EP2817434A1

EP2817434A1 - Pretreating zinc surfaces prior to a passivating process

Info

Publication number: EP2817434A1
Application number: EP13705479.7A
Authority: EP
Inventors: Andreas Arnold; Michael Wolpers; Marcel Roth; Uta Sundermeier
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2012-02-24
Filing date: 2013-02-22
Publication date: 2014-12-31
Anticipated expiration: 2033-02-22
Also published as: KR102095832B1; CN104185693B; EP2817434B1; ES2658337T3; EP3093370A1; PL3093370T3; KR20140129238A; CA2864467A1; PL2817434T3; US10227686B2; AU2013224115A1; JP2015510550A; CN104185693A; AU2013224115B2; HUE033958T2; EP3093370B1; WO2013124400A1; JP6526968B2; US20140360630A1; CA2864467C

Abstract

The invention relates to a wet-chemical pretreatment of zinc surfaces prior to applying a corrosion-protection coating. The wet-chemical pretreatment produces a deposition of a thin inorganic coating which substantially consists of oxide and/or metallic iron. An iron layer structure which is applied according to the invention, hereinafter referred to as steeling, improves the achievable corrosion protection of wet-chemical conversion coatings known from the prior art on zinc surfaces. Furthermore, the steeling process causes both a reduction of the contact corrosion of joined metal components which have zinc and iron surfaces as well as a reduction of corrosive coating migration on cut edges of galvanized steel strips with coating layer structures. In particular, the invention relates to an alkali composition for steeling purposes, said composition containing an iron ion source, a reducing agent based on oxoacids of the elements nitrogen and phosphorus, and water-soluble organic carboxylic acids with an amino group at the α, ß, or γ position with respect to the acid group and/or the water-soluble salts thereof.

Description

Pre-treatment of zinc surfaces before passivation

The present invention relates to a wet-chemical pretreatment of zinc surfaces prior to the application of a corrosion-protective coating. The wet-chemical

Pretreatment causes the deposition of a thin inorganic coating consisting essentially of oxidic and / or metallic iron. A layer of iron applied according to the invention - referred to below as icing - requires an improvement in the achievable corrosion protection of wet-chemical conversion coatings known from the prior art on zinc surfaces. Furthermore, the icing causes both a reduction in the contact corrosion of assembled metallic components having zinc and iron surfaces as well as a reduction of corrosive paint infiltration of cut edges of galvanized steel strip with

Paint layer structure. The invention particularly relates to an alkaline composition for icing containing a source of iron ions, a reducing agent based on oxo acids of the elements nitrogen and phosphorus and water-soluble organic

Carboxylic acids with an amino group in the a, ß, or γ position to the acid group and / or their water-soluble salts.

In the steel industry, a large number of surface-refined steel materials are produced, with surface-refined versions being in great demand to ensure the most sustainable possible protection against corrosion. For the production of products, such as automobile bodies, in particular thin sheet products made of different metallic materials and with different surface finish are processed. For the production of the products, the surface-treated steel strip is cut to size, formed and joined by welding or gluing process with other metallic components. In these products, therefore, a variety of combinations of metallic base and surface material are realized. This type of production is highly typical of the body shop in the automotive industry and is often called

Designated multimetal construction. In the body shop mainly galvanized steel strip is processed and joined together, for example, with non-galvanized steel strip and / or strip aluminum. Thus, car bodies consist of a large number of sheet-metal parts which are joined together by spot welding.

The metallic zinc coatings, which are applied to the steel strip either electrolytically or by hot dip coating, impart a cathodic protective effect which permits active dissolution of the nobler core material by mechanically causing injuries to the material Zinc coating effectively prevented. However, there is an economic interest in minimizing the overall corrosion rate in order to sustain the cathodic protection of the less noble metal coating as sustainably as possible. For this purpose, at the strip steel manufacturer or before painting in the paint shop of the production line of bodies at the car manufacturer Passivierungsschichten that are purely inorganic or mixed organic-inorganic nature, and / or organic primer applied as a barrier layer to further minimize the corrosion, which also Lackhaftgrund serve for a subsequent topcoat of the product.

From today's usual combination of variety of metallic strip materials in a product and the primary use of surface-coated strip steel results in the described manufacturing processes as special corrosion phenomena Schnittkanten- and bimetallic corrosion. At cutting edges and at the zinc coating caused by machining or other influences, the galvanic coupling between the core material and the metallic coating causes a local dissolution of the coating material, which in turn corrosive infiltration of the organic

Barrier layers can result in these places. The phenomenon of paint adhesion or "blistering" is therefore observed in particular at the cut edges of the sheets, and the same applies in principle to the positions of a component where different metallic materials are directly connected by joining techniques and bimetallic corrosion is the result "Defective" (cutting edge, injury in the metallic coating, spot welding point) and thus the corrosive paint release, which emanates from these "defects", is the more pronounced the larger the electrical

Potential difference between the metals in direct contact. Correspondingly good results with regard to paint adhesion to cut edges are provided by steel strips with zinc coatings alloyed with more noble metals, e.g. Iron-alloyed zinc coatings (galvannealed steel). The steel producers are increasingly turning to the application of inorganic and / or organic coatings in addition to surface finishing with metallic coatings

Protective layers, in particular the application of organic primers to integrate in the belt system. In this regard, there is a great deal in the processing industry

economic interest therein to obtain such surface-finished strip steel, whose predisposition to Schnittkanten- and bimetallic corrosion is only slightly pronounced, so that even after the production of the products, which includes stamping, cutting, forming and / or joining the strip steel, and a subsequent coating layer structure Furthermore, a good corrosion protection and a good paint adhesion can be guaranteed. Likewise, in the processing industry, there is a need for the surfaces of

different metallic band materials composite products such to pretreat that the preferred abstention of subsequently applied lacquer layers is leveled at cut edges and bimetallic contacts.

The prior art describes various pretreatments that address the problem of edge protection. An essential strategy is to improve the paint adhesion of the organic barrier layer on the surface-treated steel strip. For example, German Patent Application DE 197 33 972 A1 teaches a process for the alkaline passivating pretreatment of galvanized and alloy-galvanized

Steel surfaces in belt systems. Here, the surface-treated steel strip is brought into contact with an alkaline treatment agent containing magnesium ions, iron (III) ions and a complexing agent. At the given pH of above 9.5, the zinc surface is passivated thereby forming the corrosion protection layer. Such a passivated surface already offers, according to the teaching of DE19733972, a paint adhesion which is comparable with nickel- and cobalt-containing processes. Optionally, this pretreatment can be followed by further treatment steps such as chromium-free post-passivation to improve the corrosion protection before the paint system is applied.

Likewise, DE 10 2010 001 686 A1 pursues the passivation of galvanized steel surfaces using alkaline compositions containing iron (III) ions, phosphate ions and one or more complexing agents to prepare the zinc surfaces for subsequent acid passivation and resist coating. The alkaline passivation serves primarily to improve the corrosion protection of chromium-free

Conversion coatings. The aim is to achieve an alkaline cleaning step that leads to alkaline passivation and subsequent acidic passivation to provide a coating base which is comparable to zinc phosphating and protects against corrosion.

In contrast, DE 10 2007 021 364 A1 additionally pursues the goal of realizing a thin metallic layer coating on galvanized steel surfaces by means of electroless plating of electrolytic metal cations without external current, which together with a following

Passivation a significantly reduced corrosion at cut edges and bimetallic contacts of cut and assembled surface-coated strip steel should afford. There, in particular, the icing and tinning of galvanized and alloy-galvanized steel strip is proposed to improve the edge protection. For the icing, preferably acidic compositions containing iron ions, a complexing agent with oxygen and / or nitrogen ligands and phosphinic acid are used as the reducing agent. The object of the present invention is to further develop the icing of metallic components having zinc surfaces such that, in conjunction with subsequent wet-chemical conversion coatings, improved corrosion protection and paint adhesion on the zinc surfaces results, in particular the edge protection is to be improved at cutting edges of galvanized steel surfaces ,

Surprisingly, it could be shown that when using organic

Carboxylic acids with an amino group in the a, ß, or γ position to the acid group and / or their water-soluble salts in alkaline compositions for icing on

Zinc surfaces extremely homogeneous thin layer supports consisting essentially of oxidic and / or metallic iron are generated ("icing"), in the

Interaction with a subsequent wet-chemical conversion treatment improved corrosion protection, especially at cutting edges of galvanized

Steel surfaces, and provide an excellent Lackhaftgrund.

The present invention therefore relates in a first aspect to an alkaline

Composition for pretreatment of metallic components having zinc surfaces, having a pH of at least 8.5

a) at least 0.01 g / l of iron ions,

b) one or more water-soluble organic carboxylic acids which have at least one amino group in the a, ß, or y position to the acid group, as well as their

water-soluble salts,

c) one or more oxo acids of phosphorus or nitrogen and their water-soluble salts, wherein at least one phosphorus atom or nitrogen atom is present in a middle oxidation state.

Water solubility in the context of the present invention means that the solubility of the compound at a temperature of 25 ° C and a pressure of 1 bar in deionized

Water with a conductivity of less than "^ Scrn ^{" 1 is} greater than 1 g / l.

Oxidation stage according to the invention refers to the hypothetical charge of an atom, which consists of the number of electrons of the atom in comparison to its

Atomic number that the corresponding atom hypothesizes when electrons are attributed to the electronegativity of the elements that make up the molecule or salt, and the higher electronegativity element combines all the electrons that it shares with the elements of lower electronegativity; while electrons that be shared by the same elements, each half be awarded to the one and the other half to the other atom.

According to the invention, surfaces of galvanized steel and alloy-galvanized steel are considered as zinc surfaces in addition to surfaces of metallic zinc if the zinc coating is at least 5 g / m ² based on the element zinc and the proportion of zinc in the zinc layer on the steel is at least 40 at% ,

The source of iron ions dissolved in water are all compounds which release iron ions in water. Preferably, one or more water-soluble salts of di- or trivalent iron in a composition according to the invention can serve as a source of iron ions dissolved in water, wherein the use of water-soluble salts of divalent iron ions is preferred, such as, for example, iron (II) nitrate or iron (II) sulfate.

Particularly suitable water-soluble compounds are the corresponding salts of the α-hydroxycarboxylic acids having not more than 8 carbon atoms, which in turn are preferably selected from salts of polyhydroxymonocarboxylic acid, polyhydroxydicarboxylic acid each having at least 4 carbon atoms, tartronic acid, glycolic acid, lactic acid and / or α-hydroxybutyric acid.

For a sufficiently fast kinetics of icing from aqueous solution, preference is given to compositions according to the invention in which at least 0.1 g / l, preferably at least 1 g / l, particularly preferably at least 2 g / l, of iron ions dissolved in the aqueous phase are included. In principle, additional amounts of dissolved iron ions initially cause a further increase in the deposition kinetics, so that, depending on the

procedurally related application time is another minimum amount of iron ions in the composition of the invention is opportune. If the icing

procedurally conditional to perform within a few seconds, as is

for example, in the pretreatment of galvanized steel strip in one

Coil coating plant is the case, the composition preferably contains at least 3 g / l of iron ions. The upper limit for the amount of iron ions becomes

primarily determined by the stability of the composition and is for one

Composition according to the invention preferably at 50 g / l. The amounts with respect to the iron ions in a composition according to the invention relate

Of course, the amount of iron ions available for the freezing and thus the amount of dissolved in the aqueous phase iron ions, for example. In hydrated and / or complexed form. Iron ions in non-freezing form, ie for example, bound in undissolved iron salts do not contribute to the proportion of iron ions in the composition of the invention.

In a preferred composition according to the invention, the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts is not greater than 2: 1. Above this molar ratio, the accelerating effect of the organic carboxylic acids according to component b) decreases Icing already noticeable. Therefore, according to the invention are particularly preferred

Compositions in which the aforesaid molar ratio is not greater than 1: 1. Conversely, a reduction of the aforementioned molar ratio below 1:12 with a constant amount of iron ions, ie a further increase in the proportion of component b), causes no appreciable additional acceleration in the

Icing of zinc surfaces. It is therefore those inventive

Preferred compositions in which the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts is at least 1: 12, preferably at least 1: 8.

Furthermore, it has been found that certain organic carboxylic acids and / or their salts according to component b) in compositions according to the invention are particularly suitable for producing uniform and adequate iron coating layers on zinc surfaces in a time interval typical for wet-chemical pretreatment. Thus, those compositions are preferred according to the invention in which the organic carboxylic acids and / or their salts according to component b) are selected from water-soluble α-amino acids and their water-soluble salts, in particular from α-amino acids and their water-soluble salts, in addition to amino and carboxyl Groups have exclusively hydroxyl groups and / or carboxamide groups, wherein the α-amino acids preferably have not more than 7 carbon atoms. In a preferred embodiment, a composition according to the invention contains

Component b) lysine, serine, threonine, alanine, glycine, aspartic acid, glutamic acid, glutamine and / or their water-soluble salts, particularly preferably lysine, glycine,

Glutamic acid, glutamine and / or their water-soluble salts, particularly preferably glycine and / or its water-soluble salts.

In this connection, an alkaline composition for the pretreatment of metallic surfaces having zinc surfaces is preferred according to the invention, for which the proportion of glycine and / or its water-soluble salts of water-soluble organic carboxylic acids according to component b) and / or their water-soluble salts at least 50 wt .-%, more preferably at least 80 wt .-%, particularly preferably at least 90 wt .-% is.

The oxo acids of phosphorus or nitrogen according to component c) of the composition according to the invention have reducing properties and thus bring about rapid and homogeneous icing of the zinc surfaces brought into contact with the composition according to the invention. Preferred are those inventive

Used for the icing, which contain at least one oxo acid of phosphorus with at least one phosphorus atom in a middle oxidation state and their water-soluble salts as component c).

In a preferred composition according to the invention, the molar ratio of iron ions to oxo acids of phosphorus or nitrogen according to component c) and their water-soluble salts is for economic reasons at least 1:10, preferably at least 1: 6. On the other hand, the relative proportion of these compounds should be

Component c) be sufficiently large for a sufficient icing of the zinc surfaces. Preferably, therefore, the aforementioned molar ratio in a composition according to the invention is not greater than 3: 1, more preferably not greater than 2: 1. It is further preferred if the proportion of oxo acids of phosphorus in a

Composition according to the invention based on the total amount of components c) at least 50 mol .-%, particularly preferably at least 80 mol .-% is.

In order to increase the deposition rate, the compounds according to component c) of a composition according to the invention are preferably selected from hyposalphurous acid, hypo nitric acid, nitrous acid, hypophosphoric acid, hypodiphosphonic acid,

Diphosphorus (III, V) acid, phosphonic acid, diphosphonic acid and phosphinic acid and their water-soluble salts, with phosphinic acid and its water-soluble salts being particularly preferred.

For a sufficient stability of the inventive composition containing iron ions, it is also advantageous to use certain complexing agents to prevent the precipitation of iron hydroxides and to maintain the highest possible proportion of iron ions in the aqueous phase in a hydrated and / or complexed form.

The composition according to the invention therefore preferably additionally contains chelating complexing agents with oxygen and / or nitrogen ligands which do not contain water-soluble carboxylic acids according to component b) of the invention Compositions are. Particularly preferred in this context are compositions according to the invention which comprise as additional component d) one or more such complexing agents which are selected from water-soluble

α-hydroxycarboxylic acids which have at least one hydroxyl and one carboxyl group and are not water-soluble organic carboxylic acids according to component b), and from their water-soluble salts. Furthermore, the water-soluble a-hydroxycarboxylic acids according to component d) preferably have not more than 8 carbon atoms and are in particular selected from polyhydroxymonocarboxylic acids and / or polyhydroxydicarboxylic acids each having at least 4 carbon atoms, tartronic acid, glycolic acid, lactic acid and / or α-hydroxybutyric acid and from their water-soluble salts, most preferably selected from lactic acid and / or 2, 3,4,5, 6-pentahydroxyhexanoic acid and from their water-soluble salts.

A particularly effective formulation of the inventive composition with the aforementioned complexing agents according to component d) has a molar ratio of iron ions to water-soluble α-hydroxycarboxylic acids and their water-soluble salts of at least 1: 4, preferably of at least 1: 3, but not greater than 2: 1, preferably not greater than 1: 1.

Furthermore, in a composition according to the invention as optional

Component e) reducing accelerators are used, which are known to the person skilled in the art in the phosphating. These include hydrazine, hydroxylamine, nitroguanidine, N-methylmorpholine N-oxide, glucoheptonate, ascorbic acid and reducing sugars.

The pH of the alkaline composition according to the invention is preferably not greater than 11.0, more preferably preferably not greater than 10.5, particularly preferably not greater than 10.0.

In addition, the compositions according to the invention may contain surface-active compounds, preferably nonionic surfactants, in order to bring about additional purification and activation of the metal surfaces, so that a homogeneous icing on the surface

Zinc surfaces is additionally favored. The nonionic surfactants are preferably selected from one or more ethoxylated and / or propoxylated C10-C18

Fatty alcohols having a total of at least two but not more than 12 alkoxy groups, particularly preferably ethoxy and / or propoxy groups, which are partially end-capped with an alkyl radical, more preferably with a methyl, ethyl, propyl, butyl radical can. The proportion of nonionic surfactants in a composition according to the invention is preferably at least 0.01 g / l, particularly preferably at least 0.1 g / l, for sufficient cleaning and activation of the metal surfaces, and for economic reasons preferably not more than 10 g / l nonionic surfactants are included.

To prevent precipitations, it is further preferred that inventive

Compositions do not contain zinc ions in an amount for which the ratio of the total molar fraction of zinc ions and iron ions to the total molar fraction of water-soluble organic carboxylic acids according to component b) and water-soluble organic α-hydroxycarboxylic acids according to component d) and their respective

water-soluble salts greater than 1: 1, more preferably greater than 2: 3.

The present invention is further characterized in that no further heavy metals have to be added to a composition according to the invention in order to provide improved corrosion protection on the zinc surfaces as part of the icing in cooperation with a subsequent wet chemical conversion treatment. A composition according to the invention therefore preferably contains less than 50 ppm total of metal ions of the elements Ni, Co, Mo, Cr, Ce, V and / or Mn, particularly preferably less than 10 ppm, particularly preferably less than 1 ppm of these elements.

Furthermore, the composition according to the invention preferably contains less than 1 g / l of water-soluble or water-dispersible organic polymers, since a

Carryover of polymeric constituents from the pretreatment for icing in subsequent baths for wet-chemical conversion treatment can adversely affect the formation of the conversion layer. According to the invention, water-soluble or water-dispersible polymers are understood as meaning organic compounds which remain in the retentate during ultrafiltration with a nominal cutoff limit (NMWC) of 10,000 μ.

The present invention also includes a concentrate which, by dilution by a factor of 5-50, provides a previously described alkaline composition of the invention. A concentrate according to the invention has a pH above 8.5 and preferably contains a) 5-100 g / l of iron ions,

b) 15-200 g / l of water-soluble organic carboxylic acids having at least one amino group in the a, ß, or y position to the acid group, as well as their

water-soluble salts, c) 20-300 g / l of oxo acids of phosphorus or nitrogen and their water-soluble salts, wherein at least one phosphorus atom or nitrogen atom in a middle

Oxidation level is present.

In a second aspect, the present invention relates to a method for pretreatment ("icing") of metallic components having zinc surfaces, wherein at least the zinc surfaces of the component

i) if necessary, first cleaned and degreased with an alkaline cleaner,

ii) contacted with a previously described inventive alkaline composition, and

iii) then a passivating wet chemical conversion treatment

be subjected.

In the process according to the invention, in step ii), first of all, a coating layer consisting essentially of oxidic and / or metallic iron is produced on the zinc surfaces ("icing") .On the other surfaces of the metallic component, for example surfaces of iron, steel and / or Such an inorganic layer can not be detected, but the specific deposition of the passive layer on the zinc surfaces leads to a passivating process in the process according to the invention, in which the icing takes place

Wet chemical conversion treatment, surprisingly, leads to a marked improvement in the paint adhesion properties of these surfaces and effectively prevents the corrosion of cut edges of galvanized steel and the contact corrosion with the

Zinc surfaces bonded ferrous metals. A passivating wet chemical

Conversion treatment is a standard procedure in the steel and automotive industry for the pretreatment of an organic topcoat.

In a preferred embodiment of the method according to the invention, the metallic component has galvanized steel surfaces. Particularly advantageous is the method in the treatment of galvanized steel strip, as it has an excellent

Edge corrosion protection provides, and of components consisting of assembled and / or assembled in mixed construction metallic components made of galvanized steel, iron and / or steel and possibly aluminum, since it greatly reduces the contact corrosion.

The alkaline cleaning step i) in the process according to the invention is optional and necessary when the surfaces of zinc have impurities in the form of salts and fats, for example drawing fats and corrosion protection oils. The icing takes place in step ii) of the process according to the invention, the type of contacting with the alkaline composition according to the invention

procedurally is not limited to a particular method. Preferably, the zinc surfaces by dipping or spraying with the inventive

Composition brought into contact with the icing.

In a preferred embodiment of the method, the metallic component is for at least 3 seconds, but not more than 4 minutes at a temperature of at least 30 ° C, more preferably at least 40 ° C, but not more than 70 ° C, more preferably not more than 60 ° C brought into contact with an alkaline composition according to the invention. As already described, the compositions according to the invention cause an icing of the zinc surfaces. The formation of icing is self-limiting, ie with increasing icing of the zinc surfaces, the deposition rate of iron decreases. The preferred treatment or contact times should be selected in the method according to the invention so that the layer of iron is at least 20 mg / m ² based on the element iron. The treatment and contact times for the realization of such a minimum layer coverage vary depending on the type of application and depend in particular on the flow of the aqueous fluids acting on the metal surface to be treated. Thus, the formation of icing in processes in which the composition is applied by spraying, faster than in immersion applications. Regardless of the type of application, the coating compositions according to the invention do not show any layer deposits on iron significantly above that due to the self-limiting freezing

300 mg / m ² based on the element iron achieved.

For a sufficient layer formation and an optimal edge protection at the

Treatment of galvanized steel surfaces should immediately after the icing in step ii) with or without subsequent rinsing step iron coatings of preferably at least 20 mg / m ² , more preferably at least 50 mg / m ² , more preferably more than 100 mg / m ² , but preferably not more than 250 mg / m ^{2 in} each case based on the element iron realized realized.

The coating of iron on the zinc surfaces can be determined after dissolution of the coating by means of a spectroscopic method which is described in the examples of the present invention.

The icing in step ii) of the method according to the invention is preferably carried out without external current, ie without applying an external voltage source to the metallic component. In step iii) of the method according to the invention, a passivating wet-chemical takes place in step ii) with or without an intermediate rinsing step

Conversion treatment. Wet-chemical conversion treatment is understood according to the invention as bringing into contact at least the zinc surfaces of the metallic component with an aqueous composition which produces a passivating and substantially inorganic conversion coating on the treated zinc surfaces. In this case, a conversion coating is any inorganic coating on the metallic zinc substrate which does not represent an oxide or hydroxide coating whose cationogenic main constituent is zinc ions. A conversion coating can therefore be a

Be zinc phosphate layer.

In a preferred embodiment of the process according to the invention, a passivating wet chemical conversion treatment is carried out in step iii) by bringing into contact with an acidic aqueous composition which has a total of at least 5 ppm but not more than 1500 ppm total of water-soluble inorganic compounds of the elements Zr, Ti , Si and / or Hf based on the aforementioned elements, and preferably water-soluble inorganic compounds which release fluoride ions, for example, fluorocomplexes, hydrofluoric acid and / or metal fluorides.

Preferred in this regard are those acidic aqueous compositions in step iii) of the process according to the invention which contain as water-soluble compounds of the elements zirconium, titanium and / or hafnium only water-soluble compounds of the elements zirconium and / or titanium, more preferably water-soluble compounds of the element zirconium. As water-soluble compounds of the elements zirconium and / or titanium, both compounds which dissociate in aqueous solution into anions of fluorocomplexes of the elements titanium and / or zirconium, for example H ₂ ZrF ₆ , K ₂ ZrF ₆ , Na ₂ ZrF ₆ and (NH ₄ ) ₂ ZrF ₆ and the analogous titanium compounds, as well as fluorine-free compounds of the elements

Zirconium and / or titanium, for example (NH ₄ ) ₂ Zr (OH) ₂ (CO ₃ ) ₂ or TiO (SO ₄ ), in acidic aqueous compositions in step iii) of the process according to the invention.

In step iii) of the preferred process according to the invention, the acidic aqueous

Composition, in total at least 5 ppm, but not more than

Contains 1500 ppm of water-soluble inorganic compounds of the elements Zr, Ti, Si and / or Hf based on the aforementioned elements, preferably chromium-free, ie it contains less than 10 ppm, preferably less than 1 ppm chromium, especially no chromium (VI). In an alternative preferred embodiment of the process according to the invention, a zinc phosphating is carried out in step iii), wherein the presence of the heavy metals Ni and / or Cu in the zinc phosphating can largely be dispensed with due to the previous icing of the zinc surfaces of the metallic component in step ii). The icing of the zinc surfaces thus provides for a subsequent Zinkphosphatierung the unexpected advantage that for such phosphated zinc surfaces, a corrosion protection and a

Lacquer adhesion results comparable to the zinc phosphating of iron or steel surfaces.

In a preferred embodiment of the method according to the invention, the passivating wet-chemical conversion treatment in step iii) consists in contacting the galvanized steel surfaces pretreated in step ii) with an acidic aqueous composition having a pH in the range of 2.5-3 , 6 and

a) 0.2 to 3.0 g / L zinc (II) ions,

b) 5.0 to 30 g / L of phosphate ions calculated as P2O5, and

c) preferably each less than 0, 1 g / L of ionic compounds of the metals nickel and cobalt in each case based on the metallic element.

The pretreated metallic components, which have surfaces of zinc directly resulting from a method according to the invention, are then preferably provided with an organic covering layer, with or without an intermediate rinsing and / or drying step. The first cover layer in the pretreatment of already cut, formed and assembled components is usually an electrodeposition paint, more preferably a cathodic dip. In contrast, organic primer coatings are preferably used as the first organic cover layer in the

corrosion-protective or decorative coating of galvanized steel strip applied after the inventive method.

The treated in a method according to the invention metallic components, the

Surfaces of zinc, are used in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods. EXAMPLES

The influence of various α-amino acids with respect to the homogeneity of the icing after contacting of inventive compositions with electrolytically galvanized steel by dipping is reproduced in Table 1.

First, thin coatings of oxidic and / or metallic iron on the zinc surfaces are obtained with all compositions (C1-C4) according to the invention

("Icing"), but particularly homogeneous coatings specifically from

Compositions according to the invention (C1; C5) containing glycine are formed.

Table 1

Alkaline compositions according to the invention for icing

on electrolytically galvanized sheet steel (Gardobond® MBZE7)

regarding homogeneity of icing:

++ homogeneous dark gray coating

+ almost complete coverage with dark gray coating

O incomplete coverage with dark gray to brownish coating

inhomogeneous coverage with predominantly light gray to brownish coating

The concentration of the active components in a composition according to the invention has an immediate effect on the deposition rate, so that dilute compositions must be brought into contact with the galvanized steel surface for a longer time in order to obtain a homogeneously coated zinc surface (see C1 in comparison to C5). In the following, the effect of icing when using compositions according to the invention on the basis of process chains for the corrosion-protective pretreatment of zinc surfaces will be illustrated. Table 2 shows the corrosive infiltration of an immersion paint on electrolytically galvanized steel after the respective process chain for corrosion-protective pretreatment in Wechselklimatest and stone impact test again.

The individual process steps of the process chains listed in Table 2 for the corrosion-protective treatment of individual galvanized steel sheets (Gardobond® MBZE7) follow:

A. Alkaline Purification (pH 1 1):

3% by weight of Ridoline® 1574A (Henkel);

0.4% by weight of Ridosol® 1270 (Henkel)

Treatment time at 60 ° C: 180 seconds

B. Rinsing with demineralized water (κ <1 μεοηη ^"1 )

C. icing using a composition according to Table 1:

Treatment time at 50 ° C: 60 seconds

D. Activation:

0.1% by weight of Fixodine® 50CF (Henkel)

Remaining deionized water (κ <1 μεοηΥ ¹ )

Duration of treatment at 20 ° C: 60 seconds

E1. Acid passivation:

0.34 g / LH ₂ Zr _F 6

0.12 g / L ammonium bifluoride

0.08 g / L Cu (NO ₃ ) ₂ -3H ₂ O

Remaining deionized water (κ <1 μεοηΥ ¹ )

pH 4

Treatment time at 30 ° C: 120 seconds

E2. Nickel-free phosphating:

0, 13 wt .-% zinc

0.09 wt .-% manganese

0.12 wt.% Nitrate

1, 63 wt .-% phosphate 0.25% by weight of hydroxylamine sulfate

0.02% by weight of ammonium bifluoride

0.10% by weight of H ₂ SiF ₆

Remaining deionized water (κ <1 μβοηι ^"1 )

Free fluoride: 40 mg / L

Free acid: 1, 3 points (pH 3.6)

Total acidity: 26 points (pH 8.5)

Treatment time at 50 ° C: 180 seconds

Nickel-containing phosphating (trication-phosphating)

0.13% by weight of zinc

0.09% by weight of manganese

0, 10 wt -.% Nickel

0.32% by weight of nitrate

1, 63% by weight of phosphate

0.25% by weight of hydroxylamine sulfate

0.02% by weight of ammonium bifluoride

0.10% by weight of H ₂ SiF ₆

Remaining deionized water (κ <1 μScm ^"1 )

Free fluoride: 40 mg / L

Free acid: 1, 3 points (pH 3.6)

Total acid: 26.5 points (pH 8.5)

Treatment time at 50 ° C: 180 seconds

F. Coating structure: EV2007 (PPG company): layer thickness 17-19 m

From Table 2 it is clear that the icing in a process chain according to the invention, the wet chemical conversion by means of aqueous zirconium-containing

Passivierungslösungen (B1) compared to an analog process chain, in which the icing is omitted (V1) causes improved corrosion protection.

The same can be said for the improvement of the corrosion protection of those galvanized steel sheets subjected to nickel-free zinc phosphating. Here, too, the previous freezing (B2) results in significantly improved corrosion values compared to pure zinc phosphating (V2). The achieved with the icing

Corrosion results (B2) are even improved in comparison with the trication-phosphating (V3) frequently used in the prior art for the corrosion-protective pretreatment of components manufactured in mixed construction. Table 2

Various process sequences for the anticorrosive treatment of

electrolytically galvanized steel strip (Gardobond® MBZE7, Fa. Chemetall) and the

Results regarding infiltration at the Ritz and in the stone impact test

Rockfall and infiltration at the Ritz in accordance with DIN EN ISO 20567-1 after removal according to the climate test VDA 621-415 (10 weeks)

determined by removing the zinc phosphate layer with aqueous 5 wt .-% Cr0 ₃ , which was brought immediately after step E2 or E3 at 25 ° C for 5 min with a defined surface of the galvanized sheet in contact, and determining the phosphorus content in the same pickling solution with ICP-OES. The coating weight of zinc phosphate results from the multiplication of the area-related amount of phosphorus with the factor 6.23.

quantitative determination of the amount of iron (III) ions by means of a UV photometer (WTW, PhotoFlex®) in 300 μl sample volume of a 5% strength by weight nitric acid solution, which is used immediately after process step "C" using a measuring cell ring (Fa Helmut-Fischer) was pipetted onto a defined area of the 1.33 cm ² galvanized sheet and, after a contact time of 30 seconds at a temperature of 25 ° C., picked up by the same pipette and placed in the UV measuring cuvette in which 5 ml of a 1, 0% sodium thiocyanate solution was submitted, to determine the absorption at a wavelength of 517 nm and temperature of 25 ° C. The calibration was carried out in two-step method by determining the absorption values of identical volumes (300μΙ) of two standard solutions of iron (III) nitrate in 5% strength by weight nitric acid, which was used to determine the absorption values at 25 ° C. in the measuring cuvette containing 5 ml of a 1% sodium thiocyanate solution were transferred.

Claims

claims

An alkaline aqueous composition for pretreatment of metallic components having zinc surfaces, having a pH of at least 8.5

a) at least 0.01 g / l of iron ions,

b) one or more water-soluble organic carboxylic acids which

have at least one amino group in o, ß-, or γ-position to the acid group, and their water-soluble salts,

c) one or more oxo acids of phosphorus or nitrogen and their water-soluble salts, wherein at least one phosphorus atom or

Nitrogen atom is present in a middle oxidation state.

2. Composition according to claim 1, characterized in that at least

1 g / l, preferably at least 2 g / l, but not more than 10 g / l of iron ions are contained in total.

3. Composition according to one or both of the preceding claims, characterized in that the molar ratio of iron ions to water-soluble organic carboxylic acids according to component b) and their water-soluble salts is at least 1: 12, preferably at least 1: 8, but not greater than 2: 1, preferably not greater than 1: 1.

4. Composition according to one or more of the preceding claims,

characterized in that the water-soluble organic carboxylic acids according to component b) are selected from α-amino acids which preferably have hydroxyl groups in addition to amino and carboxyl groups, and are particularly preferably selected from lysine, serine, threonine, alanine, glycine, Aspartic acid and / or glutamic acid. Composition according to one or more of the preceding claims, characterized in that the molar ratio of iron ions to oxo acids of phosphorus or nitrogen according to component c) and their water-soluble salts at least 1:10, preferably at least 1: 6, but not greater than 3 Is 1, preferably not greater than 2: 1.

Composition according to one or more of the preceding claims, characterized in that the oxo acids of phosphorus or nitrogen according to component c) are selected from hyposporous acid,

Hypos nitric Acid, Nitrous Acid, Hypophosphorous Acid,

Hypodiphosphonic acid, diphosphorus (III, V) acid, phosphonic acid,

Diphosphonic acid and / or phosphinic acid and their water-soluble salts.

Composition according to one or more of the preceding claims, characterized in that as component d) additionally one or more water-soluble α-hydroxycarboxylic acids which have at least one hydroxyl and one carboxyl group and no water-soluble organic

Carboxylic acids according to component b), and their water-soluble salts are included.

Composition according to claim 7, characterized in that the molar ratio of iron ions to water-soluble α-hydroxycarboxylic acids according to component d) and their water-soluble salts is at least 1: 4, preferably at least 1: 3, but not greater than 2: 1, preferably not is greater than 1: 1.

Composition according to one or both of the preceding claims 7 and 8, characterized in that the water-soluble a-hydroxycarboxylic acids according to component d) have not more than 8 carbon atoms and are preferably selected from polyhydroxymonocarboxylic acids and / or polyhydroxydicarboxylic acids each having at least 4 carbon atoms, tartronic acid, glycolic acid , Lactic acid and / or α-hydroxybutyric acid.

10. The composition according to one or more of the preceding claims, characterized in that the pH is not greater than 1 1, 0, preferably not greater than 10.5, more preferably not greater than 10.0.

11. Composition according to one or more of the preceding claims,

characterized in that zinc ions are not contained in an amount for which the ratio of the total molar fraction of zinc and iron ions to the total molar fraction of water-soluble organic carboxylic acids according to component b) and water-soluble organic

α-hydroxycarboxylic acids according to component d) and their respective water-soluble salts is greater than 1: 1, preferably greater than 2: 3.

12. Process for the pretreatment of galvanized steel surfaces, thereby

characterized in that the galvanized steel surfaces

i) optionally first cleaned and degreased with an alkaline cleaner, ii) contacted with an alkaline composition according to one or more of the preceding claims, and

iii) subsequently a passivating wet-chemical

Be subjected to conversion treatment.

13. The method according to claim 12, characterized in that step ii)

without external power.

14. The method according to one or both of claims 12 and 13, characterized

characterized in that the passivating wet chemical conversion treatment is to contact the galvanized steel surfaces pretreated in step ii) with an acidic aqueous composition comprising at least 5 ppm total but not more than 1500 ppm of water-soluble inorganic compounds of the elements Zr, Ti , Si and / or Hf based on the aforementioned elements, and preferably containing water-soluble inorganic compounds which release fluoride ions.

15. The method according to one or both of claims 12 and 13, characterized in that the passivating wet chemical conversion treatment is to contact the galvanized steel surfaces pretreated in step ii) with an acidic aqueous composition having a pH in the range of Has 2.5-3.6 and

a) 0.2 to 3.0 g / L zinc (II) ions,

b) 5.0 to 30 g / L of phosphate ions calculated as P ₂ 0 ₅ , and