EP2145031B1 - Preliminary metallizing treatment of zinc surfaces - Google Patents
Preliminary metallizing treatment of zinc surfaces Download PDFInfo
- Publication number
- EP2145031B1 EP2145031B1 EP08749904.2A EP08749904A EP2145031B1 EP 2145031 B1 EP2145031 B1 EP 2145031B1 EP 08749904 A EP08749904 A EP 08749904A EP 2145031 B1 EP2145031 B1 EP 2145031B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- cations
- compounds
- galvanized
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000011282 treatment Methods 0.000 title claims description 29
- 239000011701 zinc Substances 0.000 title description 46
- 229910052725 zinc Inorganic materials 0.000 title description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 33
- 238000000034 method Methods 0.000 claims description 129
- 229910052751 metal Inorganic materials 0.000 claims description 80
- 239000002184 metal Substances 0.000 claims description 80
- 230000008569 process Effects 0.000 claims description 67
- 239000011248 coating agent Substances 0.000 claims description 61
- 238000000576 coating method Methods 0.000 claims description 49
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 150000001768 cations Chemical class 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 39
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 35
- 239000008397 galvanized steel Substances 0.000 claims description 35
- 239000003973 paint Substances 0.000 claims description 31
- 239000008139 complexing agent Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- -1 copper(II) cations Chemical class 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N iron (II) ion Substances [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
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- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
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- 239000011668 ascorbic acid Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
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- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
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- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 claims description 2
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- KCTSXBFNNAXQFG-UHFFFAOYSA-N [hydroxy(oxido)phosphaniumyl]phosphinic acid Chemical compound OP(=O)P(O)=O KCTSXBFNNAXQFG-UHFFFAOYSA-N 0.000 description 1
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- 239000000378 calcium silicate Substances 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
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- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
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- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 235000013925 ferrous lactate Nutrition 0.000 description 1
- 239000004225 ferrous lactate Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
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- 229910001425 magnesium ion Inorganic materials 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
Definitions
- the present invention relates to a process for the metallizing pretreatment of galvanized and / or alloy-galvanized steel surfaces or assembled metallic components, which at least partially comprise surfaces of zinc, in a surface treatment comprising a plurality of process steps.
- a metallic layer deposit of in particular not more than 100 mg / m 2 of iron is produced on the treated zinc surfaces.
- Such metallized zinc surfaces are outstandingly suitable as starting material for subsequent passivation and coating steps ( illustration 1 , Process II-V) and cause a significantly higher efficiency of the anti-corrosion coating, in particular after the pretreatment of galvanized metal surfaces according to the invention.
- the application of the process on galvanized steel strip prevents corrosive paint infiltration, especially at the cutting edges.
- the invention therefore comprises an uncoated or subsequently coated metallic component which has been given a metallizing pretreatment according to the invention, as well as the use of such a component in vehicle body construction in automobile manufacturing, shipbuilding, construction and for the production of white goods.
- car bodies consist of a large number of sheet-metal parts which are joined together by spot welding.
- corrosion protection which must be able to mitigate both the consequences of bimetallic corrosion and cut edge corrosion.
- metallic zinc coatings which are applied to the steel strip by electrolytic or hot-dip processes, provide a cathodic protection which prevents active dissolution of the more noble core material at cut edges and mechanically induced damage to the zinc coating, ligation is equally important for ensuring the material properties of the core material the corrosion rate itself.
- Correspondingly high are the requirements for the corrosion protection coating consisting mostly of an inorganic conversion layer and an organic barrier layer.
- the galvanic coupling between core material and metallic coating brings about an active, unimpeded local dissolution of the coating material, which in turn constitutes an activation point for the corrosive infiltration of the organic barrier layer.
- the phenomenon of paint peeling or "blistering" is especially observed at the cut edges where unimpeded corrosion of the less noble coating material takes place.
- the local activation of such a "defect" cut edge, damage in the metallic coating, spot welding point
- the corrosive paint release resulting from these "defects” is all the more pronounced the greater the electrical potential difference between the metals in direct contact.
- 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.
- the closest prior art is the German Offenlegungsschrift DE19733972 which deals with a process for the alkaline passivating pretreatment of galvanized and alloy-galvanized steel surfaces in strip lines.
- the surface-treated steel strip is brought into contact with an alkaline treatment agent containing magnesium ions, iron (III) ions and a complexing agent.
- the zinc surface is passivated thereby forming the corrosion protection layer.
- Such a passivated surface offers according to the teaching of DE19733972 already a paint adhesion, which is comparable to nickel and cobalt-containing processes.
- 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. Nevertheless, it appears that this pretreatment system can not satisfactorily suppress the paint peeling caused by the corrosion at the cut edges.
- pretreatment refers to the passivation by means of inorganic barrier layers (eg phosphating, chromating) or a process step preceding the lacquer coating for conditioning the cleaned metallic surface.
- inorganic barrier layers eg phosphating, chromating
- Such conditioning of the surface results in an improvement of the corrosion protection and the paint adhesion for the entire layer system resulting at the end of a process chain for corrosion-protecting surface treatment.
- FIG 1 are typical process chains summarized in the sense of the present invention, which benefit in particular from the pretreatment according to the invention.
- the specifying designation of the pretreatment as "metallising” is to be understood as meaning a pretreatment process which directly entails a metallic deposition of Metal cations (A) effected on the zinc surface, wherein after the metallizing pretreatment at least 50 at .-% of the element (A) according to the method defined in the example part of this application on the zinc surface in the metallic state.
- the redox potential E redox is measured directly on average (1) on a metal electrode of the metal (A) in relation to a standard commercial reference electrode, eg silver-silver chloride electrode.
- the agent (1) according to the invention comprising cations and / or compounds of the metal (A)
- E Zn which is determined at a zinc electrode in the middle (2), which differs from the agent (1) only by the absence of cations and / or compounds of the metal (A), compared to a standard commercial reference electrode: e zn in volts : Ag / AgCl / 1 M KCl / / Zn / M 2
- the method according to the invention is characterized in that a metallizing pretreatment of the zinc surface takes place when the redox potential E redox is more anodic than the electrode potential E Zn . This is the case when E Redox -E Zn > 0.
- the redox potential E redox of the cations and / or compounds of the metal (A) in the aqueous medium (1) is at least +50 mV, preferably at least +100 mV and particularly preferably at least +300 mV, but at most +800 mV anodic than the electrode potential E Zn of the zinc surface in contact with the aqueous agent (2). If the EMF is less than +50 mV, sufficient metallization of the galvanized surface can not be achieved in technically relevant contact times, so that in a subsequent passivating conversion treatment the metal deposit of the metal (A) is completely removed from the galvanized surface and the effect of the pretreatment therewith will be annulled.
- an excessively high EMF of more than +800 mV in short times can lead to a complete and massive occupation of the galvanized surface with the metal (A), so that the desired formation of an inorganic corrosion-inhibiting and adhesion-promoting layer does not occur or at least in a subsequent conversion treatment is hindered.
- the metallization is particularly effective when the concentration of cations and / or compounds of the metal (A) is at least 0.01 M, but does not exceed 0.2 M, preferably 0.1 M.
- Further cations and / or compounds of a metal, which are deposited on the galvanized surface according to the pretreatment in the metallic state, can be contained and are selected from cations and / or compounds of molybdenum, tungsten, cobalt, nickel, lead, and / or tin ,
- iron (II) ions and / or iron (II) compounds for example, iron (II) sulfate can be used.
- the organic salts iron (II) lactate and / or iron (II) gluconate are particularly preferred because of the lower corrosivity of the anions as a source of iron (II) cations.
- the redox potential E redox of the metal (A) must be determined individually and in the absence of the other metals in the aqueous medium.
- particular preference is given to those agents (1) in which only cations and / or compounds of the metal (A) and thus no cations and / or compounds of the aforementioned selection of metals are contained.
- such cations and / or compounds of the metal (A) are included which on the average (1) satisfy both the electromotive force (EMF) condition described above and a standard potential E 0 Me of the metal (A) cathodic located as the Normalpotenial e 0 H2 standard hydrogen electrode (SHE), wherein the standard potential e 0 Me of the metal (a) to the reversible redox reaction Me 0 ⁇ Me n + + ne - in an aqueous solution of the metal cation Me n + with Activity 1 at 25 ° C relates.
- EMF electromotive force
- SHE Normalpotenial e 0 H2 standard hydrogen electrode
- accelerators having a reducing action are added to the aqueous agent (1).
- Possible accelerators are oxo acids of phosphorus and salts thereof, where at least one phosphorus atom must be present in a middle oxidation state.
- Such accelerators are, for example, hypophosphoric acid, hypodiphosphonic acid, diphosphorus (III, V) acid, Phosphonic acid, diphosphonic acid and particularly preferably phosphinic acid and salts thereof.
- the molar ratio of accelerator to the concentration of the cations and / or compounds of the metal (A) in the aqueous medium (1) is preferably not greater than 2: 1, more preferably not greater than 1: 1.
- the aqueous agent (1) in the process according to the invention additionally contain small amounts of copper (II) cations, which can also be deposited metallically on the galvanized surface simultaneously with the cations and / or compounds of the metal (A).
- the aqueous agent (1) should additionally contain not more than 50 ppm, preferably not more than 10 ppm, but at least 0.1 ppm of copper (II) cations.
- the aqueous agent (1) for the metallizing pretreatment may additionally contain surfactants which are able to liberate the metallic surface from impurities without itself inhibiting the surface by forming compact adsorbate layers for the metallization.
- Nonionic surfactants with average HLB values of at least 8 and at most 14 may be used for this purpose.
- the pH of the aqueous agent is not less than 2 and not greater than 6, preferably not greater than 4, in order, on the one hand, to over-stain the galvanized steel surface low pH levels prevent this inhibits the metallization of the surface, and on the other hand to ensure the stability of the iron (II) ions in the treatment solution.
- the iron (II) -containing treatment solution may also contain chelating complexing agents with oxygen and / or nitrogen ligands for stabilization. Such a treatment solution is additionally useful for increasing the EMF for metallization since iron (II) ions are less complexed by such ligands than zinc (II) ions.
- the increase in the emf via the addition of the complexing agents is important for the setting of a shorter treatment time and an optimal iron coverage of the galvanized surface.
- Suitable chelating complexing agents are especially those which are selected from triethanolamine, diethanolamine, monoethanolamine, monoisopropanolamine, aminoethylethanolamine, 1-amino-2,3,4,5,6-pentahydroxyhexane, N- (hydroxyethyl) ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, tartaric acid, lactic acid, mucic acid, gallic acid, gluconic acid and / or glucoheptonic acid and their salts and stereoisomers as well as sorbitol, glucose and glucamine and their stereoisomers.
- a particularly effective formulation of the aqueous agent (1) with the aforementioned complexing agents is at a molar ratio of chelating complexing agent to the concentration of cations and / or bivalent iron compounds of not greater than 5: 1, preferably not greater than 2: 1, but given at least 1: 5.
- Lower molar ratios than 1: 5 change the EMF for metallization only insignificantly.
- higher molar ratios than 5: 1 in which a high proportion of free complexing agent is present, so that the EMF for metallization remains virtually unaffected and results in an uneconomical procedure.
- R 1 represents an alkyl group having not more than 4 carbon atoms
- R 2 represents a substituent of the general formula H (CHOH) m CH 2 - having a number m of hydroxymethylene groups of not more than 5 and not less than 3.
- poly (5-vinyl-2-hydroxy-N-benzyl-N-glucamine) to use because of its pronounced complexing effect.
- a molar ratio of chelating complexing agents defined as the concentration of the monomer units of the water-soluble and / or water-dispersible polymeric compound to the concentration of the cations and / or compounds of the metal (A ), not greater than 5: 1, preferably not greater than 2: 1, but at least 1: 5 particularly effective.
- the application methods customary in strip steel production and strip steel finishing are practicable. These include, in particular, dipping and spraying processes.
- the contact time or pretreatment time with the aqueous agent (1) should be at least 1 second but not longer than 30 seconds, preferably not longer than 10 seconds.
- the metallic layer support is defined as the area-related mass fraction of the element (A) on the galvanized or alloy-galvanized steel surface immediately after the pretreatment according to the invention.
- Both the preferred contact times and layer conditions as well as the preferred application methods also apply to the pretreatment according to the invention of components assembled from a plurality of metallic materials insofar as these at least partially have zinc surfaces.
- the present invention also includes those combinations of alloy-galvanized steel surfaces and aqueous compositions (1) in which an alloying constituent of the galvanized steel surface is the same element (A) as the metal (A) in the form of its cations and / or compounds in the aqueous medium (1).
- an alloying constituent of the galvanized steel surface is the same element (A) as the metal (A) in the form of its cations and / or compounds in the aqueous medium (1).
- hot-dip galvannealed ® -Feinblech according to the invention with a means (1) ferrous ions are pre-treated with the consequence containing that result in a subsequent application of corrosion protective coatings easily improved corrosion and infiltration characteristics.
- the pretreatment process according to the invention is adapted to the subsequent process steps of the surface treatment of galvanized and / or alloy-galvanized steel surfaces with regard to optimized corrosion protection and outstanding paint adhesion, especially at cut edges, surface defects and bimetal contacts. Consequently, the present invention encompasses various aftertreatment processes, ie conversion and lacquer coatings, which, in conjunction with the pretreatment described above, provide the desired results in terms of corrosion protection.
- the illustration 1 illustrates various preferred within the meaning of the present invention process chains for corrosion-protective coating of metallic surfaces in automotive manufacturing, which are already started at the steel producer ("Coil Industry") and continued and completed in the paint shop (“Paint Shop”) at the car manufacturer.
- the invention therefore relates in a further aspect to the production of a passivating conversion coating on the metallized pretreated galvanized and / or alloy-galvanized steel surface with or without intermediate rinsing and / or drying step (US Pat. illustration 1 , Method IIa).
- a chromium-containing or preferably chromium-free conversion solution can be used.
- Preferred conversion solutions with which according to the present invention pretreated metal surfaces can be treated before applying a permanent corrosion protective organic coating the DE-A-199 23 084 and the literature cited herein.
- a chromium-free aqueous conversion agent besides hexafluoro anions of Ti, Si and / or Zr may contain as further active ingredients: phosphoric acid, one or more compounds of Co, Ni, V, Fe, Mn, Mo or W, a water-soluble or water-dispersible film-forming organic polymer or copolymer and organophosphonic acids that have complexing properties.
- phosphoric acid one or more compounds of Co, Ni, V, Fe, Mn, Mo or W
- organophosphonic acids that have complexing properties.
- water-soluble and / or water-dispersible polymeric complexing agents with oxygen and / or nitrogen ligands based on Mannich addition products of polyvinylphenols with formaldehyde and aliphatic amino alcohols may be present.
- Such polymers are in the patent US 5,298,289 disclosed.
- the process parameters for a conversion treatment in the context of this invention are to be chosen such that a conversion layer is produced, the per m 2 surface at least 0.05, preferably at least 0.2, but not more than 3, Contains 5, preferably not more than 2.0 and more preferably not more than 1.0 mmol of the metal M, which is the essential component of the conversion solution.
- metals M are Cr (III), B, Si, Ti, Zr, Hf.
- the coverage of the zinc surface with the metal M can be determined, for example, by an X-ray fluorescence method.
- the chromium-free conversion medium additionally contains copper ions.
- the molar ratio of Metal atoms M selected from zirconium and / or titanium to copper atoms in such a conversion agent is preferably chosen such that this generates a conversion layer in which at least 0.1, preferably at least 0.3, but not more than 2 mmol of copper are additionally included ,
- a method (IIa), in which the metallizing pretreatment is followed by a conversion treatment to form a thin amorphous inorganic coating may also include a method (IIa).
- the metallizing pretreatment and the subsequent conversion treatment usually include further process steps for application additional layers, in particular organic paints or coating systems ( illustration 1 , Method III-V).
- Component a) is a fully reacted polycondensation product of epichlorohydrin and a bisphenol. This essentially has no epoxide groups as reactive groups more.
- the polymer is then in the form of a hydroxyl-containing polyether, which can undergo crosslinking reactions with, for example, polyisocyanates via these hydroxyl groups.
- the bisphenol component of this polymer can be selected, for example, from bisphenol A and bisphenol F.
- the average molar mass (according to the manufacturer, for example determinable by gel permeation chromatography) is preferably in the range from 20,000 to 60,000, in particular in the range from 30,000 to 50,000.
- the OH number is preferably in the range from 170 to 210 and in particular in the range from 180 to 200.
- polymers are preferred whose hydroxyl content based on the Estherharz in the range of 5 to 7 wt .-%.
- the aliphatic polyisocyanates b) and c) are preferably based on HDI, in particular on HDI trimer.
- blocking agents in the blocked aliphatic polyisocyanate b) can the usual polyisocyanate blocking agents be used. Examples which may be mentioned are: butanone oxime, dimethylpyrazole, malonate, diisopropylamine / malonic ester, diisopropylamine / triazole and ⁇ -caprolactam.
- a combination of malonic ester and diisopropylamine is used as the blocking agent.
- the content of blocked NCO groups of component b) is preferably in the range from 8 to 10% by weight, in particular in the range from 8.5 to 9.5% by weight.
- the equivalent weight is preferably in the range of 350 to 600, in particular in the range of 450 to 500 g / mol.
- the non-blocked aliphatic polyisocyanate c) preferably has an equivalent weight in the range of 200 to 250 g / mol and an NCO content in the range of 15 to 23 wt%.
- an aliphatic polyisocyanate can be selected which has an equivalent weight in the range of 200 to 230 g / mol, in particular in the range of 210 to 220 g / mol and an NCO content in the range of 18 to 22 wt .-%, preferably in the range from 19 to 21% by weight.
- Another suitable aliphatic polyisocyanate has for example an equivalent weight in the range of 220 to 250 g / mol, in particular in the range of 230 to 240 g / mol and an NCO content in the range of 15 to 20 wt .-%, preferably in the range of 16 , 5 to 19 wt .-%.
- Each of these aliphatic polyisocyanates mentioned may be component c). However, a mixture of these two polyisocyanates can also be present as component c). If a mixture of the two mentioned polyisocyanates is used, the ratio of the first-mentioned polyisocyanate to the last-mentioned polyisocyanate for component c) is preferably in the range from 1: 1 to 1: 3.
- Component d) is selected from hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates.
- a hydroxyl-containing poly (meth) acrylate having an acid number in the range of 3 to 12, in particular in the range of 4 to 9 mg KOH / g can be used.
- the content of hydroxyl groups is preferably in the range of 1 to 5 and in particular in the range of 2 to 4 wt .-%.
- the equivalent weight is preferably in the range of 500 to 700, in particular in the range of 550 to 600 g / mol.
- a hydroxyl-containing polyester is used as component d
- a branched polyester having an equivalent weight in the range from 200 to 300, in particular in the range from 240 to 280 g / mol can be selected for this purpose.
- a weakly branched polyester having an equivalent weight in the range of 300 to 500, in particular in the range of 350 to 450 g / mol is suitable.
- These different types of polyester can each individually or as a mixture form the component d).
- a mixture of hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates may also be present as component d).
- the coating composition (1) in process (III) according to the invention thus contains both a blocked aliphatic polyisocyanate b) and an unblocked aliphatic polyisocyanate c).
- the hydroxyl-containing components a) and d) are available. Possible reaction of each of components a) and d) with each of components b) and c) produces a complex polymer network of polyurethanes during curing of the agent (2).
- hydroxyl-containing poly (meth) acrylates are used as component d)
- further crosslinking via the double bonds of these components occur.
- component d) consists at least partially of hydroxyl-containing poly (meth) acrylates.
- the coating composition (1) is cured in the process (III) according to the invention, it is to be expected that initially the non-blocked aliphatic polyisocyanate c) reacts with one or both of components a) and d). If the hydroxyl groups of the components d) are more reactive than those of the component a), during curing, first of all, a reaction of the component c) with the component d) occurs.
- the coating composition (1) contains, in addition to the components a) to d), a conductive pigment or a mixture of conductive pigments. These may have a relatively low density, such as carbon black and graphite, or a relatively high density, such as metallic iron.
- the absolute content of the coating composition (1) of the conductivity pigments depends on their density, since it depends less on the mass fraction than on the volume fraction of the conductive pigment in the cured coating for the effect as a conductive pigment.
- the coating composition (1) based on the total mass of the composition, contains (0.8 to 8) .pHW .-% of conductive pigment, where p is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 means.
- the coating composition (1) preferably contains (2 to 6), based on its total mass, ⁇ % by weight of conductive pigment.
- the coating composition (1) contains only graphite having a density of 2.2 g / cm 2 as the conductive pigment, then it preferably contains at least 1.76, in particular at least 4.4, and preferably not more than 17 , 6, in particular not more than 13.2 wt .-% graphite.
- the coating composition (1) based on its total mass, preferably contains at least 6.32, in particular at least 15.8 wt .-% and not more than 63 , 2, in particular not more than 47.4 wt .-% Accordingly, the Gew.-proportions are calculated, if as a conductive pigment, for example, exclusively MoS 2 with a density of 4.8 g / cm3, aluminum with a density of 2.7 g / cm 3 or zinc with a density of 7.1 g / cm 3 is used.
- the coating composition (1) contains not only a single conductive pigment but a mixture of at least two conductive pigments, which then differ greatly in their density.
- a mixture can be used in which the first mixing partner is a light conductive pigment such as carbon black, graphite or aluminum and the second partner of the mixture is a heavy conductive pigment such as zinc or iron.
- the average density of the mixture is used, which can be calculated from the weight percentages of the components in the mixture and from their respective density.
- a specific embodiment of a coating agent (1) in process (IIIb) is characterized in that it contains both a conductive pigment having a density of less than 3 g / cm 3 and a conductive pigment having a density of greater than 4 g / cm 3 , Wherein the total amount of conductive pigment, based on the total mass of the composition (2), is (0.8 to 8) ⁇ ⁇ % by Weight, Where ⁇ is the average density of the mixture of the conductive pigments in g / cm 3 .
- the coating agent (1) as a conductive pigment, a mixture of carbon black or graphite on the one hand and iron powder on the other hand.
- the weight ratios of carbon black and / or graphite on the one hand and iron on the other hand can be in the range from 1: 0.1 to 1:10, in particular in the range from 1: 0.5 to 1: 2.
- the coating composition (1) may therefore contain aluminum flakes, graphite and / or carbon black as a light electrically conductive pigment.
- the use of graphite and / or carbon black is preferred.
- Carbon black, and especially graphite not only provide electrical conductivity of the resultant coating, but also contribute to this layer having a desirable low Mohs hardness of not more than 4 and being readily reshapeable.
- the lubricating effect of graphite contributes to a reduced wear of the forming tools. This effect can be further promoted by additionally using pigments with a lubricating effect such as molybdenum sulfide with.
- the coating agent (1) may contain waxes and / or Teflon.
- the electrically conductive pigment having a specific weight of at most 3 g / cm 3 may be in the form of small spheres or aggregates of such spheres. It is preferred that the balls or the aggregates of these balls have a diameter of less than 2 microns. However, these electrically conductive pigments are preferably in the form of platelets whose thickness is preferably less than 2 ⁇ m.
- the coating composition (1) in process (III) according to the invention comprises at least the resin components described above and also solvents.
- the resin components a) to d) are usually present in their commercial form as a solution or dispersion in organic solvents.
- the coating composition (1) prepared therefrom then also contains these solvents.
- the electrically conductive pigment such as, for example, graphite and optionally further pigments such as, in particular, anticorrosive pigments to set a viscosity which allows the coating agent (1) to be applied to the substrate in the coil coating process.
- additional solvent can be added.
- the chemical nature of the solvents is usually dictated by the choice of raw materials containing the appropriate solvent.
- solvents cyclohexanone, diacetone alcohol, diethylene glycol monobutyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol n-butyl ether, methoxypropyl acetate, n-butyl acetate, Xylene, dimethyl glutarate, dimethyl adipate and / or dimethyl succinate.
- the preferred proportion of solvent on the one hand and organic resin components on the other hand in the coating agent (1) depends on the content of conductive pigment in% by weight in the coating agent (1).
- the preferred weight percentages of solvent and resin components therefore depend on the density ⁇ of the conductivity pigment used or the average density ⁇ of a mixture of conductive pigments.
- the coating composition (1) in the process (III) according to the invention it is preferable that, based on the total mass of the coating composition (1), [(25 to 60). Adjustment factor] Wt%, preferably [(35 to 55) Fitting factor] Wt% organic solvent and [(20 to 45) Fitting factor] Wt%, preferably [(25 to 40) Fitting factor] Wt.
- % organic resin components wherein the sum of the weight percentages of organic resin component and solvent is not greater than [93 * adjustment factor] wt%, preferably not greater than [87 * adaptation factor] wt%, and wherein the adjustment factor [100 -2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
- the coating agent (1) based on the total mass of the coating agent (1), be [(2 to 8) ⁇ adjustment factor]% by weight, preferably [(3 to 5) ⁇ adjustment factor] Wt .-% of the resin component a), wherein the adjustment factor [100-2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 . From the proportion of the resin component a) can be calculated with the above-mentioned preferred ratios of the individual resin components, the preferred proportions of the resin components b) to d) in the coating agent (1).
- the proportion of components b) in the total mass of the coating agent [(2 to 9) adjustment factor] wt .-%, preferably [(3 to 6) adjustment factor] wt%, the proportion of resin components c) [(4 to 18) adjustment factor] wt%, preferably [(6 to 12) adjustment factor] wt% and the proportion of the resin components d) [(7 to 30) ⁇ adjustment factor] wt%, preferably [(10 to 20) ⁇ adjustment factor] wt%.
- the "adaptation factor" has the meaning given above.
- the layer b) additionally contains corrosion inhibitors and / or anticorrosive pigments.
- Corrosion inhibitors or anticorrosive pigments which are known in the prior art for this purpose can be used here. Examples which may be mentioned are: magnesium oxide pigments, in particular in nanoscale form, finely divided and very finely divided barium sulfate or anticorrosive pigments based on calcium silicate.
- the preferred weight fraction of the anticorrosion pigments on the total mass of the coating composition (1) in turn depends on the density of the anticorrosion pigments used.
- the coating composition (1) in the process (III) according to the invention based on the total mass of the coating composition, preferably contains [(5 to 25) adjustment factor]% by weight, in particular [(10 to 20) adjustment factor]% by weight corrosion protection pigment where the adjustment factor is [100-2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
- the mechanical and chemical properties of the coating obtained after the baking of the coating agent (1) in process (III) according to the invention can be further improved by additionally containing fillers.
- these may be selected from silicas or silicas (optionally hydrophobed), alumina (including basic alumina), titania and barium sulfate.
- the coating composition is (1) [(0.1 to 3) adjustment factor]% by weight, preferably [(0.4 to 2) adjustment factor]% by weight filler selected from silicas or Silicon dioxide, aluminum oxide, titanium dioxide and barium sulfate, where the adjustment factor is [100-2.8 p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
- steps (i-vi) are carried out as a strip treatment method, wherein the liquid coating composition (1) is applied in step (vi) in such an amount that, after curing, the desired layer thickness is in the range from 0.5 to 10 receives ⁇ m.
- the coating agent (1) is applied in the so-called coil coating process.
- continuous metal strips are continuously coated.
- the coating agent (1) can be applied by different methods, which are familiar in the prior art. For example, applicator rolls can be used to directly adjust the desired wet film thickness. Alternatively, one can immerse the metal strip in the coating agent (1) or spray it with the coating agent (1), after which the desired wet film thickness is adjusted by means of squeeze rolls.
- step (ii) If metal strips coated immediately before with a metal coating, for example with zinc or zinc alloys, electrolytically or by hot dip coating, it is not necessary to clean the metal surfaces prior to performing the metallizing pretreatment (ii). However, if the metal strips have already been stored and in particular provided with corrosion protection oils, a purification step (i) is necessary before carrying out step (ii).
- the coated sheet is heated to the required drying or crosslinking temperature for the organic coating.
- the treatment agent can also be brought to the corresponding drying or crosslinking temperature by infrared radiation, in particular by near infrared radiation.
- Such pre-coated metal sheets are tailored and converted in the automotive production for the production of bodies accordingly.
- the assembled component or the assembled body shell therefore has unprotected edges, which must be treated in addition corrosion protection.
- the so-called "paint shop” therefore, there is a further corrosion-protective treatment and, ultimately, the realization of the automobile-typical paint structure.
- the present invention therefore relates, in a further aspect, to a process (IV) which extends the process chain (i-vi) of process (III), wherein a crystalline phosphate layer is first deposited on the exposed metal surfaces, in particular on the cut edges, in order to subsequently to provide a final corrosion protection by means of dip paint, in particular protection against infiltration of the paint system at the cutting edges.
- a process (IV) which extends the process chain (i-vi) of process (III), wherein a crystalline phosphate layer is first deposited on the exposed metal surfaces, in particular on the cut edges, in order to subsequently to provide a final corrosion protection by means of dip paint, in particular protection against infiltration of the paint system at the cutting edges.
- the present invention is distinguished by the fact that the zinc surfaces pretreated in a metallizing manner according to the invention in particular excellently prevent edge corrosion.
- a process chain according to the invention which comprises the electrodeposition coating (KTL, ATL) in process (IV) and the application of further paint layers in a process (V), therefore, the amount of deposited dip paint per m 2 of the component consisting of zinc surfaces pretreated according to the invention (US Pat.
- illustration 1 , Method I) and / or the amount of filler to be applied which has the main task of protecting the body panels against stone chipping and compensate for any unevenness of the metal surface, in the secondary coating ( illustration 1 , Method V) are significantly reduced, without a loss of performance in terms of corrosion protection and paint adhesion is the result.
- the present invention relates to the galvanized and / or alloy-galvanized steel surface and the metallic component, which consists at least partially of a zinc surface which has been pretreated by metallizing in accordance with the process according to the invention with the aqueous agent (1) or subsequently this pretreatment with further passivating Conversion layers and / or paints, for example according to the inventive method (II-IV) coated.
- a treated steel surface or treated component is used in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods.
- the measuring chain consists of two galvanic half cells, one half cell containing the agent (1) containing cations and / or compounds of one metal (A), while the other half cell contains the means (2) differing from the agent (1), that it does not have any of cations and / or compounds of a metal (A). Both half-cells are connected to a salt bridge and the voltage difference between a metal electrode of the metal (A) in the middle (1) and a zinc electrode in the middle (2) is measured without current.
- a positive EMF means that the redox potential E redox of the cations and / or compounds of the metal (A) on the average (1) is more anodic than the electrode potential E Zn .
- the EMF is measured according to a measuring chain analogous to Figure 2 documented for an agent (1) containing iron (II) cations, which is suitable for the metallizing pretreatment according to the invention.
- the layer coating of iron on the electrolytically galvanized steel surface can be brought into solution immediately after the process step (ii) wet-chemically in 10 wt .-% hydrochloric acid and determined by atomic absorption spectroscopy (AAS) or alternatively in comparative experiments on pure zinc substrates (99, 9% Zn) by means of X-ray fluorescence analysis (RFA).
- AAS atomic absorption spectroscopy
- RMA X-ray fluorescence analysis
- the process (III) according to the invention is modified in such a way that the process step (ii), ie the metallizing pretreatment, is omitted.
- inventive method (III) is modified in such a way that instead of the process step (ii) an alkaline passivating pretreatment with the commercial product of the applicant (Granodine ® 1303) according to the German laid-open specification DE19733972 (see Tab.1, Ex.1 there) specified formulation based on iron (III) nitrate.
- Tab. 2 shows the results regarding corrosive paint infiltration at the cutting edge after 10 weeks of alternating climate test. Since the coating infiltration progresses differently at different points of the cut edge, Table 2 contains the respective maximum infiltration in mm for the corresponding coating system. Table 2 Infiltration at the cutting edge according to VDA Senstitest (621-415) Examples Infiltration at the cutting edge / mm V1 7.9 V2 6.5 V3 9.4 B1 1.5
- the conversion treatment carried out after an intermediate rinsing with deionized water was carried out in an acidic aqueous composition of 750 ppm Zr as H 2 ZrF 6 20 ppm Cu as Cu (NO 3 ) 2 10 ppm Si as SiO 2 200 ppm Zn as Zn (NO 3 ) 2 at a pH of 4 and a contact time of 90 seconds at a temperature of 20 ° C ( illustration 1 , Method IIa).
- a cathodic dip coating (CathoGuard 500) was applied in a layer thickness of 20 microns and cured sheets in a convection oven at 180 ° C for 30 min before the surface in the center of the sheet along several centimeters down to the steel substrate carved with a scribe's mark to Clemen.
- Table 3 shows the sub-migration values resulting from this experiment at the Ritz after VDA climate change test.
- Table 3 Undercrossing at the Ritz of according to a process chain I ⁇ IIa ⁇ IVa (see illustration 1 ) Coated steel sheets (test sheets Gardobond ®, Fa.
- Figures 6 and 7 again show from the X-ray photoelectronic (XPS) detail spectra of Fe (2p 3/2 ) that the thin iron coating applied in the process according to the invention has a metallic character and significantly more than 50 at% of the iron atoms are present in metallic form. Qualitatively, this is recognizable by the significant shift in the overall peak intensity in favor of peak 1 (FIG. Fig. 7 ) at lower binding energies compared to the intensity of this single peak in alkaline passivation (V2).
- the quantification is done by default using a numerical fit process of the XP detail spectrum using Gaussian single peaks, which allow the determination of the single peak area.
- Table 4 gives quantitatively the chemical bonding state of the iron overlay immediately after the respective exemplary (V2) or inventive (B1) pretreatments.
- Table 4 Percentage Shares of Different Bonding States of Iron on Galvanized Steel Surfaces Determined by X-ray Photoelectron Spectroscopy (XPS) example Fe, metallic / At .-% Fe, oxidic / At .-% V2 28 72 B1 63 37
Description
Die vorliegende Erfindung betrifft ein Verfahren zur metallisierenden Vorbehandlung verzinkter und/oder legierungsverzinkter Stahloberflächen oder zusammengefügter metallischer Bauteile, die zumindest teilweise Oberflächen aus Zink aufweisen, in einer mehrere Prozessschritte umfassenden Oberflächenbehandlung. Im erfindungsgemäßen Verfahren wird eine metallische Schichtauflage von insbesondere nicht mehr als 100 mg/m2 an Eisen auf den behandelten Zinkoberflächen erzeugt. Derart metallisierte Zinkoberflächen eignen sich hervorragend als Ausgangsmaterial für nachfolgende Passivierungs- und Beschichtungsschritte (
Gegenwärtig wird in der Stahlindustrie eine Vielzahl oberflächenveredelter Stahlwerkstoffe hergestellt und nahezu 80 % der Feinblechprodukte in Deutschland werden heute in oberflächenveredelter Ausführung geliefert. Für die Produktion von Erzeugnissen werden diese Feinblechprodukte weiterverarbeitet, so dass unterschiedlichste metallische Werkstoffe oder verschiedenste Kombinationen von metallischem Grund- und Oberflächenmaterial in einem Bauteil vorliegen können und für bestimmte Produktanforderungen vorliegen müssen. Bei der Weiterverarbeitung, speziell von oberflächenveredelten Bandstählen, wird der Werkstoff zugeschnitten, umgeformt und mittels Schweiß- oder Klebeverfahren zusammengefügt. Diese Verarbeitungsprozesse sind im hohen Maße typisch für den Karosseriebau in der Automobilindustrie. Dort wird hauptsächlich verzinkter Bandstahl aus der Coil-Coating-Industrie weiterverarbeitet und beispielsweise mit unverzinktem Bandstahl und/oder Bandaluminium zusammengefügt. So bestehen Autokarosserien aus einer Vielzahl von Blechteilen, die durch Punktschweißen miteinander verbunden werden.
Aus dieser Kombinationsvielfalt von metallischer Bandmaterialien in einem Bauteil und der vornehmlichen Verwendung von oberflächenveredelten Bandstählen ergeben sich besondere Anforderungen an den Korrosionschutz, der in der Lage sein muss, sowohl die Folgen der Bimetallkorrosion als auch der Schnittkantenkorrosion abzumindern. Zwar vermitteln metallische Zinküberzüge, die elektrolytisch oder im Schmelztauchverfahren auf das Stahlband aufgebracht werden, eine kathodische Schutzwirkung, die eine aktive Auflösung des edleren Kernmaterials an Schnittkanten und mechanisch hervorgerufenen Verletzungen des Zinküberzuges verhindert, doch ebenso bedeutend für die Gewährleistung der Materialeigenschaften des Kernmaterials ist die Unterbindung der Korrosionsrate an sich. Entsprechend hoch sind die Anforderungen an die Korrosionsschutzbeschichtung bestehend zumeist aus einer anorganischen Konversionsschicht und einer organischen Barriereschicht.At present, a large number of surface-refined steel materials are produced in the steel industry, and nearly 80% of the thin-plate products in Germany are today supplied in a surface-refined design. For the production of products these thin sheet products are further processed, so that a wide variety of metallic materials or various combinations of metallic base and surface material can be present in a component and must be available for certain product requirements. During further processing, especially of surface-treated strip steels, the material is cut to size, formed and assembled by means of welding or gluing methods. These processing processes are highly typical of the body shop in the automotive industry. There is mainly galvanized steel strip the coil coating industry further processed and assembled, 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.
From this combination of variety of metallic strip materials in a component and the primary use of surface-treated strip steel, there are special requirements for corrosion protection, which must be able to mitigate both the consequences of bimetallic corrosion and cut edge corrosion. Although metallic zinc coatings, which are applied to the steel strip by electrolytic or hot-dip processes, provide a cathodic protection which prevents active dissolution of the more noble core material at cut edges and mechanically induced damage to the zinc coating, ligation is equally important for ensuring the material properties of the core material the corrosion rate itself. Correspondingly high are the requirements for the corrosion protection coating consisting mostly of an inorganic conversion layer and an organic barrier layer.
An Schnittkanten und an durch die Bearbeitung oder sonstige Einflüsse auftretenden Verletzungen an der Zinkauflage bewirkt die galvanische Kopplung zwischen Kernmaterial und metallischem Überzug eine aktive, ungehinderte lokale Auflösung des Überzugsmaterials, die wiederum eine Aktivierungsstelle für die korrosive Unterwanderung der organischen Barriereschicht darstellt. Das Phänomen der Lackenthaftung oder des "Blistering" wird speziell an den Schnittkanten beobachtet, an denen eine ungehinderte Korrosion des unedleren Überzugsmaterials stattfindet. Gleiches gilt prinzipiell für die Stellen eines Bauteils, an denen unterschiedliche metallische Materialien durch Fügetechniken unmittelbar miteinander verbundenen sind. Die lokale Aktivierung eines solchen "Defektes" (Schnittkante, Verletzung im metallischen Überzug, Punktschweißstelle) und damit die korrosive Lackenthaftung, die von diesen "Defekten" ausgeht, ist umso ausgeprägter je größer der elektrische Potentialunterschied zwischen den Metallen im unmittelbaren Kontakt ist. Entsprechend gute Ergebnisse bezüglich der Lackhaftung an Schnittkanten bietet Bandstahl mit Zinküberzügen, die mit edleren Metallen legiert sind, z.B. eisenlegierte Zinküberzüge (Galvannealed Steel).
Da die Bandstahlproduzenten verstärkt dazu übergehen, neben der Oberflächenveredelung mit metallischen Überzügen weitere Korrosionsbeschichtungen, insbesondere Lackbeschichtungen, in der Bandanlage zu integrieren, besteht dort und in der verarbeitenden Industrie, insbesondere in der automobilen Fertigung, ein erhöhter Bedarf an Korrosionsschutzbehandlungen, die die mit der Schnittkanten- und Kontaktkorrosion verbundenen Probleme in der Lackhaftung effektiv verhindern.At cutting edges and at the zinc coating caused by the machining or other influences, the galvanic coupling between core material and metallic coating brings about an active, unimpeded local dissolution of the coating material, which in turn constitutes an activation point for the corrosive infiltration of the organic barrier layer. The phenomenon of paint peeling or "blistering" is especially observed at the cut edges where unimpeded corrosion of the less noble coating material takes place. The same applies in principle to the locations of a component to which different metallic materials are directly connected by joining techniques. The local activation of such a "defect" (cut edge, damage in the metallic coating, spot welding point) and thus the corrosive paint release resulting from these "defects" is all the more pronounced the greater the electrical potential difference between the metals in direct contact. Correspondingly, good results with regard to paint adhesion at cut edges are offered by steel strips with zinc coatings alloyed with nobler metals, eg iron-alloyed zinc coatings (galvannealed steel).
As the steel strip producers increasingly turn to this, in addition to surface finishing with metallic coatings, further corrosion coatings, in particular Lacquer coatings to integrate into the belt line, there and in the processing industry, particularly in automotive manufacturing, have an increased need for anti-corrosive treatments that effectively prevent the problems associated with cut edge and contact corrosion problems in paint adhesion.
Im Stand der Technik sind verschiedene Vorbehandlungen beschrieben, die das Problem des Kantensschutzes adressieren. Als wesentliche Strategie wird dabei die Verbesserung der Lackhaftung der organischen Barriereschicht auf dem oberflächenveredelten Bandstahl verfolgt.
Als nächstliegender Stand der Technik ist die deutsche Offenlegungsschrift
The closest prior art is the German Offenlegungsschrift
Es stellt sich also als Aufgabe der vorliegenden Erfindung, ein Verfahren zur Vorbehandlung von verzinkten und legierungsverzinkten Stahloberflächen bereitzustellen, welches die von Defekten in der Zinkauflage des Bandstahls ausgehende Lackenthaftung, insbesondere an den Schnittkanten, im Vergleich zum Stand der Technik deutlich verbessert.It is therefore an object of the present invention to provide a method for the pretreatment of galvanized and alloy-galvanized steel surfaces, which significantly improves the Lackenthaftung emanating from defects in the zinc coating of the steel strip, especially at the cut edges, compared to the prior art.
Diese Aufgabe wurde gelöst durch ein Verfahren zur metallisierenden Vorbehandlung von verzinkten oder legierungsverzinkten Stahloberflächen, wobei die verzinkte oder legierungsverzinkte Stahloberfläche mit einem wässrigen Mittel (1) in Kontakt gebracht wird, dessen pH-Wert nicht kleiner als 2 und nicht größer als 6 ist, dadurch gekennzeichnet, dass im Mittel (1)
- (a) Kationen und/oder Verbindungen eines Metalls (A), die ausgewählt sind aus Kationen und/oder Verbindungen von Eisen in einer Konzentration von mindestens 0,001 M,
- (b) Beschleuniger ausgewählt aus Oxosäuren von Phosphor sowie deren Salze, wobei mindestens ein Phosphoratom in einer mittleren Oxidationsstufe vorliegt, enthalten sind,
Das erfindungsgemäße Verfahren eignet sich für sämtliche Metalloberflächen, beispielsweise Bandstahl, und/oder zusammengefügten metallischen Bauteile, die zumindest teilweise auch aus Zinkoberflächen bestehen, beispielsweise Automobilkarosserien. Bevorzugt ist die Werkstoffkombination aus Eisen-haltigen Oberflächen und Zinkoberflächen.This object has been achieved by a method for metallizing pretreatment of galvanized or alloy-galvanized steel surfaces, wherein the galvanized or alloy-galvanized steel surface is brought into contact with an aqueous agent (1), whose pH is not less than 2 and not greater than 6, characterized in that on average (1)
- (a) cations and / or compounds of a metal (A) selected from cations and / or compounds of iron in a concentration of at least 0.001 M,
- (b) accelerators selected from oxo acids of phosphorus and salts thereof, wherein at least one phosphorus atom is present in a middle oxidation state,
The method according to the invention is suitable for all metal surfaces, for example strip steel, and / or assembled metallic components, which at least partially also consist of zinc surfaces, for example automobile bodies. The material combination of iron-containing surfaces and zinc surfaces is preferred.
Unter Vorbehandlung wird im Sinne dieser Erfindung ein der Passivierung mittels anorganischer Barriereschichten (z.B. Phosphatierung, Chromatierung) oder ein der Lackbeschichtung vorausgehender Prozessschritt zur Konditionierung der gereinigten metallischen Oberfläche bezeichnet. Eine solche Konditionierung der Oberfläche bewirkt für das gesamte, am Ende einer Prozesskette zur korrosionsschützenden Oberflächenbehandlung resultierende Schichtsystem eine Verbesserung des Korrosionsschutzes und der Lackhaftung. In der
In der spezifizierenden Bezeichnung der Vorbehandlung als "metallisierend" ist ein Vorbehandlungsprozess zu verstehen, der unmittelbar eine metallische Abscheidung von Metall-Kationen (A) auf der Zinkoberfläche bewirkt, wobei nach erfolgter metallisierender Vorbehandlung mindestens 50 At.-% des Elements (A) entsprechend der im Beispielteil dieser Anmeldung definierten Analysenmethode auf der Zinkoberfläche im metallischen Zustand vorliegen.
Das Redoxpotential ERedox wird erfindungsgemäß direkt im Mittel (1) an einer Metallelektrode des Metalls (A) gegenüber einer kommerziellen Standardreferenzelektrode, z.B. Silber-Silberchlorid-Elektrode, gemessen. Beispielsweise in einer elektrochemischen Messkette der folgender Art:
The specifying designation of the pretreatment as "metallising" is to be understood as meaning a pretreatment process which directly entails a metallic deposition of Metal cations (A) effected on the zinc surface, wherein after the metallizing pretreatment at least 50 at .-% of the element (A) according to the method defined in the example part of this application on the zinc surface in the metallic state.
According to the invention, the redox potential E redox is measured directly on average (1) on a metal electrode of the metal (A) in relation to a standard commercial reference electrode, eg silver-silver chloride electrode. For example, in an electrochemical measuring chain of the following type:
Gleiches gilt für das Elektrodenpotential EZn, welches an einer Zinkelektrode im Mittel (2), welches sich vom Mittel (1) lediglich durch die Abwesenheit der Kationen und/oder Verbindungen des Metalls (A) unterscheidet, gegenüber einer kommerziellen Standardrferenzelektrode bestimmt wird:
Das erfindungsgemäße Verfahren kennzeichnet sich nun dadurch aus, dass eine metallisierende Vorbehandlung der Zinkoberfläche dann erfolgt, wenn das Redoxpotential ERedox anodischer liegt als das Elektrodenpotential EZn. Dies ist der Fall, wenn ERedox-EZn > 0 ist.The method according to the invention is characterized in that a metallizing pretreatment of the zinc surface takes place when the redox potential E redox is more anodic than the electrode potential E Zn . This is the case when E Redox -E Zn > 0.
Als elektromotorische Kraft (EMK), also als thermodynamische Triebkraft für die stromlose metallisierende Vorbehandlung, ist die Potentialdifferenz von Redoxpotential ERedox und Elektrodenpotential EZn gemäß obigen Definitionen anzusehen. Die elektromotorische Kraft (EMK) entspricht dabei einer elektrochemischen Messkette der folgenden Art:
- mit M(1) das Mittel (1) enthaltend Kationen und/oder Verbindungen des Metalls (A) bezeichnend, und
- mit M(2) das Mittel (2) bezeichnend, welches sich von M(1) nur dadurch unterscheidet, dass es keine Kationen und/oder Verbindungen des Metalls (A) enthält.
- denoting M (1) the agent (1) containing cations and / or compounds of the metal (A), and
- denoting M (2) the agent (2) which differs from M (1) only in that it contains no cations and / or compounds of the metal (A).
Für das erfindungsgemäße Verfahren ist es dabei vorteilhaft, wenn das Redoxpotential ERedox der Kationen und/oder Verbindungen des Metalls (A) im wässrigen Mittel (1) um mindestens +50 mV, vorzugsweise mindestens +100 mV und besonders bevorzugt mindestens +300 mV, aber höchstens +800 mV anodischer liegt als das Elektrodenpotential EZn der Zinkoberfläche im Kontakt mit dem wässrigen Mittel (2). Ist die EMK kleiner als +50 mV kann eine hinreichende Metallisierung der verzinkten Oberfläche in technisch relevanten Kontaktzeiten nicht erzielt werden, so dass in einer nachfolgenden passivierenden Konversionsbehandlung die Metallauflage des Metalls (A) vollständig von der verzinkten Oberfläche entfernt wird und die Wirkung der Vorbehandlung damit aufgehoben wird. Umgekehrt kann eine zu hohe EMK von mehr als +800 mV in kurzen Zeiten zu einer vollständigen und massiven Belegung der verzinkten Oberfläche mit dem Metall (A) führen, so dass in einer nachfolgenden Konversionsbehandlung die gewünschte Ausbildung einer anorganischen korrosionsschützenden und haftvermittelnden Schicht ausbleibt oder zumindest gehindert ist. Es zeigt sich, dass die Metallisierung besonders effektiv ist, wenn die Konzentration an Kationen und/oder Verbindungen des Metalls (A) mindestens 0,01 M beträgt, aber 0,2 M, vorzugsweise 0,1 M nicht überschreitet.
Weitere Kationen und/oder Verbindungen eines Metall, welche gemäß der Vorbehandlung im metallischen Zustand auf der verzinkten Oberfläche abgeschieden werden, können enthalten sein und sind ausgewählt aus Kationen und/oder Verbindungen von Molybdän, Wolfram, Cobalt, Nickel, Blei, und/oder Zinn. Als Eisen(II)-Ionen und/oder Eisen(II)-Verbindungen kann beispielsweise Eisen(II)sulfat eingesetzt werden. Gegenüber dem Sulftat sind insbesondere die organischen Salze Eisen(II)lactat und/oder Eisen(II)gluconat aufgrund der geringeren Korrosivität der Anionen als Quelle für Eisen(II)-Kationen bevorzugt.It is advantageous for the process according to the invention if the redox potential E redox of the cations and / or compounds of the metal (A) in the aqueous medium (1) is at least +50 mV, preferably at least +100 mV and particularly preferably at least +300 mV, but at most +800 mV anodic than the electrode potential E Zn of the zinc surface in contact with the aqueous agent (2). If the EMF is less than +50 mV, sufficient metallization of the galvanized surface can not be achieved in technically relevant contact times, so that in a subsequent passivating conversion treatment the metal deposit of the metal (A) is completely removed from the galvanized surface and the effect of the pretreatment therewith will be annulled. Conversely, an excessively high EMF of more than +800 mV in short times can lead to a complete and massive occupation of the galvanized surface with the metal (A), so that the desired formation of an inorganic corrosion-inhibiting and adhesion-promoting layer does not occur or at least in a subsequent conversion treatment is hindered. It turns out that the metallization is particularly effective when the concentration of cations and / or compounds of the metal (A) is at least 0.01 M, but does not exceed 0.2 M, preferably 0.1 M.
Further cations and / or compounds of a metal, which are deposited on the galvanized surface according to the pretreatment in the metallic state, can be contained and are selected from cations and / or compounds of molybdenum, tungsten, cobalt, nickel, lead, and / or tin , As iron (II) ions and / or iron (II) compounds, for example, iron (II) sulfate can be used. Compared with the sulphate, the organic salts iron (II) lactate and / or iron (II) gluconate are particularly preferred because of the lower corrosivity of the anions as a source of iron (II) cations.
Liegen im Mittel (1) zusätzlich Metalle entsprechend der zuvor genannten Auswahl vor, so ist das Redoxpotential ERedox des Metalls (A) einzeln und in Abwesenheit der jeweils anderen Metalle im wässrigen Mittel zu bestimmen.
Besonders bevorzugt sind jedoch solche Mittel (1), in denen lediglich Kationen und oder Verbindungen des Metalls (A) und damit keine Kationen und/oder Verbindungen der zuvor genannten Auswahl an Metallen enthalten sind.If, in addition, metals (1) are present in accordance with the selection mentioned above, the redox potential E redox of the metal (A) must be determined individually and in the absence of the other metals in the aqueous medium.
However, particular preference is given to those agents (1) in which only cations and / or compounds of the metal (A) and thus no cations and / or compounds of the aforementioned selection of metals are contained.
Erfindungsgemäß sind solche Kationen und/oder Verbindungen des Metalls (A) enthalten, die im Mittel (1) sowohl die Bedingung für die elektromotorische Kraft (EMK) wie zuvor beschrieben erfüllen als auch ein Standardpotential E0 Me des Metalls (A) aufweisen, das kathodischer liegt als das Normalpotenial E0 H2 der Standardwasserstoffelektrode (SHE), wobei sich das Standardpotential E0 Me des Metalls (A) auf die reversible Redoxreaktion Me0 → Men+ + n e- in einer wässrigen Lösung des Metall-Kations Men+ mit der Aktivität 1 bei 25 °C bezieht.
Läge diese zweite Bedingung nicht erfüllt vor, so würden in einer dem erfindungsgemäßen Verfahren nachfolgenden Konversionsbehandlung aufgrund reduzierter Beizraten der Substratoberfläche Passivierungsschichten ausgebildet, die weniger homogen sind und vermehrt Defekte aufweisen. Im Extremfall unterbliebe im nachfolgenden Verfahrensschritt die passivierende Konversion der im erfindungsgemäßen Verfahren vorbehandelten Substratoberfläche. Gleiches gilt für eine der erfindungsgemäßen Vorbehandlung unmittelbar nachfolgenden organischen Beschichtung, die auf einen Selbstabscheidungsprozess beruht, der durch den Beizangriff des Substrates eingeleitet wird (Autophoretische Tauchlackbeschichtung, Abk.: AC für "Autodepositable Coating").According to the invention, such cations and / or compounds of the metal (A) are included which on the average (1) satisfy both the electromotive force (EMF) condition described above and a standard potential E 0 Me of the metal (A) cathodic located as the Normalpotenial e 0 H2 standard hydrogen electrode (SHE), wherein the standard potential e 0 Me of the metal (a) to the reversible redox reaction Me 0 → Me n + + ne - in an aqueous solution of the metal cation Me n + with
If this second condition were not met, passivation layers which are less homogeneous and have more defects would be formed in a conversion treatment following the method according to the invention due to reduced pickling rates of the substrate surface. In the extreme case, the passivating conversion of the substrate surface pretreated in the process according to the invention would be omitted in the subsequent process step. The same applies to an organic coating immediately following the pretreatment according to the invention, which is based on a self-deposition process which is initiated by the pickling attack of the substrate (autophoretic dip coating, abbreviation: AC for "autodepositable coating").
Im erfindungsgemäßen Vorbehandlungsverfahren werden zur Erhöhung der Abscheidungsrate der Kationen und/oder Verbindungen des Metalls (A), also der Metallisierung der verzinkten oder legierungsverzinkten Oberfläche, Beschleuniger mit Reduktionswirkung dem wässrigen Mittel (1) hinzugesetzt. Als mögliche Beschleuniger kommen Oxosäuren von Phosphor sowie deren Salze in Frage, wobei mindestens ein Phosphoratom in einer mittleren Oxidationsstufe vorliegen muss. Derartige Beschleuniger sind beispielsweise Hypophosphorsäure, Hypodiphosphonsäure, Diphosphor(III, V)-säure, Phosphonsäure, Diphosphonsäure und besonders bevorzugt Phosphinsäure sowie deren Salze.
Des Weiteren können Beschleuniger eingesetzt werden, die dem Fachmann aus dem Stand der Technik in der Phosphatierung bekannt sind. Diese haben neben ihren Reduktionseigenschaften auch depolarisierende Eigenschaften, d.h. sie wirken als Wasserstofffänger, und begünstigen so zusätzlich die Metallisierung der verzinkten Stahloberfläche. Hierzu gehören Hydrazin, Hydroxylamin, Nitroguanidin, N-Methylmorpholin-N-oxid, Glucoheptonat, Ascorbinsäure und reduzierende Zucker.
Das molare Verhältnis von Beschleuniger zur Konzentration der Kationen und/oder Verbindungen des Metalls (A) im wässrigen Mittel (1) ist vorzugsweise nicht größer ist als 2:1, besonders bevorzugt nicht größer als 1:1.In the pretreatment process of the present invention, in order to increase the deposition rate of the cations and / or compounds of the metal (A), that is, the metallization of the galvanized or alloy-galvanized surface, accelerators having a reducing action are added to the aqueous agent (1). Possible accelerators are oxo acids of phosphorus and salts thereof, where at least one phosphorus atom must be present in a middle oxidation state. Such accelerators are, for example, hypophosphoric acid, hypodiphosphonic acid, diphosphorus (III, V) acid, Phosphonic acid, diphosphonic acid and particularly preferably phosphinic acid and salts thereof.
Furthermore, it is possible to use accelerators known to the person skilled in the art in phosphating. In addition to their reduction properties, these also have depolarizing properties, ie they act as hydrogen scavengers, thus additionally promoting the metallization of the galvanized steel surface. These include hydrazine, hydroxylamine, nitroguanidine, N-methylmorpholine N-oxide, glucoheptonate, ascorbic acid and reducing sugars.
The molar ratio of accelerator to the concentration of the cations and / or compounds of the metal (A) in the aqueous medium (1) is preferably not greater than 2: 1, more preferably not greater than 1: 1.
Optional kann das wässrige Mittel (1) im erfindungsgemäßen Verfahren zusätzlich geringe Mengen an Kupfer(II)-Kationen enthalten, die ebenfalls simultan mit den Kationen und/oder Verbindungen des Metalls (A) auf der verzinkten Oberfläche metallisch abgeschieden werden können. Allerdings ist hier zu beachten, dass keine massive, nahezu vollständig oberflächenbedeckende Zementation von Kupfer eintritt, da sonst eine nachfolgende Konversionsbehandlung vollständig unterbunden wird und/oder sich die Lackhaftung deutlich verschlechtert. Daher sollte das wässrige Mittel (1) nicht mehr als 50 ppm, vorzugsweise nicht mehr als 10 ppm, aber mindestens 0,1 ppm Kupfer(II)-Kationen zusätzlich enthalten.Optionally, the aqueous agent (1) in the process according to the invention additionally contain small amounts of copper (II) cations, which can also be deposited metallically on the galvanized surface simultaneously with the cations and / or compounds of the metal (A). However, it should be noted here that no massive, almost completely surface-covering cementation of copper occurs, since otherwise a subsequent conversion treatment is completely prevented and / or the paint adhesion deteriorates significantly. Therefore, the aqueous agent (1) should additionally contain not more than 50 ppm, preferably not more than 10 ppm, but at least 0.1 ppm of copper (II) cations.
Darüber hinaus kann das wässrige Mittel (1) für die metallisierende Vorbehandlung zusätzlich Tenside enthalten, die die metallische Oberfläche von Verunreinigungen zu befreien vermag, ohne selbst die Oberfläche durch die Ausbildung kompakter Adsorbatschichten für die Metallisierung zu inhibieren. Hierfür können vorzugsweise Niotenside mit mittleren HLB-Werten von mindestens 8 und höchstens 14 eingesetzt werden.In addition, the aqueous agent (1) for the metallizing pretreatment may additionally contain surfactants which are able to liberate the metallic surface from impurities without itself inhibiting the surface by forming compact adsorbate layers for the metallization. Nonionic surfactants with average HLB values of at least 8 and at most 14 may be used for this purpose.
Da Kationen und/oder Verbindungen von Eisen(II) für das erfindungsgemäße Vorbehandlungsverfahren verwendet werden, ist der pH-Wert des wässrigen Mittels nicht kleiner als 2 und nicht größer als 6, vorzugsweise nicht größer als 4, um einerseits ein Überbeizen der verzinkten Stahloberfläche bei niedrigen pH-Werten zu verhindern, da dies die Metallisierung der Oberfläche inhibiert, und andererseits die Stabilität der Eisen(II)-Ionen in der Behandlungslösung zu gewährleisten.
Die Eisen(II)-haltige Behandlungslösung kann zur Stabilisierung ferner chelatisierende Komplexbildner mit Sauerstoff- und/oder Stickstoff-Liganden enthalten. Eine solche Behandlungslösung eignet sich zusätzlich zur Erhöhung der EMK für die Metallisierung, da Eisen(II)-lonen weniger stark durch derartige Liganden komplexiert werden als Zink(II)-Ionen. Die Erhöhung der EMK über den Zusatz der Komplexbildner ist für die Einstellung einer kürzeren Behandlungsdauer und einer optimalen Eisenbelegung der verzinkten Oberfläche bedeutsam.Since cations and / or compounds of iron (II) are used for the pretreatment process according to the invention, the pH of the aqueous agent is not less than 2 and not greater than 6, preferably not greater than 4, in order, on the one hand, to over-stain the galvanized steel surface low pH levels prevent this inhibits the metallization of the surface, and on the other hand to ensure the stability of the iron (II) ions in the treatment solution.
The iron (II) -containing treatment solution may also contain chelating complexing agents with oxygen and / or nitrogen ligands for stabilization. Such a treatment solution is additionally useful for increasing the EMF for metallization since iron (II) ions are less complexed by such ligands than zinc (II) ions. The increase in the emf via the addition of the complexing agents is important for the setting of a shorter treatment time and an optimal iron coverage of the galvanized surface.
Als chelatisierende Komplexbildner kommen dabei speziell solche in Frage, die ausgewählt sind aus Triethanolamin, Diethanolamin, Monoethanolamin, Monoisopropanolamin, Aminoethylethanolamin, 1-Amino-2,3,4,5,6-pentahydroxyhexan, N-(Hydroxyethyl)-ethylendiamintriessigsäure, Ethylendiamintetraessigsäure, Diethylentriaminpentaessigsäure, 1,2-Diaminopropantetraessigsäure, 1,3-Diaminopropantetraessigsäure, Weinsäure, Milchsäure, Schleimsäure, Gallussäure, Gluconsäure und/oder Glucoheptonsäure sowie deren Salze und Stereoisomere als auch Sorbit, Glucose und Glucamin sowie deren Stereoisomere.Suitable chelating complexing agents are especially those which are selected from triethanolamine, diethanolamine, monoethanolamine, monoisopropanolamine, aminoethylethanolamine, 1-amino-2,3,4,5,6-pentahydroxyhexane, N- (hydroxyethyl) ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, tartaric acid, lactic acid, mucic acid, gallic acid, gluconic acid and / or glucoheptonic acid and their salts and stereoisomers as well as sorbitol, glucose and glucamine and their stereoisomers.
Eine besonders effektive Formulierung des wässrigen Mittels (1) mit vorstehend genannten Komplexbildnern ist bei einem molaren Verhältnis von chelatisierenden Komplexbildner zur Konzentration der Kationen und/oder Verbindungen des zweiwertigen Eisens von nicht größer ist als 5:1, vorzugsweise nicht größer 2:1, aber von mindestens 1:5 gegeben. Geringere molare Verhältnisse als 1:5 verändern die EMK für die Metallisierung nur unwesentlich. Ähnliches gilt für höhere molare Verhältnisse als 5:1, bei denen ein hoher Anteil an freien Komplexbildner vorliegt, so dass die EMK für die Metallisierung nahezu unbeeinflusst bleibt und eine unwirtschaftliche Verfahrensweise resultiert.A particularly effective formulation of the aqueous agent (1) with the aforementioned complexing agents is at a molar ratio of chelating complexing agent to the concentration of cations and / or bivalent iron compounds of not greater than 5: 1, preferably not greater than 2: 1, but given at least 1: 5. Lower molar ratios than 1: 5 change the EMF for metallization only insignificantly. The same applies to higher molar ratios than 5: 1, in which a high proportion of free complexing agent is present, so that the EMF for metallization remains virtually unaffected and results in an uneconomical procedure.
Des Weiteren finden wasserlösliche und/oder wasserdispergierbare polymere Komplexbildner mit Sauerstoff- und/oder Stickstoff-Liganden auf der Basis von Mannich-Additionsprodukten von Polyvinylphenolen mit Formaldehyd und aliphatischen Aminoalkoholen Verwendung. Derartige Polymere sind in der Patentschrift
Analog zur Komplexierung der Eisen(II)-Ionen mit niedermolekularen Komplexbildnern ist für die polymeren Verbindungen ein molares Verhältnis von chelatisierenden Komplexbildner, definiert als Konzentration der Monomereinheiten der wasserlöslichen und/oder wasserdispergierbaren polymeren Verbindung zur Konzentration der Kationen und/oder Verbindungen des Metalls (A), von nicht größer ist als 5:1, vorzugsweise von nicht größer 2:1, aber von mindestens 1:5 besonders effektiv.Analogously to the complexing of the iron (II) ions with low molecular weight complexing agents, a molar ratio of chelating complexing agents, defined as the concentration of the monomer units of the water-soluble and / or water-dispersible polymeric compound to the concentration of the cations and / or compounds of the metal (A ), not greater than 5: 1, preferably not greater than 2: 1, but at least 1: 5 particularly effective.
Für das erfindungsgemäße Vorbehandlungsverfahren, welches einen Teil der Prozesskette der Oberflächenbehandlung von verzinkten und/oder legierungsverzinkten Stahloberflächen darstellt, sind die in der Bandstahlherstellung und Bandstahlveredelung üblichen Applikationsmethoden praktikabel. Hierzu gehören insbesondere Tauch- und Spritzverfahren. Die Kontaktzeit oder Vorbehandlungsdauer mit dem wässrigen Mittel (1) sollte jedoch mindestens 1 Sekunde, aber nicht länger als 30 Sekunden, vorzugsweise nicht länger als 10 Sekunden betragen. Innerhalb dieser Kontaktzeit resultieren bei erfindungsgemäßer Ausführung des Verfahrens metallische Überzüge des Metalls (A) mit einer Schichtauflage von vorzugsweise mindestens 1 mg/m2, aber von vorzugsweise nicht mehr als 100 mg/m2, und besonders bevorzugt von nicht mehr als 50 mg/m2. Die metallische Schichtauflage ist im Sinne der vorliegenden Erfindung definiert als flächenbezogener Massenanteil des Elements (A) auf der verzinkten oder legierungsverzinkten Stahloberfläche unmittelbar nach der erfindungsgemäßen Vorbehandlung.For the pretreatment process according to the invention, which forms part of the process chain of the surface treatment of galvanized and / or alloy-galvanized steel surfaces, the application methods customary in strip steel production and strip steel finishing are practicable. These include, in particular, dipping and spraying processes. However, the contact time or pretreatment time with the aqueous agent (1) should be at least 1 second but not longer than 30 seconds, preferably not longer than 10 seconds. Within this contact time result in the inventive embodiment of the method metallic coatings of the metal (A) with a layer of preferably at least 1 mg / m 2 , but preferably not more than 100 mg / m 2 , and particularly preferably not more than 50 mg / m 2 . For the purposes of the present invention, the metallic layer support is defined as the area-related mass fraction of the element (A) on the galvanized or alloy-galvanized steel surface immediately after the pretreatment according to the invention.
Sowohl die bevorzugten Kontaktzeiten und Schichtauflagen als auch die bevorzugten Applikationsmethoden gelten ebenso für die erfindungsgemäße Vorbehandlung von aus mehreren metallischen Werkstoffen zusammengefügten Bauteilen, insofern diese zumindest teilweise Zinkoberflächen aufweisen.Both the preferred contact times and layer conditions as well as the preferred application methods also apply to the pretreatment according to the invention of components assembled from a plurality of metallic materials insofar as these at least partially have zinc surfaces.
Zum vorliegenden Erfindungsgegenstand gehören auch diejenigen Kombinationen von legierungsverzinkten Stahloberflächen und wässrigen Mittel (1), bei denen ein Legierungsbestandteil der verzinkten Stahloberfläche dasselbe Element (A) darstellt wie das Metall (A) in Form seiner Kationen und/oder Verbindungen im wässrigen Mittel (1). So kann beispielsweise auch feuerverzinktes Galvannealed®-Feinblech erfindungsgemäß mit einem Mittel(1) enthaltend Eisen-Ionen mit der Konsequenz vorbehandelt werden, dass in einer nachfolgenden Aufbringung von korrosionsschützenden Schichten leicht verbesserte Korrosions- und Unterwanderungseigenschaften resultieren.The present invention also includes those combinations of alloy-galvanized steel surfaces and aqueous compositions (1) in which an alloying constituent of the galvanized steel surface is the same element (A) as the metal (A) in the form of its cations and / or compounds in the aqueous medium (1). , Thus, for example, hot-dip galvannealed ® -Feinblech according to the invention with a means (1) ferrous ions are pre-treated with the consequence containing that result in a subsequent application of corrosion protective coatings easily improved corrosion and infiltration characteristics.
Das erfindungsgemäße Vorbehandlungsverfahren ist auf die nachfolgenden Prozessschritte der Oberflächenbehandlung von verzinkten und/oder legierungsverzinkten Stahloberflächen hinsichtlich eines optimierten Korrosionsschutzes und einer hervorragenden Lackhaftung insbesondere an Schnittkanten, Oberflächendefekten und Bimetallkontakten abgestimmt. Konsequenterweise werden von der vorliegenden Erfindung verschiedene Nachbehandlungsverfahren, also Konversions- und Lackbeschichtungen, umfasst, die in Verbindung mit der zuvor beschriebenen Vorbehandlung die gewünschten Ergebnisse hinsichtlich des Korrosionsschutzes liefern. Die
Die Erfindung betrifft daher in einem weiteren Aspekt die Erzeugung einer passivierenden Konversionsbeschichtung auf der metallisierend vorbehandelten verzinkten und/oder legierungsverzinkten Stahloberfläche mit oder ohne dazwischenliegendem Spül- und/oder Trocknungsschritt (
Hierfür kann eine chromhaltige oder vorzugsweise chromfreie Konversionslösung eingesetzt werden. Bevorzugte Konversionslösungen, mit denen die gemäß der vorliegenden Erfindung vorbehandelten Metalloberflächen vor den Aufbringen einer permanent korrosionsschützenden organischen Beschichtung behandelt werden können, können der
Im Anschluss hieran offenbart dieses Dokument eine sehr umfangreiche Liste komplexbildender Organophosphonsäuren als weitere mögliche Komponenten der Konversionslösungen. Konkrete Beispiele dieser Komponenten können der genannten
Des Weiteren können wasserlösliche und/oder wasserdispergierbare polymere Komplexbildner mit Sauerstoff- und/oder Stickstoff-Liganden auf der Basis von Mannich-Additionsprodukten von Polyvinylphenolen mit Formaldehyd und aliphatischen Aminoalkoholen enthalten sein. Derartige Polymere sind in der Patentschrift
The invention therefore relates in a further aspect to the production of a passivating conversion coating on the metallized pretreated galvanized and / or alloy-galvanized steel surface with or without intermediate rinsing and / or drying step (US Pat.
For this purpose, a chromium-containing or preferably chromium-free conversion solution can be used. Preferred conversion solutions with which according to the present invention pretreated metal surfaces can be treated before applying a permanent corrosion protective organic coating, the
Following this, this document discloses a very extensive list of complex-forming organophosphonic acids as further possible components of the conversion solutions. Concrete examples of these components may be mentioned
Furthermore, water-soluble and / or water-dispersible polymeric complexing agents with oxygen and / or nitrogen ligands based on Mannich addition products of polyvinylphenols with formaldehyde and aliphatic amino alcohols may be present. Such polymers are in the patent
Die Verfahrensparameter für eine Konversionsbehandlung im Sinne dieser Erfindung wie beispielsweise Behandlungstemperatur, Behandlungsdauer und Kontaktzeit sind dabei derart zu wählen, dass eine Konversionsschicht erzeugt wird, die pro m2 Oberfläche mindestens 0,05, vorzugsweise mindestens 0,2, aber nicht mehr als 3,5, vorzugsweise nicht mehr als 2,0 und besonders bevorzugt nicht mehr als 1,0 mmol des Metalls M enthält, das die wesentliche Komponente der Konversionslösung darstellt. Beispiele für Metalle M sind Cr(III), B, Si, Ti, Zr, Hf. Die Belegungsdichte der Zinkoberfläche mit dem Metall M kann beispielsweise mit einer Röntgenfluoreszenzmethode ermittelt werden.The process parameters for a conversion treatment in the context of this invention, such as treatment temperature, treatment time and contact time are to be chosen such that a conversion layer is produced, the per m 2 surface at least 0.05, preferably at least 0.2, but not more than 3, Contains 5, preferably not more than 2.0 and more preferably not more than 1.0 mmol of the metal M, which is the essential component of the conversion solution. Examples of metals M are Cr (III), B, Si, Ti, Zr, Hf. The coverage of the zinc surface with the metal M can be determined, for example, by an X-ray fluorescence method.
In einem besonderen Aspekt eines erfindungsgemäßen Verfahrens (IIa), das eine der metallisierenden Vorbehandlung folgende Konversionsbehandlung umfasst, enthält das chromfreie Konversionsmittel zusätzlich Kupfer-Ionen. Das molare Verhältnis von Metallatomen M ausgewählt aus Zirkon und/oder Titan zu Kupferatomen in einem solchen Konversionsmittel ist dabei vorzugsweise derart gewählt, dass dieses eine Konversionsschicht erzeugt, in der mindestens 0,1, vorzugsweise mindestens 0,3, aber nicht mehr als 2 mmol Kupfer zusätzlich enthalten sind.In a particular aspect of a process (IIa) according to the invention, which comprises a conversion treatment following the metallizing pretreatment, the chromium-free conversion medium additionally contains copper ions. The molar ratio of Metal atoms M selected from zirconium and / or titanium to copper atoms in such a conversion agent is preferably chosen such that this generates a conversion layer in which at least 0.1, preferably at least 0.3, but not more than 2 mmol of copper are additionally included ,
Die vorliegende Erfindung betrifft also auch ein Verfahren (IIa), welches folgende Prozessschritte einschließlich der metallisierenden Vorbehandlung und einer Konversionsbehandlung der verzinkten und/oder legierungsverzinkten Stahloberfläche umfasst:
- i) gegebenenfalls Reinigung / Entfettung der Werkstoffoberfläche
- ii) metallisierende Vorbehandlung mit einem wässrigen Mittel (1) gemäß der vorliegenden Erfindung
- iii) gegebenenfalls Spül- und/oder Trocknungsschritt
- iv) chrom(VI)freie Konversionsbehandlung, bei der eine Konversionsschicht erzeugt wird, die pro m2 Oberfläche 0,05
3,5 mmol des Metalls M enthält, das die wesentliche Komponente der Konversionslösung darstellt, wobei die Metalle M ausgewählt sind aus Cr(III), B, Si, Ti, Zr, Hf.bis
- i) optionally cleaning / degreasing the material surface
- ii) metallizing pretreatment with an aqueous agent (1) according to the present invention
- iii) optionally rinsing and / or drying step
- iv) chromium (VI) free conversion treatment in which a conversion layer containing, per m 2 of surface area, 0.05 to 3.5 mmol of the metal M which is the essential component of the conversion solution, the metals M being selected from Cr (III), B, Si, Ti, Zr, Hf.
Alternativ kann zu einem Verfahren (IIa), in dem der metallisierenden Vorbehandlung eine Konversionsbehandlung unter Ausbildung einer dünnen amorphen anorganischen Beschichtung folgt, auch ein Verfahren (
Darüber hinaus schließen sich der metallisierenden Vorbehandlung und der nachfolgenden Konversionsbehandlung üblicherweise weitere Verfahrensschritte zur Aufbringung zusätzlicher Schichten, insbesondere organischer Lacke oder Lacksysteme an (
Die vorliegende Erfindung betrifft daher in einem weiteren Aspekt ein Verfahren (III), welches die Prozesskette (i-iv) des Verfahrens (II) erweitert, wobei ein organisches Beschichtungsmittel (1) aufgebracht wird, das in einem organischen Lösungsmittel oder Lösungsmittelgemisch gelöste oder dispergierte organische Harzkomponenten enthält, dadurch gekennzeichnet, dass das Beschichtungsmittel (1) mindestens folgende organische Harzkomponenten enthält:
- a) als Hydroxylguppen-haltiger Polyether vorliegendes Epoxidharz auf Basis eines Bisphenol-Epichlorhydrin-Polykondensationsproduktes,
- b) blockiertes aliphatisches Polyisocyanat,
- c) nicht blockiertes aliphatisches Polyisocyanat,
- d) mindestens eine Reaktionskomponente ausgewählt aus Hydroxylgruppen-haltigen Polyestern und Hydroxylgruppen-haltigen Poly(meth)acrylaten.
- a) epoxy resin present as hydroxyl group-containing polyether based on a bisphenol-epichlorohydrin polycondensation product,
- b) blocked aliphatic polyisocyanate,
- c) unblocked aliphatic polyisocyanate,
- d) at least one reaction component selected from hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates.
Bei der Komponente a) handelt es sich um ein durchreagiertes Polykondensationsprodukt von Epichlorhydrin und einem Bisphenol. Dieses weist im Wesentlichen keine Epoxidgruppen als reaktive Gruppen mehr auf. Das Polymer liegt dann in Form eines Hydroxylgruppen-haltigen Polyethers vor, der über diese Hydroxylgruppen Vernetzungsreaktionen mit beispielsweise Polyisocyanaten eingehen kann.Component a) is a fully reacted polycondensation product of epichlorohydrin and a bisphenol. This essentially has no epoxide groups as reactive groups more. The polymer is then in the form of a hydroxyl-containing polyether, which can undergo crosslinking reactions with, for example, polyisocyanates via these hydroxyl groups.
Die Bisphenol-Komponente dieses Polymers kann beispielsweise ausgewählt sein aus Bisphenol A und Bisphenol F. Die mittlere Molmasse (gemäß Herstellerangaben, beispielsweise bestimmbar durch Gelpermeationschromotographie) liegt vorzugsweise im Bereich von 20.000 bis 60.000, insbesondere im Bereich von 30.000 bis 50.000. Die OH-Zahl liegt vorzugsweise im Bereich von 170 bis 210 und insbesondere im Bereich von 180 bis 200. Insbesondere sind Polymere bevorzugt, deren Hydroxylgehalt bezogen auf das Estherharz im Bereich von 5 bis 7 Gew.-% liegt.The bisphenol component of this polymer can be selected, for example, from bisphenol A and bisphenol F. The average molar mass (according to the manufacturer, for example determinable by gel permeation chromatography) is preferably in the range from 20,000 to 60,000, in particular in the range from 30,000 to 50,000. The OH number is preferably in the range from 170 to 210 and in particular in the range from 180 to 200. In particular, polymers are preferred whose hydroxyl content based on the Estherharz in the range of 5 to 7 wt .-%.
Die aliphatischen Polyisocyanate b) und c) basieren vorzugsweise auf HDI, insbesondere auf HDI-Trimer. Als Blockierungsmittel in dem blockierten aliphatischen Polyisocyanat b) können die üblichen Polyisocyanat-Blockierungsmittel eingesetzt sein. Beispielsweise seien genannt: Butanonoxim, Dimethylpyrazol, Malonester, Düsopropylamin/Malonester, Düsopropylamin/Triazol sowie ε-Caprolactam. Bevorzugt wird eine Kombination von Malonester und Diisopropylamin als Blockierungsmittel verwendet.
Der Gehalt an blockierten NCO-Gruppen der Komponente b) liegt vorzugsweise im Bereich von 8 bis 10 Gew.-%, insbesondere im Bereich von 8,5 bis 9,5 Gew.-%. Das Äquivalentgewicht liegt vorzugsweise im Bereich vor 350 bis 600, insbesondere im Bereich von 450 bis 500 g/mol.The aliphatic polyisocyanates b) and c) are preferably based on HDI, in particular on HDI trimer. As blocking agents in the blocked aliphatic polyisocyanate b) can the usual polyisocyanate blocking agents be used. Examples which may be mentioned are: butanone oxime, dimethylpyrazole, malonate, diisopropylamine / malonic ester, diisopropylamine / triazole and ε-caprolactam. Preferably, a combination of malonic ester and diisopropylamine is used as the blocking agent.
The content of blocked NCO groups of component b) is preferably in the range from 8 to 10% by weight, in particular in the range from 8.5 to 9.5% by weight. The equivalent weight is preferably in the range of 350 to 600, in particular in the range of 450 to 500 g / mol.
Das nicht-blockierte aliphatische Polyisocyanat c) hat vorzugsweise ein Äquivalentgewicht im Bereich von 200 bis 250 g/mol und einen NCO-Gehalt im Bereich von 15 bis 23 Gew.-%. Beispielsweise kann ein aliphatisches Polyisocyanat ausgewählt werden, das ein Äquivalentgewicht im Bereich von 200 bis 230 g/mol, insbesondere im Bereich von 210 bis 220 g/mol und einen NCO-Gehalt im Bereich von 18 bis 22 Gew.-%, vorzugsweise im Bereich von 19 bis 21 Gew.-% aufweist. Ein weiteres geeignetes aliphatisches Polyisocyanat hat beispielsweise ein Äquivalentgewicht im Bereich von 220 bis 250 g/mol, insbesondere im Bereich von 230 bis 240 g/mol und einen NCO-Gehalt im Bereich von 15 bis 20 Gew.-%, vorzugsweise im Bereich von 16,5 bis 19 Gew.-%. Dabei kann jedes dieser genannten aliphatischen Polyisocyanate die Komponente c) darstellen. Als Komponente c) kann jedoch auch ein Gemisch dieser beiden Polyisocyanate vorliegen. Setzt man ein Gemisch der beiden genannten Polyisocyanate ein, so liegt das Mengenverhältnis des erstgenannten Polyisocyanats zum letztgenannten Polyisocyanat für die Komponente c) vorzugsweise im Bereich von 1 : 1 bis 1 : 3.The non-blocked aliphatic polyisocyanate c) preferably has an equivalent weight in the range of 200 to 250 g / mol and an NCO content in the range of 15 to 23 wt%. For example, an aliphatic polyisocyanate can be selected which has an equivalent weight in the range of 200 to 230 g / mol, in particular in the range of 210 to 220 g / mol and an NCO content in the range of 18 to 22 wt .-%, preferably in the range from 19 to 21% by weight. Another suitable aliphatic polyisocyanate has for example an equivalent weight in the range of 220 to 250 g / mol, in particular in the range of 230 to 240 g / mol and an NCO content in the range of 15 to 20 wt .-%, preferably in the range of 16 , 5 to 19 wt .-%. Each of these aliphatic polyisocyanates mentioned may be component c). However, a mixture of these two polyisocyanates can also be present as component c). If a mixture of the two mentioned polyisocyanates is used, the ratio of the first-mentioned polyisocyanate to the last-mentioned polyisocyanate for component c) is preferably in the range from 1: 1 to 1: 3.
Die Komponente d) ist ausgewählt aus Hydroxylgruppen-haltigen Polyestern und Hydroxylgruppen-haltigen Poly(meth)acrylaten. Beispielsweise kann ein Hydroxylgruppenhaltiges Poly(meth)acrylat mit einer Säurezahl im Bereich von 3 bis 12, insbesondere im Bereich von 4 bis 9 mg KOH/g eingesetzt werden. Der Gehalt an Hydroxylgruppen liegt vorzugsweise im Bereich von 1 bis 5 und insbesondere im Bereich von 2 bis 4 Gew.-%. Das Äquivalentgewicht liegt vorzugsweise im Bereich von 500 bis 700, insbesondere im Bereich von 550 bis 600 g/mol.Component d) is selected from hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates. For example, a hydroxyl-containing poly (meth) acrylate having an acid number in the range of 3 to 12, in particular in the range of 4 to 9 mg KOH / g can be used. The content of hydroxyl groups is preferably in the range of 1 to 5 and in particular in the range of 2 to 4 wt .-%. The equivalent weight is preferably in the range of 500 to 700, in particular in the range of 550 to 600 g / mol.
Setzt man als Komponente d) einen Hydroxylgruppen-haltigen Polyester ein, so kann man hierfür einen verzweigten Polyester mit einem Äquivalentgewicht im Bereich von 200 bis 300, insbesondere im Bereich von 240 bis 280 g/mol auswählen. Weiterhin ist beispielsweise ein schwach verzweigter Polyester mit einem Äquivalentgewicht im Bereich von 300 bis 500, insbesondere im Bereich von 350 bis 450 g/mol geeignet. Diese unterschiedlichen Polyester-Typen können jedes für sich oder als Gemisch die Komponente d) bilden. Selbstverständlich kann als Komponente d) auch eine Mischung von Hydroxylgruppen-haltigen Polyestern und Hydroxylgruppen-haltigen Poly(meth)acrylaten vorliegen.If a hydroxyl-containing polyester is used as component d), a branched polyester having an equivalent weight in the range from 200 to 300, in particular in the range from 240 to 280 g / mol, can be selected for this purpose. Furthermore, for example, a weakly branched polyester having an equivalent weight in the range of 300 to 500, in particular in the range of 350 to 450 g / mol is suitable. These different types of polyester can each individually or as a mixture form the component d). Of course, a mixture of hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates may also be present as component d).
Das Beschichtungsmittel (1) im erfindungsgemäße Verfahren (III) enthält also sowohl ein blockiertes aliphatisches Polyisocyanat b) als auch ein nicht-blockiertes aliphatisches Polyiscyanat c). Als potenzielle Reaktionskomponenten für diese beiden Polyisocyanat-Typen stehen die Hydroxylgruppen-haltigen Komponenten a) und d) zur Verfügung. Durch mögliche Reaktion jeder der Komponenten a) und d) mit jeder der Komponenten b) und c) entsteht beim Aushärten des Mittels (2) ein komplexes Polymer-Netzwerk aus Polyurethanen. Zusätzlich können in dem Fall, dass als Komponente d) Hydroxylgruppen-haltige Poly(meth)acrylate eingesetzt werden, weitere Vernetzungen über die Doppelbindungen dieser Komponenten eintreten. Soweit nicht alle Doppelbindungen der Poly(meth)acrylate beim Aushärten vernetzen, können insbesondere oberflächlich vorhandene Doppelbindungen eine verbesserte Verknüpfung zu einem nachträglich aufgebrachten Lack bewirken, falls dieser ebenfalls Komponenten mit polymerisierbaren Doppelbindungen enthält. Unter diesem Gesichtspunkt ist es bevorzugt, dass die Komponente d) zumindest teilweise aus Hydroxylgruppen-haltigen Poly(meth)acrylaten besteht.The coating composition (1) in process (III) according to the invention thus contains both a blocked aliphatic polyisocyanate b) and an unblocked aliphatic polyisocyanate c). As potential reaction components for these two types of polyisocyanate, the hydroxyl-containing components a) and d) are available. Possible reaction of each of components a) and d) with each of components b) and c) produces a complex polymer network of polyurethanes during curing of the agent (2). In addition, in the case where hydroxyl-containing poly (meth) acrylates are used as component d), further crosslinking via the double bonds of these components occur. Insofar as not all double bonds of the poly (meth) acrylates crosslink during curing, especially double bonds present on the surface can bring about improved bonding to a subsequently applied lacquer, if it also contains components with polymerizable double bonds. From this point of view, it is preferred that component d) consists at least partially of hydroxyl-containing poly (meth) acrylates.
Beim Aushärten des Beschichtungsmittels (1) im erfindungsgemäßen Verfahren (III) ist zu erwarten, dass zunächst das nicht-blockierte aliphatische Polyisocyanat c) mit einer oder beiden der Komponenten a) und d) reagiert. Sofern die Hydroxylgruppen der Komponenten d) reaktiver sind als diejenigen der Komponente a), tritt beim Aushärten zunächst bevorzugt eine Reaktion der Komponente c) mit der Komponente d) ein.When the coating composition (1) is cured in the process (III) according to the invention, it is to be expected that initially the non-blocked aliphatic polyisocyanate c) reacts with one or both of components a) and d). If the hydroxyl groups of the components d) are more reactive than those of the component a), during curing, first of all, a reaction of the component c) with the component d) occurs.
Dem gegenüber reagiert das blockierte aliphatische Polyisocyanat b) erst dann mit einer oder beiden der Komponenten a) und d), wenn die Deblockierungstemperatur erreicht ist. Zur Polyurethanbildung steht dann nur noch derjenige der Reaktionspartner a) und d) zur Verfügung, der die weniger reaktionsfreudigen OH-Gruppen aufweist. Für das sich ausbildende Polyurethan-Netzwerk bedeutet dies beispielsweise, dass dann, wenn die OH-Gruppen der Komponenten a) reaktionsträger sind als diejenigen Komponenten d), sich zwei Polyurethan-Netzwerke aus der Reaktion der Komponenten c) und d) einerseits und der Komponenten a) und b) andererseits aufbauen.
Das Beschichtungsmittel (1) im erfindungsgemäßen Verfahren (III) enthält die Komponenten a) und b) einerseits und c) und d)- andererseits vorzugsweise in folgenden relativen Gewichtsverhältnissen:
- a): b) = 1: 0,8 bis 1 : 1,3
- c) : d) = 1 : 1,4 bis 1 : 2,3
The coating composition (1) in process (III) according to the invention contains the components a) and b) on the one hand and c) and d) - on the other hand preferably in the following relative weight ratios:
- a): b) = 1: 0.8 to 1: 1.3
- c): d) = 1: 1.4 to 1: 2.3
Die Komponenten a) und d) einerseits sowie b) und c) andererseits liegen vorzugsweise in folgendem relativen Gewichtsverhältnis vor:
- a) : d) = 1 : 2 bis 1: 6 und (vorzugsweise 1 : 3 bis 1 : 5)
- b) : c) = 1 : 0,5 bis 1 : 5 (vorzugsweise 1 : 1 bis 1 : 3).
- a): d) = 1: 2 to 1: 6 and (preferably 1: 3 to 1: 5)
- b): c) = 1: 0.5 to 1: 5 (preferably 1: 1 to 1: 3).
Bevorzugte absolute Mengenbereiche der genannten vier Komponenten a) bis d) werden weiter unten angegeben, da diese von der Dichte fakultativ vorhandener Leitfähigkeitspigmente (
Allgemein gilt, dass das Beschichtungsmittel (1), bezogen auf die Gesamtmasse des Mittels, (0,8 bis 8)·ρ Gew.-% an Leitfähigkeitspigment enthält, wobei p die Dichte des Leitfähigkeitspigments oder die mittlere Dichte der Mischung von Leitfähigkeitspigmenten in g/cm3 bedeutet. Vorzugsweise enthält das Beschichtungsmittel (1) bezogen auf seine Gesamtmasse (2 bis 6)·ρ Gew.-% an Leitfähigkeitspigment.In general, the coating composition (1), based on the total mass of the composition, contains (0.8 to 8) .pHW .-% of conductive pigment, where p is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 means. The coating composition (1) preferably contains (2 to 6), based on its total mass, ρ% by weight of conductive pigment.
Beispielsweise bedeutet dies: Enthält das Beschichtungsmittel (1) als Leitfähigkeitspigment nur Graphit mit einer Dichte von 2,2 g/cm2, so enthält es vorzugsweise mindestens 1,76, insbesondere mindestens 4,4 Gew.-% und vorzugsweise nicht mehr als 17,6, insbesondere nicht mehr als 13,2 Gew.-% Graphit. Wird Eisenpulver mit einer Dichte von 7,9 g/cm2 als alleiniges Leitfähigkeitspigment verwendet, enthält das Beschichtungsmittel (1), bezogen auf seine Gesamtmasse, vorzugsweise mindestens 6,32, insbesondere mindestens 15,8 Gew.-% und nicht mehr als 63,2, insbesondere nicht mehr als 47,4 Gew.-% Entsprechend errechnen sich die Gew.-Anteile, wenn als Leitfähigkeitspigment beispielsweise ausschließlich MoS2 mit einer Dichte von 4,8 g/cm3, Aluminium mit einer Dichte von 2,7 g/cm3 oder Zink mit einer Dichte von 7,1 g/cm3 eingesetzt wird.For example, if the coating composition (1) contains only graphite having a density of 2.2 g / cm 2 as the conductive pigment, then it preferably contains at least 1.76, in particular at least 4.4, and preferably not more than 17 , 6, in particular not more than 13.2 wt .-% graphite. If iron powder having a density of 7.9 g / cm 2 is used as the sole conductive pigment, the coating composition (1), based on its total mass, preferably contains at least 6.32, in particular at least 15.8 wt .-% and not more than 63 , 2, in particular not more than 47.4 wt .-% Accordingly, the Gew.-proportions are calculated, if as a conductive pigment, for example, exclusively MoS 2 with a density of 4.8 g / cm3, aluminum with a density of 2.7 g / cm 3 or zinc with a density of 7.1 g / cm 3 is used.
Es kann jedoch zu einer günstigen Eigenschaften-Kombination kommen, wenn das Beschichtungsmittel (1) nicht nur ein einziges Leitfähigkeitspigment, sondern eine Mischung aus mindestens zwei Leitfähigkeitspigmenten enthält, die sich dann vorzugsweise in ihrer Dichte stark unterscheiden. Beispielsweise kann eine Mischung eingesetzt werden, bei der der erste Mischungspartner ein leichtes Leitfähigkeitspigment wie beispielsweise Ruß, Graphit oder Aluminium und der zweite Partner der Mischung ein schweres Leitfähigkeitspigment wie beispielsweise Zink oder Eisen darstellt. In diesen Fällen wird für die Dichte ρ in der vorstehend genannten Formel die mittlere Dichte der Mischung eingesetzt, die sich aus den Gew.-Anteilen der Komponenten in der Mischung und aus ihrer jeweiligen Dichte errechnen lässt.However, a favorable combination of properties may occur if the coating composition (1) contains not only a single conductive pigment but a mixture of at least two conductive pigments, which then differ greatly in their density. For example, a mixture can be used in which the first mixing partner is a light conductive pigment such as carbon black, graphite or aluminum and the second partner of the mixture is a heavy conductive pigment such as zinc or iron. In these cases, for the density ρ in the aforementioned formula, the average density of the mixture is used, which can be calculated from the weight percentages of the components in the mixture and from their respective density.
Demgemäß ist eine spezielle Ausführungsform eines Beschichtungsmittels (1) im Verfahren (IIIb) dadurch gekennzeichnet, dass es sowohl ein Leitfähigkeitspigment mit einer Dichte von kleiner als 3 g/cm3 als auch ein Leitfähigkeitspigment mit einer Dichte von größer als 4 g/cm3 enthält, wobei die Gesamtmenge an Leitfähigkeitspigment, bezogen auf die Gesamtmasse des Mittels (2), (0,8 bis 8)·ρ Gew.-% beträgt, wobei ρ die mittlere Dichte der Mischung der Leitfähigkeitspigmente in g/cm3 bedeutet.Accordingly, a specific embodiment of a coating agent (1) in process (IIIb) is characterized in that it contains both a conductive pigment having a density of less than 3 g / cm 3 and a conductive pigment having a density of greater than 4 g / cm 3 , Wherein the total amount of conductive pigment, based on the total mass of the composition (2), is (0.8 to 8) × ρ% by Weight, Where ρ is the average density of the mixture of the conductive pigments in g / cm 3 .
Beispielsweise kann das Beschichtungsmittel (1) als Leitfähigkeitspigment eine Mischung aus Ruß oder Graphit einerseits und Eisenpulver andererseits enthalten. Dabei können die Gewichtsverhältnisse von Ruß und/oder Graphit einerseits und Eisen andererseits im Bereich von 1 : 0,1 bis 1 : 10, insbesondere im Bereich von 1 : 0,5 bis 1 : 2 liegen.For example, the coating agent (1) as a conductive pigment, a mixture of carbon black or graphite on the one hand and iron powder on the other hand. On the other hand, the weight ratios of carbon black and / or graphite on the one hand and iron on the other hand can be in the range from 1: 0.1 to 1:10, in particular in the range from 1: 0.5 to 1: 2.
Das Beschichtungsmittel (1) kann also als leichtes elektrisch leitfähiges Pigment Aluminiumflocken, Graphit und/oder Ruß enthalten. Dabei ist die Verwendung von Graphit und/oder Ruß bevorzugt. Ruß und insbesondere Graphit bewirken nicht nur eine elektrische Leitfähigkeit der erhaltenen Beschichtung, sondern tragen auch dazu bei, dass diese Schicht eine erwünschte geringe Mohs'sche Härte von nicht mehr als 4 aufweist und gut umformbar ist. Insbesondere die Schmierwirkung von Graphit trägt zu einem verringerten Verschleiß der Umformwerkzeuge bei. Diese Wirkung kann noch gefördert werden, indem man zusätzlich Pigmente mit Schmierwirkung wie beispielsweise Molybdänsulfid mit einsetzt. Als weitere Gleitmittel oder Umformhilfen kann das Beschichtungsmittel (1) Wachse und/oder Teflon enthalten.The coating composition (1) may therefore contain aluminum flakes, graphite and / or carbon black as a light electrically conductive pigment. The use of graphite and / or carbon black is preferred. Carbon black, and especially graphite, not only provide electrical conductivity of the resultant coating, but also contribute to this layer having a desirable low Mohs hardness of not more than 4 and being readily reshapeable. In particular, the lubricating effect of graphite contributes to a reduced wear of the forming tools. This effect can be further promoted by additionally using pigments with a lubricating effect such as molybdenum sulfide with. As further lubricants or forming aids, the coating agent (1) may contain waxes and / or Teflon.
Das elektrisch leitfähige Pigment mit einem spezifischen Gewicht von maximal 3 g/cm3 kann in Form kleiner Kugeln oder Aggregate solcher Kugeln vorliegen. Dabei ist es bevorzugt, dass die Kugeln bzw. die Aggregate dieser Kugeln einen Durchmesser von weniger als 2 µm aufweisen. Vorzugsweise liegen diese elektrisch leitfähigen Pigmente jedoch in Form von Plättchen vor, deren Dicke vorzugsweise geringer ist als 2 µm.The electrically conductive pigment having a specific weight of at most 3 g / cm 3 may be in the form of small spheres or aggregates of such spheres. It is preferred that the balls or the aggregates of these balls have a diameter of less than 2 microns. However, these electrically conductive pigments are preferably in the form of platelets whose thickness is preferably less than 2 μm.
Das Beschichtungsmittel (1) im erfindungsgemäßen Verfahren (III) enthält zumindest die weiter oben beschriebenen Harzkomponenten sowie Lösungsmittel. Die Harzkomponenten a) bis d) liegen in ihrer Handelsform in der Regel als Lösung bzw. Dispersion in organischen Lösungsmitteln vor. Das hieraus zubereitete Beschichtungsmittel (1) enthält dann ebenfalls diese Lösungsmittel.The coating composition (1) in process (III) according to the invention comprises at least the resin components described above and also solvents. The resin components a) to d) are usually present in their commercial form as a solution or dispersion in organic solvents. The coating composition (1) prepared therefrom then also contains these solvents.
Diese sind erwünscht, um trotz der zusätzlichen Anwesenheit des elektrisch leitfähigen Pigments wie beispielsweise Graphit und ggf. weiterer Pigmente wie insbesondere Korrosionsschutzpigmente eine Viskosität einzustellen, die es erlaubt, das Beschichtungsmittel (1) im Coil-Coating-Verfahren auf das Substrat aufzubringen. Erforderlichenfalls kann zusätzlich Lösungsmittel zugesetzt werden. Die chemische Natur der Lösungsmittel ist in der Regel durch die Wahl der Rohstoffe, die das entsprechende Lösungsmittel enthalten, vorgegeben. Beispielsweise kann als Lösungsmittel vorliegen: Cyclohexanon, Diacetonalkohol, Diethylenglykolmonobutyletheracetat, Diethylenglykol, Propylenglykolmethylether, Propylenglykol-n-Butylether, Methoxypropylacetat, n-Butylacetat, Xylol, Glutarsäuredimethylester, Adipinsäuredimethylester und/oder Bernsteinsäuredimethylester.These are desirable in order, in spite of the additional presence of the electrically conductive pigment such as, for example, graphite and optionally further pigments such as, in particular, anticorrosive pigments to set a viscosity which allows the coating agent (1) to be applied to the substrate in the coil coating process. If necessary, additional solvent can be added. The chemical nature of the solvents is usually dictated by the choice of raw materials containing the appropriate solvent. For example, the following may be present as solvents: cyclohexanone, diacetone alcohol, diethylene glycol monobutyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol n-butyl ether, methoxypropyl acetate, n-butyl acetate, Xylene, dimethyl glutarate, dimethyl adipate and / or dimethyl succinate.
Der bevorzugte Anteil an Lösungsmittel einerseits und organischen Harzkomponenten andererseits in dem Beschichtungsmittel (1) hängt, wenn man ihn in Gew.-% ausdrückt, von dem Anteil an Leitfähigkeitspigment in Gew.-% in dem Beschichtungsmittel (1) ab. Je höher die Dichte des Leitfähigkeitpigments, desto höher ist dessen bevorzugter Gewichtsanteil an dem gesamten Beschichtungsmittel (1), und desto geringer sind die Gewichtsanteile an Lösungsmittel und Harzkomponenten. Die bevorzugten Gew.-Anteile von Lösungsmittel und Harzkomponenten hängen daher von der Dichte ρ des eingesetzten Leitfähigkeitspigments bzw. der mittleren Dichte ρ einer Mischung von Leitfähigkeitspigmenten ab.The preferred proportion of solvent on the one hand and organic resin components on the other hand in the coating agent (1), expressed in% by weight, depends on the content of conductive pigment in% by weight in the coating agent (1). The higher the density of the conductive pigment, the higher its preferred weight ratio of the total coating agent (1), and the lower the weight proportions of solvent and resin components. The preferred weight percentages of solvent and resin components therefore depend on the density ρ of the conductivity pigment used or the average density ρ of a mixture of conductive pigments.
Allgemein gilt für das Beschichtungsmittel (1) im erfindungsgemäßen Verfahren (III), dass es vorzugsweise, bezogen auf die Gesamtmasse des Beschichtungsmittels (1), [(25 bis 60). Anpassungsfaktor] Gew.-%, vorzugsweise [(35 bis 55) · Anpassungsfaktor] Gew.-% organisches Lösungsmittel und [(20 bis 45) · Anpassungsfaktor] Gew.-%, vorzugsweise [(25 bis 40) · Anpassungsfaktor] Gew.-%, organische Harzkomponenten enthält, wobei die Summe der Gewichtsprozentanteile von organischer Harzkomponente und Lösungsmittel nicht größer als [93 · Anpassungsfaktor] Gew.-%, vorzugsweise nicht größer als [87 · Anpassungsfaktor] Gew.-% ist und wobei der Anpassungsfaktor [100-2,8p]:93,85 ist und ρ die Dichte des Leitfähigkeitspigments oder die mittlere Dichte der Mischung von Leitfähigkeitspigmenten in g/cm3 bedeutet.In general, for the coating composition (1) in the process (III) according to the invention, it is preferable that, based on the total mass of the coating composition (1), [(25 to 60). Adjustment factor] Wt%, preferably [(35 to 55) Fitting factor] Wt% organic solvent and [(20 to 45) Fitting factor] Wt%, preferably [(25 to 40) Fitting factor] Wt. % organic resin components, wherein the sum of the weight percentages of organic resin component and solvent is not greater than [93 * adjustment factor] wt%, preferably not greater than [87 * adaptation factor] wt%, and wherein the adjustment factor [100 -2.8p]: 93.85 and ρ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
Hinsichtlich der einzelnen Harzkomponente a) gilt vorzugsweise, dass das Beschichtungsmittel (1), bezogen auf die Gesamtmasse des Beschichtungsmittels (1), [(2 bis 8) · Anpassungsfaktor] Gew.-%, vorzugsweise [(3 bis 5) · Anpassungsfaktor] Gew.-% der Harzkomponente a) enthält, wobei der Anpassungsfaktor [100-2,8p]:93,85 ist und ρ die Dichte des Leitfähigkeitspigments oder die mittlere Dichte der Mischung von Leitfähigkeitspigmenten in g/cm3 bedeutet. Aus dem Mengenanteil der Harzkomponente a) lassen sich mit den weiter oben angegebenen bevorzugten Mengenverhältnissen der einzelnen Harzkomponenten die bevorzugten Mengenanteile der Harzkomponenten b) bis d) im Beschichtungsmittel (1) berechnen. Beispielsweise kann der Anteil der Komponenten b) an der Gesamtmasse des Beschichtungsmittels [(2 bis 9) · Anpassungsfaktor] Gew.-%, vorzugsweise [(3 bis 6) · Anpassungsfaktor] Gew.-% betragen, der Anteil der Harzkomponenten c) [(4 bis 18) · Anpassungsfaktor] Gew.-%, vorzugsweise [(6 bis 12) · Anpassungsfaktor] Gew.-% und der Anteil der Harzkomponenten d) [(7 bis 30) · Anpassungsfaktor] Gew.-%, vorzugsweise [(10 bis 20) · Anpassungsfaktor] Gew.-%. Der "Anpassungsfaktor" hat dabei die vorstehend angegebene Bedeutung.
Weiterhin ist es bevorzugt, dass die Schicht b) zusätzlich Korrosionsinhibitoren und/oder Korrosionsschutzpigmente enthält. Hierbei können Korrosioninhibitoren oder Korrosionsschutzpigmente eingesetzt werden, die im Stand der Technik für diesen Zweck bekannt sind. Beispielsweise genannt seien: Magnesiumoxidpigmente, insbesondere in nanoskaliger Form, feinteiliges und sehr feinteiliges Bariumsulfat oder Korrosionsschutzpigmente basieren auf Calciumsilicat. Der bevorzugte Gewichtsanteil der Korrosionsschutzpigmente an der Gesamtmasse des Beschichtungsmittels (1) hängt wiederum von der Dichte der eingesetzten Korrosionsschutzpigmente ab. Vorzugsweise enthält das Beschichtungsmittel (1) im erfindungsgemäßen Verfahren (III), bezogen auf die Gesamtmasse des Beschichtungsmittels, [(5 bis 25) · Anpassungsfaktor] Gew.-%, insbesondere [(10 bis 20) · Anpassungsfaktor] Gew.-% Korrosionsschutzpigment, wobei der Anpassungsfaktor [100-2,8p]:93,85 ist und ρ die Dichte des Leitfähigkeitspigments oder die mittlere Dichte der Mischung von Leitfähigkeitspigmenten in g/cm3 bedeutet.With respect to the individual resin component a), it is preferable that the coating agent (1), based on the total mass of the coating agent (1), be [(2 to 8) · adjustment factor]% by weight, preferably [(3 to 5) · adjustment factor] Wt .-% of the resin component a), wherein the adjustment factor [100-2.8p]: 93.85 and ρ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 . From the proportion of the resin component a) can be calculated with the above-mentioned preferred ratios of the individual resin components, the preferred proportions of the resin components b) to d) in the coating agent (1). For example, the proportion of components b) in the total mass of the coating agent [(2 to 9) adjustment factor] wt .-%, preferably [(3 to 6) adjustment factor] wt%, the proportion of resin components c) [(4 to 18) adjustment factor] wt%, preferably [(6 to 12) adjustment factor] wt% and the proportion of the resin components d) [(7 to 30) · adjustment factor] wt%, preferably [(10 to 20) · adjustment factor] wt%. The "adaptation factor" has the meaning given above.
Furthermore, it is preferred that the layer b) additionally contains corrosion inhibitors and / or anticorrosive pigments. Corrosion inhibitors or anticorrosive pigments which are known in the prior art for this purpose can be used here. Examples which may be mentioned are: magnesium oxide pigments, in particular in nanoscale form, finely divided and very finely divided barium sulfate or anticorrosive pigments based on calcium silicate. The preferred weight fraction of the anticorrosion pigments on the total mass of the coating composition (1) in turn depends on the density of the anticorrosion pigments used. The coating composition (1) in the process (III) according to the invention, based on the total mass of the coating composition, preferably contains [(5 to 25) adjustment factor]% by weight, in particular [(10 to 20) adjustment factor]% by weight corrosion protection pigment where the adjustment factor is [100-2.8p]: 93.85 and ρ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
Die mechanischen und chemischen Eigenschaften der nach dem Einbrennen des Beschichtungsmittels (1) im erfindungsgemäßen Verfahren (III) erhaltenen Beschichtung können weiterhin dadurch verbessert werden, dass diese zusätzlich Füllstoffe enthält. Beispielsweise können diese ausgewählt sein aus Kieselsäuren oder Siliziumoxiden (gegebenenfalls hydrophobiert), Aluminiumoxiden (einschließlich basischen Aluminiumoxid), Titandioxid und Bariumsulfat. Hinsichtlich deren bevorzugten Mengen gilt, dass das Beschichtungsmittel (1) [(0,1 bis 3) · Anpassungsfaktor] Gew.-%, vorzugsweise [(0,4 bis 2) · Anpassungsfaktor] Gew.-% Füllstoff ausgewählt aus Kieselsäuren bzw. Siliziumoxiden, Aluminiumoxiden, Titandioxid und Bariumsulfat enthält, wobei der Anpassungsfaktor [100-2,8 p]:93,85 ist und ρ die Dichte des Leitfähigkeitspigments oder die mittlere Dichte der Mischung von Leitfähigkeitspigmenten in g/cm3 bedeutet.The mechanical and chemical properties of the coating obtained after the baking of the coating agent (1) in process (III) according to the invention can be further improved by additionally containing fillers. For example, these may be selected from silicas or silicas (optionally hydrophobed), alumina (including basic alumina), titania and barium sulfate. With regard to their preferred amounts, the coating composition is (1) [(0.1 to 3) adjustment factor]% by weight, preferably [(0.4 to 2) adjustment factor]% by weight filler selected from silicas or Silicon dioxide, aluminum oxide, titanium dioxide and barium sulfate, where the adjustment factor is [100-2.8 p]: 93.85 and ρ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
Werden Gleitmittel oder Umformhilfen zusätzlich mit eingesetzt, so gilt, dass das Beschichtungsmittel (1) bezogen, auf seine Gesamtmasse, Gleitmittel oder Umformhilfen, vorzugsweise ausgewählt aus Wachsen, Molybdänsulfid und Teflon, vorzugsweise in einer Menge von [(0,5 bis 20) · Anpassungsfaktor], insbesondere in einer Menge von [(1 bis 10) · Anpassungsfaktor] Gew.-% enthält, wobei der Anpassungsfaktor [100-2,8p]:93,85 ist und ρ die Dichte des Leitfähigkeitspigments oder die mittlere Dichte der Mischung von Leitfähigkeitspigmenten in g/cm3 bedeutet.
Das erfindungsgemäße Verfahren (III), welches die Aufbringung organischer Lacke mit umfasst, besteht demgemäß aus folgender Prozesskette:
- i) gegebenenfalls Reinigung / Entfettung der Werkstoffoberfläche
- ii) metallisierende Vorbehandlung mit einem wässrigen Mittel (1) gemäß der vorliegenden Erfindung
- iii) gegebenenfalls Spül- und/oder Trocknungsschritt
- iv) chrom(VI)freie Konversionsbehandlung, bei der eine Konversionsschicht erzeugt wird, die pro m2 Oberfläche 0,01
bis 0,7 mmol des Metalls M enthält, das die wesentliche Komponente der Konversionslösung darstellt, wobei die Metalle M ausgewählt sind aus Cr(III), B, Si, Ti, Zr, Hf. - v) gegebenenfalls Spül- und/oder Trocknungsschritt
- vi) Beschichtung mit einem Beschichtungsmittel (1) gemäß vorstehender Beschreibung und Aushärten bei einer Substrattemperatur im Bereich von 120 bis 260 °C, vorzugsweise im Bereich von 150 bis 170 °C.
The process (III) according to the invention, which comprises the application of organic paints, accordingly consists of the following process chain:
- i) optionally cleaning / degreasing the material surface
- ii) metallizing pretreatment with an aqueous agent (1) according to the present invention
- iii) optionally rinsing and / or drying step
- iv) chromium (VI) free conversion treatment which produces a conversion layer containing, per m 2 of surface, 0.01 to 0.7 mmol of the metal M which is the essential component of the conversion solution, the metals M being selected from Cr (III), B, Si, Ti, Zr, Hf.
- v) optionally rinsing and / or drying step
- vi) coating with a coating agent (1) as described above and curing at a substrate temperature in the range of 120 to 260 ° C, preferably in the range of 150 to 170 ° C.
Dabei führt man vorzugsweise sämtliche Schritte (i-vi) als Bandbehandlungsverfahren durch, wobei man im Schritt (vi) das flüssige Beschichtungsmittel (1) in einer solchen Menge aufbringt, dass man nach dem Aushärten die gewünschte Schichtdicke im Bereich von 0,5 bis 10 µm erhält. Vorzugsweise wird also das Beschichtungsmittel (1) im so genannten Coil-Coating-Verfahren aufgebracht. Hierbei werden laufende Metallbänder kontinuierlich beschichtet. Das Beschichtungsmittel (1) kann dabei nach unterschiedlichen Verfahren aufgetragen werden, die im Stand der Technik geläufig sind. Beispielsweise können Auftragswalzen verwendet werden, mit denen sich direkt die erwünschte Nassfilm-Dicke einstellen lässt. Alternativ hierzu kann man das Metallband in das Beschichtungsmittel (1) eintauchen oder es mit dem Beschichtungsmittel (1) besprühen, wonach man mit Hilfe von Abquetschwalzen die erwünschte Nassfilmdicke einstellt.In this case, preferably all steps (i-vi) are carried out as a strip treatment method, wherein the liquid coating composition (1) is applied in step (vi) in such an amount that, after curing, the desired layer thickness is in the range from 0.5 to 10 receives μm. Preferably, therefore, the coating agent (1) is applied in the so-called coil coating process. Here, continuous metal strips are continuously coated. The coating agent (1) can be applied by different methods, which are familiar in the prior art. For example, applicator rolls can be used to directly adjust the desired wet film thickness. Alternatively, one can immerse the metal strip in the coating agent (1) or spray it with the coating agent (1), after which the desired wet film thickness is adjusted by means of squeeze rolls.
Sofern Metallbänder beschichtet werden, die unmittelbar zuvor mit einer Metallauflage, beispielsweise mit Zink oder Zinklegierungen, elektrolytisch oder im Schmelztauchverfahren überzogen wurden, ist eine Reinigung der Metalloberflächen vor der Durchführung der metallisierenden Vorbehandlung (ii) nicht erforderlich. Sind die Metallbänder jedoch bereits gelagert worden und insbesondere mit Korrosionsschutzölen versehen, ist ein Reinigungsschritt (i) notwendig, bevor man den Schritt (ii) durchführt.If metal strips coated immediately before with a metal coating, for example with zinc or zinc alloys, electrolytically or by hot dip coating, it is not necessary to clean the metal surfaces prior to performing the metallizing pretreatment (ii). However, if the metal strips have already been stored and in particular provided with corrosion protection oils, a purification step (i) is necessary before carrying out step (ii).
Nach dem Auftragen des flüssigen Beschichtungsmittels (1) im Schritt (vi) wird das beschichtete Blech auf die erforderliche Trocknungs- bzw. Vernetzungstemperatur für die organische Beschichtung erwärmt. Das Erwärmen des beschichteten Substrats auf die erforderliche Substrattemperatur ("Peak-metal-temperature" = TMP) im Bereich von 120 bis 260°C, vorzugsweise im Bereich von 150 bis 170°C kann in einem aufgeheizten Durchlaufofen erfolgen. Das Behandlungsmittel kann jedoch auch durch Infrarotstrahlung, insbesondere durch nahe Infrarotstrahlung, auf die entsprechende Trocknungs- bzw. Vernetzungstemperatur gebracht werden.After applying the liquid coating agent (1) in step (vi), the coated sheet is heated to the required drying or crosslinking temperature for the organic coating. The heating of the coated substrate to the required substrate temperature ("peak-metal-temperature" = TMP) in the range of 120 to 260 ° C, preferably in the range of 150 to 170 ° C can take place in a heated continuous furnace. However, the treatment agent can also be brought to the corresponding drying or crosslinking temperature by infrared radiation, in particular by near infrared radiation.
Derart vorbeschichtete Metallbleche werden in der automobilen Fertigung für die Herstellung von Karosserien entsprechend zugeschnitten und umgeformt. Das zusammengefügte Bauteil bzw. die zusammengefügte Rohkarosse weist folglich ungeschützte Schnittkanten auf, die zusätzlich korrosionsschützend behandelt werden müssen. Im sogenannten "Paint Shop" erfolgt daher eine weitere korrosionsschützende Behandlung und letztendlich die Realisierung des automobiltypischen Lackaufbaus.Such pre-coated metal sheets are tailored and converted in the automotive production for the production of bodies accordingly. The assembled component or the assembled body shell therefore has unprotected edges, which must be treated in addition corrosion protection. In the so-called "paint shop", therefore, there is a further corrosion-protective treatment and, ultimately, the realization of the automobile-typical paint structure.
Die vorliegende Erfindung betrifft daher in einem weiteren Aspekt ein Verfahren (IV), welches die Prozesskette (i-vi) des Verfahrens (III) erweitert, wobei zunächst auf den freiliegenden Metalloberflächen, insbesondere auf den Schnittkanten, eine kristalline Phosphatschicht abgeschieden wird, um anschließend mittels Tauchlack einen finalen Korrosionsschutz, insbesondere Schutz vor Unterwanderung des Lacksystems an den Schnittkanten zu realisieren. Für den Fall, dass die Erstbeschichtung im Verfahren (III) mit einem organischen Beschichtungsmittel (1) zu einer leitfähigen Beschichtung führt, kann das gesamte metallische Bauteil einschließlich der phosphatierten Schnittkanten und der im Verfahren (III) erstbeschichteten Flächen elektrotauchlackiert werden (
Die vorliegende Erfindung betrifft in einem weiteren Aspekt die verzinkte und/oder legierungsverzinkte Stahloberfläche sowie das metallische Bauteil, welches zumindest teilweise aus einer Zinkoberfläche besteht, das gemäß dem erfindungsgemäßen Verfahren mit dem wässrigen Mittel (1) metallisierend vorbehandelt ist oder nachfolgend dieser Vorbehandlung mit weiteren passivierenden Konversionsschichten und/oder Lacken, z.B. entsprechend der erfindungsgemäßen Verfahren (II-IV), beschichtet ist.
Eine derartig behandelte Stahloberfläche oder behandeltes Bauteil findet Verwendung im Karosseriebau bei der automobilen Fertigung, im Schiffsbau, im Baugewerbe sowie für die Herstellung Weißer Ware.In a further aspect, the present invention relates to the galvanized and / or alloy-galvanized steel surface and the metallic component, which consists at least partially of a zinc surface which has been pretreated by metallizing in accordance with the process according to the invention with the aqueous agent (1) or subsequently this pretreatment with further passivating Conversion layers and / or paints, for example according to the inventive method (II-IV) coated.
Such a treated steel surface or treated component is used in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods.
Eine elektrochemische Messkette zur Bestimmung der elektromotorischen Kraft (EMK) für die erfindungsgemäße metallisierende Vorbehandlung ist in
Zur beispielhaften Darlegung der Verbesserung des Schnittkantenschutzes nach erfolgter erfindungsgemäßer metallisierender Vorbehandlung ("Vereisenung") von verzinktem Bandstahl wird im Folgenden die Prozesskette des erfindungsgemäßen Verfahrens (III) auf elektrolytisch verzinkten Stahlblechen (DC04, ZE 75/75, Automobilqualität) durchgeführt. Die derartig behandelten und beschichteten verzinkten Stahlbleche wurden an den Schnittkanten in einem Buchenholzblock eingeklemmt und im VDA-Wechselklimatest (621-415) für 10 Wochen dauerfeucht ausgelagert.The process chain of process (III) according to the invention on electrolytically galvanized steel sheets (DC04, ZE 75/75, automobile grade) is described below as an example of the improvement of the cut edge protection after the metallizing pretreatment ("icing") of galvanized steel strip according to the invention. The galvanized steel sheets treated and coated in this way were clamped at the cut edges in a beech wood block and permanently aged for a period of 10 weeks in the VDA climate change test (621-415).
Das erfindungsgemäße Verfahren (III) ist einschließlich der eingesetzten Formulierungen im Folgenden detailliert aufgeschlüsselt:
- (i) Das elektrolytisch verzinkte Stahlblech (ZE) wird mit alkalischen Reinigern (z.B. Ridoline® C 72, Ridoline® 1340; Tauch-, Spritzreinigungsprodukte der Anmelderin) entfettet,
- (ii) die metallisierende Vorbehandlung ("Vereisenung") erfolgt bei einer Temperatur des wässrigen Mittels (1) von 50 °C bei einen pH-
2,5 im Tauchverfahren mit einer Kontaktzeit von t = 2 sec (B1) bzw. t = 5 sec (B2), wobei das Mittel (1) zusammengesetzt ist aus:Wert von - B1: 27,8 g/l FeSO4·7H2O
- B2: 13,9 g/l FeSO4·7H2O
9,9 g/l H3PO2
3,0 g/l Milchsäure
- (iii) Spülschritt durch Eintauchen des vorbehandelten Bleches in Stadtwasser;
- (iv) eine kommerzielle Vorbehandlungslösung auf Basis Phosphorsäure, Manganphosphat, H2TiF6 und Aminomethyl-substituiertem Polyvinylphenol (Granodine® 1455T der Anmelderin) wird mit dem Chemcoater (Walzenauftragsverfahren) auf der Metalloberfläche aufgetragen. Es erfolgt eine Trocknung bei 80 °C und die resultierende Schichtauflage an Titan bestimmt mittels Röntgenfluoreszenzanalyse liegt zwischen 10-15 mg/m2;
- (v) Spülschritt durch Eintauchen des vorbehandelten Bleches in Stadtwasser;
- (vi) ein kommerzielles Beschichtungsmittel (1) enthaltend Graphit als Leitfähigkeitspigment auf Basis der in der deutschen Anmeldung (
DE 102007001654.0 Trockenfilmschichtdicken von 1,8 µm
- (i) The electrolytically galvanized sheet steel (ZE) is treated with alkaline cleaners (eg Ridoline ® C 72, Ridoline ® 1340; dip, spray cleaning products of the applicant) degreased,
- (ii) the metallizing pretreatment ("icing") takes place at a temperature of the aqueous medium (1) of 50 ° C. at a pH of 2.5 in the dipping method with a contact time of t = 2 sec (B1) or t = 5 sec (B2), wherein the means (1) is composed of:
- B1: 27.8 g / l FeSO 4 .7H 2 O
- B2: 13.9 g / l FeSO 4 .7H 2 O
9.9 g / l H 3 PO 2
3.0 g / L lactic acid
- (iii) rinsing step by immersing the pretreated sheet in city water;
- (iv) a commercial pretreatment solution based on phosphoric acid, manganese phosphate, H 2 TiF 6 and aminomethyl-substituted polyvinyl phenol (1455T Granodine ® of the applicant) is applied with a Chemcoater (roll coating method) on the metal surface. It is dried at 80 ° C and the resulting layer of titanium determined by X-ray fluorescence analysis is 10-15 mg / m 2 ;
- (v) rinsing step by immersing the pretreated sheet in city water;
- (vi) a commercial coating composition (1) containing graphite as a conductive pigment based on the process described in the German application (
DE 102007001654.0
Die Schichtauflage an Eisen auf der elektrolytisch verzinkten Stahloberfläche kann unmittelbar nach dem Prozessschritt (ii) nasschemisch in 10 Gew.-% Salzsäure in Lösung gebracht und mittels Atom-Absorbtions-Spektroskopie (AAS) bestimmt werden oder alternativ in Vergleichsversuchen auf reinen Zinksubstraten (99,9 % Zn) mittels Röntgenfluoreszenzanalytik (RFA). Sie beträgt bei der metallisierenden Vorbehandlung gemäß B1 im Prozessschritt (ii) cirka 20 mg/m2 Fe.The layer coating of iron on the electrolytically galvanized steel surface can be brought into solution immediately after the process step (ii) wet-chemically in 10 wt .-% hydrochloric acid and determined by atomic absorption spectroscopy (AAS) or alternatively in comparative experiments on pure zinc substrates (99, 9% Zn) by means of X-ray fluorescence analysis (RFA). In the case of the metallizing pretreatment according to B1 in process step (ii), it amounts to approximately 20 mg / m 2 Fe.
Das erfindungsgemäße Verfahren (III) wird in der Weise abgeändert, dass der Prozessschritt (ii), also die metallisierende Vorbehandlung entfällt.The process (III) according to the invention is modified in such a way that the process step (ii), ie the metallizing pretreatment, is omitted.
Das erfindungsgemäße Verfahren (III) wird in der Weise abgeändert, dass anstelle des Prozessschrittes (ii) eine alkalisch passivierende Vorbehandlung mit dem kommerziellen Produkt der Anmelderin (Granodine® 1303) gemäß der in deutschen Offenlegungsschrift
Nach einer Entfettung mit einem alkalischen Reinigersystem der Anmelderin (Ridoline® 1565 / Ridosol® 1237) wird das Blech in einer kommerziellen Aktivierlösung (Fixodine® 9112) aktiviert und in einem Tri-Kationen-Phosphatierbad der Anmelderin (Granodine® 958A) passiviert bevor es analog zum Prozessschritt (vi) mit dem Lacksystem beschichtet wird.After a degreasing with an alkaline cleaner system of the applicant (Ridoline ® 1565 / Ridosol ® 1237) is passivated before analogously the sheet in a commercial activating solution (FIXODINE ® 9112) is activated and in a tri-cation phosphating the Applicant (Granodine ® 958A) to the process step (vi) is coated with the paint system.
Im Anschluss an die Prozesskette gemäß dem Verfahren (III) werden sämtliche Bleche zur Erzeugung der Schnittkante zugeschnitten und erneut einer Phosphatierung wie im Versuchsbeispiel V3 angegeben unterzogen.
Auf sämtlichen derart behandelten und beschichteten Blechen wird nachträglich ein kathodischer Tauchlack (EV 2005, PPG Industries) mit einer Schichtdicke von 18-20 µm abgeschieden und im Umluftofen bei 175 °C für 20 min eingebrannt. Demnach wird insgesamt eine Prozesskette beginnend mit der korrosionsschützenden Vorbehandlung des Zinksubstrates beim Stahlhersteller (
On all such treated and coated sheets, a cathodic dip coating (EV 2005, PPG Industries) with a layer thickness of 18-20 microns is subsequently deposited and baked in a convection oven at 175 ° C for 20 min. Accordingly, a process chain beginning with the corrosion-protective pretreatment of the zinc substrate at the steel manufacturer (
Tab. 2 gibt die Ergebnisse bezüglich der korrosiven Lackunterwanderung an der Schnittkante nach 10 Wochen Wechselklimatest wieder. Da die Lackunterwanderung an verschiedenen Stellen der Schnittkante unterschiedlich stark voranschreitet, enthält die Tabelle 2 die jeweils maximale Unterwanderung in mm für das entsprechende Beschichtungssystem.
Anhand der Ergebnisse im VDA-Wechselklimatest wird der gegenüber den konventionellen Behandlungsmethoden überlegene Korrosionsschutz der erfindungsgemäßen metallisierenden Vorbehandlung ("Vereisenung") an der Schnittkante deutlich. Die im Stand der Technik beschriebene alkalische Passivierung mittels Eisen(III)-haltiger Lösungen weist zwar verglichen mit phosphatierten Blechen (V3) und Blechen, die keine passivierende Vorbehandlung erhalten haben (V1) einen verbesserten Schnittkantenschutz auf, jedoch ist dieses Verfahren weitaus weniger effektiv als die erfindungsgemäße metallische Vorbehandlung (B1).Based on the results in the VDA climate change test, the corrosion protection of the metallizing pretreatment according to the invention ("icing"), which is superior to the conventional treatment methods, becomes clear at the cut edge. Although the alkaline passivation by means of iron (III) -containing solutions described in the prior art has, compared to phosphated sheets (V3) and sheets, which have not received passivating pretreatment (V1) improved edge protection, but is this method is much less effective than the inventive metallic pretreatment (B1).
Das hervorragende Ergebnis hinsichtlich der Minimierung der Kantenkorrosion und der Unterwanderung des Lacksystems an der Schnittkante bei erfindungsgemäßer Vorbehandlung (B1, B2) im Vergleich zu einer alkalisch vorbehandelten Zinkoberfläche (V2) für ein Beschichtungssystem gemäß einer Prozesskette IIa → IIIa → IVb (siehe
Eine Verbesserung der Ergebnisse im Steinschlagtest mittels der metallisierenden Vorbehandlung ("Vereisenung") ist ebenfalls evident. Die Bildaufnahmen in
Auch die korrosive Unterwanderung am Ritz belegt die Vorteile der erfindungsgemäßen Vorbehandlung ("Vereisenung" der Zinkoberfläche) wie aus
In einer alternativen Prozesskette, in der der erfindungsgemäßen Vorbehandlung (
Hierzu wurden zunächst die verzinkten Stahlbleche (ZE, Z) entsprechend der zuvor beschriebenen Vorgehensweise gereinigt und entfettet, um anschließend nach erfolgter Zwischenspülung mit entionisiertem Wasser (κ < 1 µScm-1) erfindungsgemäß mit einem Mittel, das entsprechend dem Beispiel B1 zusammengesetzt ist, bei einem bestimmten pH-Wert für 2 sec und einer Temperatur von 50 °C metallisierend vorbehandelt zu werden (
750 ppm Zr als H2ZrF6
20 ppm Cu als Cu(NO3)2
10 ppm Si als SiO2
200 ppm Zn als Zn(NO3)2
bei einem pH-Wert von 4 und einer Kontaktzeit von 90 sec bei einer Temperatur von 20 °C (
For this purpose, first the galvanized steel sheets (ZE, Z) were cleaned and degreased according to the procedure described above, and then after intermediate rinsing with deionized water (κ <1 μScm -1 ) according to the invention with an agent which is composed according to Example B1 pretreating to a specific pH for 2 seconds and a temperature of 50 ° C. (
750 ppm Zr as H 2 ZrF 6
20 ppm Cu as Cu (NO 3 ) 2
10 ppm Si as SiO 2
200 ppm Zn as Zn (NO 3 ) 2
at a pH of 4 and a contact time of 90 seconds at a temperature of 20 ° C (
Die Abbildungen 6 und 7 belegen anhand der röntgenphotoelektronischen (XPS) Detailspektren der Fe(2p3/2) nochmals, dass die im erfindungsgemäßen Verfahren aufgebrachte dünne Eisenauflage metallischen Charakter hat und deutlich mehr als 50 At-% der Eisenatome in metallischer Form vorliegen. Qualitativ ist dies erkennbar, an der deutlichen Verschiebung der gesamten Peak-Intensität zugunsten des Peaks 1 (
Claims (12)
- A method for metallizing pretreatment of galvanized or alloy-galvanized steel surfaces, whereby the galvanized or alloy-galvanized steel surface is brought into contact with an aqueous agent (1) whose pH is not less than 2 and not greater than 6, characterized in that agent (1) contains(a) cations and/or compounds of a metal (A), which is selected from cations and/or compounds of iron in a concentration of at least 0.001 M,(b) accelerators selected from oxoacids of phosphorus and the salts thereof, whereby at least one phosphorus atom is present in a medium oxidation state,whereby iron(II) ions and/or iron(II) compounds are used as cations and/or compounds of metal (A), and the molar ratio of accelerators to the concentration of the cations and/or compounds of metal (A) does not fall below the value of 1:5 and the redox potential ERedox of the cations and/or compounds of metal (A), measured on a metal electrode of metal (A) at a predetermined process temperature and concentration of cations and/or compounds of metal (A) in the aqueous agent (1), is more anodic than the electrode potential EZn of the galvanized or alloy-galvanized steel surface in contact with an aqueous agent (2), differing from agent (1) only in that it does not contain any cations and/or compounds of metal (A).
- The method according to claim 1, characterized in that the redox potential ERedox of the cations and/or compounds of metal (A) in aqueous agent (1) is more anodic than the electrode potential EZn of the galvanized or alloy-galvanized steel surface in contact with aqueous agent (2) by at least +50 mV but at most +800 mV
- The method according to one or both of claims 1 and 2, characterized in that the concentration of cations and/or compounds of metal (A) is at least 0.01 M but does not exceed 0.2 M.
- The method according to claim 3, characterized in that the pH of the aqueous agent is no greater than 4.
- The method according to one or more of the preceding claims, characterized in that the aqueous agent additionally contains chelating complexing agents having oxygen and/or nitrogen ligands.
- The method according to claim 5, characterized in that the chelating complexing agents are selected from triethanolamine, diethanolamine, monoethanolamine, monoisopropanolamine, aminoethylethanolamine, 1-amino-2,3,4,5,6-pentahydroxyhexane, N-(hydroxyethyl)ethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, tartaric acid, lactic acid, mucic acid, gluconic acid, and/or glucoheptonic acid, and salts and stereoisomers thereof, as well as sorbitol, glucose, and glucamine, and stereoisomers thereof.
- The method according to claim 6, characterized in that the molar ratio of chelating complexing agents to the concentration of cations and/or compounds of metal (A) is no greater than 5:1 but is at least 1:5.
- The method according to one or more of claims 1 to 7, characterized in that the aqueous agent additionally contains accelerators selected from hydrazine, hydroxylamine, nitroguanidine, N-methylmorpholine N-oxide, glucoheptonate, ascorbic acid, and reducing sugars.
- The method according to one or more of claims 1 to 8, characterized in that the aqueous agent additionally contains no more than 50 ppm but at least 0.1 ppm of copper(II) cations
- The method according to one or more of claims 1 to 9, characterized in that there is a metallic coating with metal (A) in a layer overlay of at least 1 mg/m2 but no more than 100 mg/m2 after the contacting of the galvanized or alloy-galvanized steel surface with the aqueous agent.
- The method according to one or more of claims 1 to 10, characterized in that a passivating conversion treatment of the metallized pretreated galvanized or alloy-galvanized steel surface is performed after the contacting of the galvanized or alloy-galvanized steel surface with the aqueous agent with or without an intermediate rinsing and/or drying step.
- The method according to claim 11, characterized in that further process steps for applying additional layers, in particular paint or paint systems follow.
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EP10187987.2A EP2292808B1 (en) | 2007-05-04 | 2008-04-30 | Metallising pre-treatment of zinc surfaces |
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DE102007021364A DE102007021364A1 (en) | 2007-05-04 | 2007-05-04 | Metallizing pretreatment of zinc surfaces |
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-
2007
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CA2686380A1 (en) | 2008-11-13 |
CA2686380C (en) | 2016-04-05 |
RU2482220C2 (en) | 2013-05-20 |
AU2008248694B2 (en) | 2012-10-04 |
US20100209732A1 (en) | 2010-08-19 |
WO2008135478A2 (en) | 2008-11-13 |
PT2292808T (en) | 2016-09-08 |
WO2008135478A3 (en) | 2009-01-08 |
JP2010526206A (en) | 2010-07-29 |
PT2145031E (en) | 2016-06-16 |
RU2009144881A (en) | 2011-06-10 |
BRPI0811537A2 (en) | 2014-11-18 |
EP2145031A2 (en) | 2010-01-20 |
ZA200907724B (en) | 2011-04-28 |
US8293334B2 (en) | 2012-10-23 |
PL2292808T3 (en) | 2016-12-30 |
JP2016074985A (en) | 2016-05-12 |
KR20100028542A (en) | 2010-03-12 |
EP2292808B1 (en) | 2016-06-08 |
ES2589380T3 (en) | 2016-11-14 |
EP2292808A1 (en) | 2011-03-09 |
CN101675181A (en) | 2010-03-17 |
MX2009011876A (en) | 2010-02-24 |
DE102007021364A1 (en) | 2008-11-06 |
CN101675181B (en) | 2012-10-24 |
PL2145031T3 (en) | 2016-09-30 |
HUE030515T2 (en) | 2017-05-29 |
ES2575993T3 (en) | 2016-07-04 |
JP5917802B2 (en) | 2016-05-18 |
AU2008248694A1 (en) | 2008-11-13 |
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