EP0121155B1 - Preparation of iron or steel surfaces for painting - Google Patents
Preparation of iron or steel surfaces for painting Download PDFInfo
- Publication number
- EP0121155B1 EP0121155B1 EP84102646A EP84102646A EP0121155B1 EP 0121155 B1 EP0121155 B1 EP 0121155B1 EP 84102646 A EP84102646 A EP 84102646A EP 84102646 A EP84102646 A EP 84102646A EP 0121155 B1 EP0121155 B1 EP 0121155B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- iron
- solids
- steel surfaces
- phosphate
- phosphating solution
- 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.)
- Expired
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 17
- 229910000831 Steel Inorganic materials 0.000 title claims description 16
- 239000010959 steel Substances 0.000 title claims description 16
- 238000010422 painting Methods 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 2
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 5
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims description 2
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 25
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 2
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 16
- 239000004922 lacquer Substances 0.000 description 13
- 239000003513 alkali Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/10—Orthophosphates containing oxidants
Definitions
- the invention relates to a method for applying high-solids lacquers to iron or steel surfaces, the iron or steel surfaces being prepared by applying a phosphate layer.
- High-solids coatings which usually have a solids content of 50 to 60% by weight and more, are becoming increasingly important due to the reduced solvent emission for reasons of environmental protection.
- the high-solids coatings are given the viscosity that is suitable for spraying, for example, by means of polymers which - compared to conventional coatings - have lower molecular weights. Due to the lower molecular weight, such paints are considerably more sensitive to defects in the surface of the phosphate layers produced and have a tendency to form craters around defects in the layer. This may be related to the tendency of such formulations to achieve a lower viscosity during solvent evaporation and to run off bumps on the surface.
- the object of the invention is to provide a method for applying high-solids lacquers to iron or steel surfaces, the iron or steel surfaces being prepared by applying a phosphate layer, which does not have the disadvantages mentioned above and which can be carried out flawlessly in a simple manner leads to high-solids lacquer films.
- the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the iron or steel surface is brought into contact with a phosphating solution based on alkali metal phosphate which has a pH of 4.2 to 6, dihydrogen phosphate in a concentration of 3 to 60 g / I and as an accelerator contains meta-nitrobenzenesulfonate in an amount of 0.1-3.0 g / I, rinses, dries and then applies the high-solids paint.
- a phosphating solution based on alkali metal phosphate which has a pH of 4.2 to 6, dihydrogen phosphate in a concentration of 3 to 60 g / I and as an accelerator contains meta-nitrobenzenesulfonate in an amount of 0.1-3.0 g / I, rinses, dries and then applies the high-solids paint.
- Alkali phosphate-based means that the majority of the cations in solution are alkali or ammonium ions.
- dihydrogen phosphate includes mixtures of orthophosphate and pyrophosphate.
- GB-PS 715 607 describes a process for applying phosphate layers by means of solutions which contain alkali, inorganic or organic ammonium phosphate and which can be accelerated with meta-nitrobenzenesulfonate, among other things, and the suitability of these phosphate layers as the basis for paints, Lacquers and the like mentioned. From today's point of view, however, these were conventional paint or lacquer systems with comparatively low solids contents, the flow properties of which are completely different compared to those of high-solids lacquers.
- Preferred embodiments of the invention provide for the iron or steel surface to be brought into contact with a phosphating solution which has a pH of 4.5 to 5.5 or the dihydrogen phosphate in an amount of 4 to 10 g / l or which contains meta-nitrobenzenesulfonate in an amount of 0.1 to 1.5 g / 1.
- the phosphating solutions can be used at a temperature which is usually above 21 ° C. and can reach values at which decomposition of the meta-nitrobenzenesulfonate begins.
- the upper limit of the temperature of the phosphating solution is normally around 49 ° C.
- the phosphating solution can be applied in the customary manner, for example by spraying, dipping or flooding. Depending on the form of the application and The desired duration of the phosphate layer, for example with regard to layer thickness, can be from 5 seconds to a few minutes.
- the layer weight of the phosphate layer produced is generally between 0.1 and 1.0 g / m 2 . Depending on the treatment conditions, higher layer weights can also be achieved. If a separate pH adjustment is required, it is generally done with phosphoric acid.
- the phosphating solution to be used in the process according to the invention can contain various types of surfactants or emulsifiers, e.g. which are also used in metal cleaning. Of course, they must be compatible with the phosphating solution and the organic accelerator so that their phosphating function is retained at the same time.
- the usual treatment measures can be taken before and after the phosphating step. So the metal surfaces are usually previously with a cleaning treatment to remove grease and dirt, e.g. B. with the help of an alkaline cleaner. If necessary, pickling treatment to remove rust can follow. Between cleaning, possibly pickling, and phosphating, it is generally rinsed thoroughly with water.
- the final treatment is the application of the high-solids lacquer, which may be followed by the application of a further lacquer structure. After painting or the individual painting steps, it is usually baked.
- High-solids paints, high-solids or low-solvent paints usually have solids contents of 50 to 60% by weight and more and are becoming increasingly important due to the reduced solvent emission for reasons of environmental protection. Your e.g. Viscosity suitable for spray application is obtained from polymers that - compared to conventional paints - have lower molecular weights.
- Viscosity suitable for spray application is obtained from polymers that - compared to conventional paints - have lower molecular weights.
- a solvent-thinned single-layer high-solids paint (from PPG Inc., with the designation Duracron 200) was then applied to the first sheet and a single-layer high-solids black paint (from Sherwin-Williams, with the Designation 4653), each applied by spraying. Both paint films were burned in with circulating air at 163 ° C for 15 minutes.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Saccharide Compounds (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Aufbringung von high-solids-Lacken auf Eisen- oder Stahloberflächen, wobei die Eisen- oder Stahloberflächen durch Aufbringen einer Phosphatschicht vorbereitet werden.The invention relates to a method for applying high-solids lacquers to iron or steel surfaces, the iron or steel surfaces being prepared by applying a phosphate layer.
Die Eignung von Eisenphosphatüberzügen auf Eisen- oder Stahloberflächen zwecks Verbesserung des Korrosionswiderstandes und der Haftung eines anschliessend aufgebrachten organischen Überzuges oder Lackes ist seit langem bekannt. Es ist übliche Praxis, den Alkaliphosphatierverfahren, die derartige Eisenphosphatüberzüge erzeugen, verschiedene anorganische Oxidationsmittel, wie Nitrit, Chlorat, Bromat, Molybdat und Fluorid, zuzusetzen, um damit die Schichtbildungsgeschwindigkeit auf ein wirtschaftlich sinnvolles Mass zu erfiöhen und weiterhin die Qualität und Struktur der erzeugten Phosphatschicht zu verbessern im Vergleich zu solchen Alkaliphosphatiersystemen, die ohne Oxidationsmittel arbeiten. Während nach der vorgenannten Weise erzeugte Phosphatschichten zufriedenstellend sind, wenn anschliessend ein konventioneller, lösungsmittelverdünnter organischer Lack aufgebracht wird, treten Schwierigkeiten in Form von lokalen Oberflächenverfärbungen und/oder Rauhigkeiten und/oder Glanzverlust auf, wenn die Phosphatschicht mit einem sogenannten «high-solids»-Lack versehen wird.The suitability of iron phosphate coatings on iron or steel surfaces for the purpose of improving the corrosion resistance and the adhesion of a subsequently applied organic coating or lacquer has long been known. It is common practice to add various inorganic oxidizing agents, such as nitrite, chlorate, bromate, molybdate and fluoride, to the alkali phosphating processes that produce such iron phosphate coatings in order to increase the rate of film formation to an economically reasonable level and also to improve the quality and structure of the phosphate layer produced to be improved compared to those alkali phosphating systems which work without oxidizing agents. While phosphate layers produced according to the aforementioned manner are satisfactory if a conventional, solvent-diluted organic lacquer is subsequently applied, difficulties arise in the form of local surface discoloration and / or roughness and / or loss of gloss if the phosphate layer is coated with a so-called «high-solids» - Paint is provided.
High-solids-Lacke, die üblicherweise einen Feststoffgehalt von 50 bis 60 Gew.-% und mehr aufweisen, gewinnen wegen der verringerten Lösungsmittelemission aus Gründen des Umweltschutzes zunehmend an Bedeutung. Die beispielsweise zur Spritzanwendung geeignete Viskosität erhalten die high-solids-Lacke durch Polymere, die - gegenüber konventionellen Lacken - niedrigere Molekulargewichte aufweisen. Bedingt durch das geringere Molekulargewicht reagieren derartige Lacke erheblich empfindlicher auf Mängel in der Oberfläche der erzeugten Phosphatschichten und haben eine Tendenz zur Kraterbildung um Fehlstellen in der Schicht. Dies hängt möglicherweise mit der Tendenz derartiger Formulierungen, während der Lösungsmittelverdampfung eine niedrigere Viskosität zu erreichen und von Erhebungen auf der Oberfläche abzulaufen, zusammen.High-solids coatings, which usually have a solids content of 50 to 60% by weight and more, are becoming increasingly important due to the reduced solvent emission for reasons of environmental protection. The high-solids coatings are given the viscosity that is suitable for spraying, for example, by means of polymers which - compared to conventional coatings - have lower molecular weights. Due to the lower molecular weight, such paints are considerably more sensitive to defects in the surface of the phosphate layers produced and have a tendency to form craters around defects in the layer. This may be related to the tendency of such formulations to achieve a lower viscosity during solvent evaporation and to run off bumps on the surface.
Das bei der Verwendung der allgemein üblichen, mit anorganischen Oxidationsmitteln arbeitenden Alkaliphosphatiersystemen vor der Beschichtung mit high-solids-Lacken auftretende Problem ist auch darin begründet, dass im rauhen Betrieb in der Behandlungslinie ein Auftropfen oder Aufspritzen von Phosphatierungslösung auf bereits getrocknete Phosphatschichten nicht gänzlich zu vermeiden ist. Derartige Tropfen oder Spritzer führen zur Bildung lokalisierter Ablagerungen von Salzen auf der phosphatierten Oberfläche, die nach Aufbringung und anschliessender Härtung des high-solids-Lackes dazu neigen, durch den Lackaufbau «durchzubluten». Nach der Lackierung führen sie zu deutlich erkennbar weissen Ringen und zu einem matten Aussehen des Lackes im Inneren der Ringe. Diese Beeinträchtigung der fertigen Lackoberfläche ist häufig so schwerwiegend, dass das Werkstück nach aufwendiger Entfernung der fehlerhaften Überzüge zur erneuten Behandlung in den Verfahrensgang zurückgeführt werden muss.The problem that arises when using the generally customary alkali phosphating systems which work with inorganic oxidizing agents before coating with high-solids lacquers is also due to the fact that in rough operation in the treatment line, dripping or spraying on of phosphating solution onto already dried phosphate layers cannot be completely avoided is. Such drops or splashes lead to the formation of localized deposits of salts on the phosphated surface, which after application and subsequent hardening of the high-solids lacquer tend to "bleed through" through the lacquer structure. After painting, they lead to clearly recognizable white rings and to a matt appearance of the paint inside the rings. This impairment of the finished paint surface is often so severe that the workpiece has to be returned to the process for further treatment after extensive removal of the defective coatings.
Aufgabe der Erfindung ist es, ein Verfahren zur Aufbringung von high-solids-Lacken auf Eisen- oder Stahloberflächen, wobei die Eisen- oder Stahloberflächen durch Aufbringen einer Phosphatschicht vorbereitet werden, bereitzustellen, das die zuvor genannten Nachteile nicht aufweist und bei einfacher Durchführungsweise zu einwandfreien high-solids-Lackfilmen führt.The object of the invention is to provide a method for applying high-solids lacquers to iron or steel surfaces, the iron or steel surfaces being prepared by applying a phosphate layer, which does not have the disadvantages mentioned above and which can be carried out flawlessly in a simple manner leads to high-solids lacquer films.
Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, dass man die Eisen- oder Stahloberfläche mit einer Phosphatierungslösung auf Basis Alkaliphosphat in Berührung bringt, die einen pH-Wert von 4,2 bis 6 aufweist, Dihydrogenphosphat in einer Konzentration von 3 bis 60 g/I und als Beschleuniger meta-Nitrobenzolsulfonat in einer Menge von 0,1-3,0 g/I enthält, spült, trocknet und anschliessend den high-solids-Lack aufbringt.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the iron or steel surface is brought into contact with a phosphating solution based on alkali metal phosphate which has a pH of 4.2 to 6, dihydrogen phosphate in a concentration of 3 to 60 g / I and as an accelerator contains meta-nitrobenzenesulfonate in an amount of 0.1-3.0 g / I, rinses, dries and then applies the high-solids paint.
Auf Basis Alkalkiphosphat bedeutet, dass der überwiegende Teil der in Lösung befindlichen Kationen Alkali- oder Ammoniumionen sind. Die Bezeichnung Dihydrogenphosphat schliesst Gemische von Orthophosphat und Pyrophosphat ein.Alkali phosphate-based means that the majority of the cations in solution are alkali or ammonium ions. The term dihydrogen phosphate includes mixtures of orthophosphate and pyrophosphate.
Zwar ist in der GB-PS 715 607 ein Verfahren zur Aufbringung von Phosphatschichten mittels Lösungen, die Alkali-, anorganisches oder organisches Ammoniumphosphat enthalten und die unter anderem mit meta-Nitrobenzolsulfonat beschleunigt werden können, beschrieben und die Eignung dieser Phosphatschichten als Basis für Farben, Lacke und dgl. erwähnt. Hierbei handelte es sich jedoch um - aus heutiger Sicht - konventionelle Farb- bzw. Lacksysteme mit vergleichsweise geringen Feststoffgfehalten, deren Verlaufseigenschaften - verglichen mit denen von high-solids-Lacken - gänzlich verschieden sind. Es war daher keineswegs vorhersehbar, dass sich aus der Vielzahl der unterschiedlichen Alkaliphosphatierverfahren, insbesondere hinsichtlich der eingesetzten Beschleuniger, gerade das im erfindungsgemässen Verfahren zum Einsatz kommende Alkaliphosphatverfahren in besonderer Weise für die Vorbereitung von Eisen- oder Stahloberflächen für die anschliessende Aufbringung von high-solids-Lacken eignen würde.GB-PS 715 607 describes a process for applying phosphate layers by means of solutions which contain alkali, inorganic or organic ammonium phosphate and which can be accelerated with meta-nitrobenzenesulfonate, among other things, and the suitability of these phosphate layers as the basis for paints, Lacquers and the like mentioned. From today's point of view, however, these were conventional paint or lacquer systems with comparatively low solids contents, the flow properties of which are completely different compared to those of high-solids lacquers. It was therefore by no means foreseeable that from the multitude of different alkali phosphating processes, particularly with regard to the accelerators used, it is precisely the alkali phosphate process used in the process according to the invention that is particularly suitable for the preparation of iron or steel surfaces for the subsequent application of high-solids Paints would be suitable.
Bevorzugte Ausgestaltungen der Erfindung sehen vor, die Eisen- oder Stahloberfläche mit einer Phosphatierungslösung in Berührung zu bringen, die einen pH-Wert von 4,5 bis 5,5 aufweist bzw. die Dihydrogenphosphat in einer Menge von 4 bis 10 g/I bzw. die meta-Nitrobenzolsulfonat in einer Menge von 0,1 bis 1,5 g/1 enthält.Preferred embodiments of the invention provide for the iron or steel surface to be brought into contact with a phosphating solution which has a pH of 4.5 to 5.5 or the dihydrogen phosphate in an amount of 4 to 10 g / l or which contains meta-nitrobenzenesulfonate in an amount of 0.1 to 1.5 g / 1.
Die Phosphatierungslösungen können mit einer Temperatur eingesetzt werden, die üblicherweise über 21 °C liegt und Werte erreichen kann, bei denen eine Zersetzung des meta-Nitrobenzolsulfonats beginnt. Normalerweise liegt jedoch die obere Grenze der Temperatur der Phosphatierungslösung bei ca. 49°C.The phosphating solutions can be used at a temperature which is usually above 21 ° C. and can reach values at which decomposition of the meta-nitrobenzenesulfonate begins. However, the upper limit of the temperature of the phosphating solution is normally around 49 ° C.
Die Applikation der Phosphatierungslösung kann auf übliche Weise, z.B. durch Spritzen, Tauchen oder Fluten, erfolgen. Je nach Form der Applikation und erwünschter Beschaffenheit der Phosphatschicht, z.B. hinsichtlich Schichtdicke, kann die Behandlungsdauer 5 Sekunden bis einige Minuten betragen. Das Schichtgewicht der erzeugten Phosphatschicht liegt im allgemeinen zwischen 0,1 und 1,0 g/m2. Je nach Behandlungsbedingungen können auch höhere Schichtgewichte erreicht werden. Sofern eine gesonderte pH-Wert-Einstellung erforderlich ist, erfolgt sie im allgemeinen mit Phosphorsäure.The phosphating solution can be applied in the customary manner, for example by spraying, dipping or flooding. Depending on the form of the application and The desired duration of the phosphate layer, for example with regard to layer thickness, can be from 5 seconds to a few minutes. The layer weight of the phosphate layer produced is generally between 0.1 and 1.0 g / m 2 . Depending on the treatment conditions, higher layer weights can also be achieved. If a separate pH adjustment is required, it is generally done with phosphoric acid.
Die im erfindungsgemässen Verfahren einzusetzende Phosphatierungslösung kann Tenside oder Emulgiermittel unterschiedlichster Art, z.B. die auch bei der Metallreinigung Verwendung finden, enthalten. Sie müssen selbstverständlich mit der Phosphatierungslösung und dem organischen Beschleuniger verträglich sein, damit auch bei der Phosphatierung ihre gleichzeitig reinigende Funktion erhalten bleibt.The phosphating solution to be used in the process according to the invention can contain various types of surfactants or emulsifiers, e.g. which are also used in metal cleaning. Of course, they must be compatible with the phosphating solution and the organic accelerator so that their phosphating function is retained at the same time.
Vor und nach der Stufe der Phosphatierung können die üblichen Behandlungsmassnahmen ergriffen werden. So werden die Metalloberflächen üblicherweise zuvor mit einer Reinigungsbehandlung zur Entfernung von Fett und Schmutz, z. B. mit Hilfe eines alkalischen Reinigers, unterworfen. Sofern nötig, kann sich eine Beizbehandlung zur Entfernung von Rost anschliessen. Zwischen Reinigen, gegebenenfalls Beizen, und Phosphatieren wird in der Regel gründlich mit Wasser gespült.The usual treatment measures can be taken before and after the phosphating step. So the metal surfaces are usually previously with a cleaning treatment to remove grease and dirt, e.g. B. with the help of an alkaline cleaner. If necessary, pickling treatment to remove rust can follow. Between cleaning, possibly pickling, and phosphating, it is generally rinsed thoroughly with water.
Nach der Phosphatierung findet im allgemeinen eine Wasserspülung und eine Nachbehandlung mit beliebigen Nachspülmitteln, wie Chrom(VI)/Chrom(III)-Lösungen statt. Nach einer gegebenenfalls erneuten Wasserspülung wird die Metalloberfläche schliesslich getrocknet.After phosphating, there is generally a water rinse and an aftertreatment with any rinse aid, such as chromium (VI) / chromium (III) solutions. After possibly rinsing the water again, the metal surface is finally dried.
Als abschliessende Behandlung erfolgt die Aufbringung des high-solids-Lackes, an die sich gegebenenfalls die Aufbringung eines weiteren Lackaufbaues anschliesst. Nach der Lackierung oder den einzelnen Lackierstufen wird üblicherweise eingebrannt.The final treatment is the application of the high-solids lacquer, which may be followed by the application of a further lacquer structure. After painting or the individual painting steps, it is usually baked.
High-solids-Lacke, feststoffreiche bzw. lösungsmittelarme Lacke weisen üblicherweise Feststoffgehalte von 50 bis 60 Gew.-% und mehr auf und gewinnen wegen der verringerten Lösungsmittelemission aus Gründen des Umweltschutzes zunehmend an Bedeutung. Ihre z.B. zur Spritzanwendung geeignete Viskosität erhalten sie durch Polymere, die - gegenüber konventionellen Lacken - niedrigere Molekulargewichte aufweisen. Zur Technologie der Beschichtung mit feststoffreichen Lacken wird verwiesen auf: R.N. Price, «High-Solids Coatings: Past, Present, Future», American Paint and Coatings Journal, June 21, 1982; J.C. Dean, «High-Solids Coatings», Modern Paint and Coatings, March 1982; D.E. Brody, «Trends in Water-Borne, High-Solids Coatings», American Paint and Coatings Journal, July 12, 1982, and R.R. Kuhn et al., «High-Solids Acrylic Resins for Baking Enamels», Modern Paint and Coatings, April 1981. Die besonderen Vorzüge des erfindungsgemässen Verfahrens liegen darin, dass Spritzer oder Tropfen der Phosphatierungslösung auf bereits getrockneten und phosphatierten Metalloberflächen keine Probleme, z.B. in Form einer Verfärbung der Lackschicht, verursachen.High-solids paints, high-solids or low-solvent paints usually have solids contents of 50 to 60% by weight and more and are becoming increasingly important due to the reduced solvent emission for reasons of environmental protection. Your e.g. Viscosity suitable for spray application is obtained from polymers that - compared to conventional paints - have lower molecular weights. For the technology of coating with high-solids paints, reference is made to: R.N. Price, "High-Solids Coatings: Past, Present, Future," American Paint and Coatings Journal, June 21, 1982; J.C. Dean, High-Solids Coatings, Modern Paint and Coatings, March 1982; D.E. Brody, "Trends in Water-Borne, High-Solids Coatings", American Paint and Coatings Journal, July 12, 1982, and R.R. Kuhn et al., "High-Solids Acrylic Resins for Baking Enamels", Modern Paint and Coatings, April 1981. The particular advantages of the process according to the invention are that splashes or drops of the phosphating solution on metal surfaces that have already been dried and phosphated are no problem, e.g. in the form of discoloration of the paint layer.
Die Erfindung wird anhand der nachfolgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples, for example and in more detail.
Zwei gereinigte Stahlbleche wurden mit einer Phosphatierungslösung, die aus
- 9,5 g/I NaH2P04 und
- 5,2 g/i NaCl03
angesetzt worden war und einen pH-Wert von ca. 5 aufwies, bei einer Temperatur von 71 °C eine Minute lang im Spritzverfahren behandelt. Diese Bleche wurden anschliessend wassergespült und mit Luft trockengeblasen.Two cleaned steel sheets were covered with a phosphating solution
- 9.5 g / l NaH 2 P0 4 and
- 5.2 g / i NaCl0 3
was prepared and had a pH of about 5, treated at a temperature of 71 ° C for one minute by spraying. These sheets were then rinsed with water and blown dry with air.
Um die in der Produktion üblicherweise herrschenden Betriebsbedingungen zu simulieren, wurde ein Tropfen der vorgenannten Phosphatierungslösung auf die Bleche aufgebracht und die Bleche in horizontaler Lage 10 Minuten durch Umluft von 49°C getrocknet.In order to simulate the normal operating conditions in production, a drop of the aforementioned phosphating solution was applied to the sheets and the sheets were dried in a horizontal position for 10 minutes by circulating air at 49 ° C.
Anschliessend wurde auf das erste Blech ein lösungsmittelverdünnter Einschicht-high-solids-Lack (der Firma PPG Inc., mit der Bezeichnung Duracron 200) und auf das zweite Blech ein Einschicht-high-solids-Schwarzlack (der Firma Sherwin-Williams, mit der Bezeichnung 4653), jeweils im Spritzen, aufgebracht. Beide Lackfilme wurden mit Umluft von 163°C während 15 Minuten eingebrannt.A solvent-thinned single-layer high-solids paint (from PPG Inc., with the designation Duracron 200) was then applied to the first sheet and a single-layer high-solids black paint (from Sherwin-Williams, with the Designation 4653), each applied by spraying. Both paint films were burned in with circulating air at 163 ° C for 15 minutes.
In beiden Fällen war an der Auftropfstelle der Phosphatierungslösung ein durch den Lack scheinender weisser Ring sichtbar. Im Inneren des Ringes war der Lack matt.In both cases, a white ring shining through the paint was visible at the spot where the phosphating solution was applied. The inside of the ring was matt.
Es wurde die gleiche Arbeitsweise, wie in Beispiel 1 angegeben, wiederholt, jedoch eine Phosphatierungslösung eingesetzt, die aus
- 9,5 g/1 NaH2P04 und
- 1,3 g/l Natrium-meta-Nitrobenzolsulfonat
angesetzt worden war.The same procedure as given in Example 1 was repeated, but a phosphating solution was used, which consists of
- 9.5 g / 1 NaH 2 P0 4 and
- 1.3 g / l sodium meta-nitrobenzenesulfonate
had been scheduled.
Es wurden Bleche erhalten, die weder einen feststellbaren Ring noch eine irgendwie geartete Verfärbung des Lackes aufwiesen.Sheets were obtained which showed neither a detectable ring nor any kind of discoloration of the paint.
Ebenfalls nach der Arbeitsweise von Beispiel 1 und Beispiel 2 wurde mit einer Phosphatierungslösung gearbeitet, die neben den Bestandteilen der Phosphatierungslösung des Beispiels 2 zusätzlich
- 0,7 g/I Tensid
enthielt. Auch in diesem Fall waren weder Ringe noch Verfärbungen im Lack erkennbar.In the same way as in Example 1 and Example 2, a phosphating solution was used which, in addition to the constituents of the phosphating solution in Example 2, additionally
- 0.7 g / l surfactant
contained. In this case, too, there were no rings or discolourations in the paint.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84102646T ATE24206T1 (en) | 1983-03-15 | 1984-03-10 | PREPARING IRON OR STEEL SURFACES FOR PAINTING. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47328283A | 1983-03-15 | 1983-03-15 | |
| US473282 | 1983-03-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0121155A1 EP0121155A1 (en) | 1984-10-10 |
| EP0121155B1 true EP0121155B1 (en) | 1986-12-10 |
Family
ID=23878915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84102646A Expired EP0121155B1 (en) | 1983-03-15 | 1984-03-10 | Preparation of iron or steel surfaces for painting |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0121155B1 (en) |
| JP (1) | JPS59177378A (en) |
| AT (1) | ATE24206T1 (en) |
| DE (2) | DE3461653D1 (en) |
| GB (1) | GB2136455B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2609724B1 (en) * | 1987-01-21 | 1989-05-12 | Parker Ste Continentale | PROCESS FOR FORMING CONVERSION LAYERS ON STEEL AND TIN SURFACES USING PHOSPHATATION SOLUTION |
| US20040118483A1 (en) * | 2002-12-24 | 2004-06-24 | Michael Deemer | Process and solution for providing a thin corrosion inhibiting coating on a metallic surface |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB715607A (en) * | 1948-07-23 | 1954-09-15 | Pyrene Co Ltd | Improvements in or relating to the coating of ferrous surfaces |
| FR1258855A (en) * | 1960-02-18 | 1961-04-21 | Parker Ste Continentale | Advanced process for phosphating metal surfaces |
| FR2248330B1 (en) * | 1973-10-22 | 1979-03-23 | Brugarolas Sa | |
| US4008101A (en) * | 1975-03-20 | 1977-02-15 | Diamond Shamrock Corporation | Methylene chloride phosphatizing |
| SE441105B (en) * | 1976-04-05 | 1985-09-09 | Amchem Prod | PROCEDURE FOR PREPARING AN AMORPH, LIGHT, HARD FIXED PHOSPHATE COATING |
| DE2632742C3 (en) * | 1976-07-21 | 1980-05-08 | Hoechst Ag, 6000 Frankfurt | Process for phosphating metals and means for producing a phosphating solution |
| JPS53138937A (en) * | 1977-05-11 | 1978-12-04 | Nippon Paint Co Ltd | Chemical treating method for iron phosphate film |
| DE2738281A1 (en) * | 1977-08-25 | 1979-03-01 | Metallgesellschaft Ag | METHOD FOR PHOSPHATING METALS |
| GB2072225B (en) * | 1980-03-21 | 1983-11-02 | Pyrene Chemical Services Ltd | Process and composition for coating metal surfaces |
-
1984
- 1984-03-10 AT AT84102646T patent/ATE24206T1/en not_active IP Right Cessation
- 1984-03-10 EP EP84102646A patent/EP0121155B1/en not_active Expired
- 1984-03-10 DE DE8484102646T patent/DE3461653D1/en not_active Expired
- 1984-03-10 DE DE19843408787 patent/DE3408787A1/en not_active Withdrawn
- 1984-03-12 JP JP59046978A patent/JPS59177378A/en active Pending
- 1984-03-15 GB GB08406784A patent/GB2136455B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATE24206T1 (en) | 1986-12-15 |
| JPS59177378A (en) | 1984-10-08 |
| GB2136455A (en) | 1984-09-19 |
| EP0121155A1 (en) | 1984-10-10 |
| DE3408787A1 (en) | 1984-09-20 |
| DE3461653D1 (en) | 1987-01-22 |
| GB2136455B (en) | 1986-06-18 |
| GB8406784D0 (en) | 1984-04-18 |
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