqueous colloidal activating agent in the form of titanium phosphate, titanyl phosphate, disodium phosphate and / or dipotassium phosphate.

11. The method according to any one of the preceding claims, characterized in that the total content of the aqueous activating agent of cobalt, copper or / and nickel in the range of 0.00001 to 0.1 g / L.

12. The method according to any one of the preceding claims, characterized in that the activating agent in each case at least one / an anionically modified polysaccharide, water-soluble organic copoly mer, carboxylic acid, phosphonic acid, diphosphonic acid, triphosphonic acid, polyphosphonic acid, polyelectrolyte or / and derivatives thereof.

13. The method according to any one of the preceding claims, characterized in that the activating agent is also a content of a detergent, at least one surfactant or / and at least one

Contains hydrotrope.

14. The method according to any one of the preceding claims, characterized in that the activating agent also contains a content of at least one biocide, wetting agent, softening agent, complexing agents, sequestering agents and / or markers.

15. The method according to any one of the preceding claims, characterized in that the activating agent is a colloidal solution or colloidal dispersion or a powdered activating agent, the latter being dissolved and dispersed for use in a coating process.

16. The method according to any one of the preceding claims, characterized in that the activating agent is applied at a temperature in the range of 10 to 80 ⁰ C on the metallic surfaces.

17. The method according to any one of the preceding claims, characterized in that the activating agent by flooding, swelling, spraying,

Dipping and / or rolling and optionally squeezing on the metallic surfaces is applied.

18. The method according to any one of the preceding claims, characterized in that the metallic surfaces are cleaned before degreasing, degreased or / and pickled and / or rinsed after activation and before phosphating with water.

19. The method according to any one of the preceding claims, characterized in that the metallic surfaces after activation phosphated, rinsed and / or provided with at least one organic coating.

20. Aqueous colloidal activating agent based on titanium phosphate and at least one other titanium-free phosphate for the treatment of metallic surfaces before phosphating, characterized in that the activating agent contains at least one water-soluble silicon compound having at least one organic group.

21. Aqueous colloidal activating agent A, which was prepared in essence by mixing, kneading or / and granulating the components, or aqueous colloidal activating agent C, which was prepared from an aqueous colloidal activating agent A via a powdered activating agent B and in which powdered activating agent B was then dissolved and dispersed in water for application, or aqueous colloidal activating agent E prepared from an aqueous colloidal activating agent A over an aqueous colloidal activating agent D and wherein the aqueous activating agent E was prepared by dilution with water or aqueous colloidal activating agent G which has been prepared from a powdered activating agent F, wherein the pulverulent activating agent F has been prepared essentially by mixing, kneading or / and granulating the components, and wherein the aqueous colloidal activating agent G was prepared therefrom by dissolving and dispersing in water, the term "colloidal" being based only on titanium phosphate colloids, wherein the colloidal activating agent contains titanium phosphate and at least one further, non-titanium-containing phosphate and in the Concentration for a treatment bath of Treatment of metallic surfaces before phosphating is used, in which the colloidal activating agent also contains at least one water-soluble silicon compound having at least one organic group.

22. Activation agent according to claim 20 or 21, characterized in that it has a composition according to one of claims 1 to 19.

23. Use of an activating agent according to any one of claims 20 to 22 in a cleaning agent.

24. Use of the coated according to the method of any one of claims 1 to 19 substrates as wire, wire mesh, tape, sheet metal, profile, paneling, part of a vehicle or missile, element for a household appliance, element in construction, frame, guard rail, radiator - or fence element, molded part of complicated geometry or small part.