EP0572941B1 - Vorrichtung und Verfahren zum elektrophoretischen Lackieren von Metallstrukturen, insbesondere von gewickelten Metallblechen - Google Patents

Vorrichtung und Verfahren zum elektrophoretischen Lackieren von Metallstrukturen, insbesondere von gewickelten Metallblechen Download PDF

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Publication number
EP0572941B1
EP0572941B1 EP93108657A EP93108657A EP0572941B1 EP 0572941 B1 EP0572941 B1 EP 0572941B1 EP 93108657 A EP93108657 A EP 93108657A EP 93108657 A EP93108657 A EP 93108657A EP 0572941 B1 EP0572941 B1 EP 0572941B1
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Prior art keywords
counter
electrodes
metal
electrode
parts
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EP93108657A
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English (en)
French (fr)
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EP0572941A1 (de
Inventor
Achille Bardelli
Osvaldo Colombo
Ezio Pedroni
Luca Cioni
Ferruccio Stazzi
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SALCHI SpA
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SALCHI SpA
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/16—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes

Definitions

  • the present invention concerns a new apparatus and a new process for the electrophoretic anti-corrosion coating of metal sheet coils.
  • the protective coat makes it possible to stamp the metal sheets without using lubricating oils, to electrically weld them, and it can, because of its composition, be removed by means of alcaline degreasing agents.
  • the optimum thickness of the paint coat was found to be 3 ⁇ m, plus or minus 0.5 ⁇ m.
  • the possibility of welding the sheets depends on the thickness of the protective coat, which, acting as an insulation, presents to the passage of an electric current a resistance which is directly proportional to the thickness of the protective coat.
  • a thickness higher than 3.5 ⁇ m requires voltages unacceptable for point welding, producing large amounts of fumes and carbon residues which reduce to a considerable extent the life of counter-electrodes.
  • the thickness of the protective paint film on at least one face of the coil is not constant throughout; this is the cause of the problems which arise in the welding and stamping, as said.
  • the deposition of protective films of the special paint having a rigorously constant thickness (optimum value: 3 ⁇ m), with very limited departures ( ⁇ 0.5 ⁇ m) from the nominal value, may be obtained.
  • the basic component of an electrophoretic paint is the binder, in practice a polymer or a resin.
  • the resin may be of various types (alkyd, epoxy, acrylic, polybutadiene, polyester, etc.) depending on the mechanical, physical and chemical characteristics to be obtained. For instance, an acrylic resin shows a good light resistance, while an epoxy resin resists to corrosion. As said, in the case of coils epoxy resins are commonly employed to protect them from corrosion.
  • the resin In paints for anaphoresis, the resin will be of RCOOH type, while in cathaphoresis it will be of R3N type, R being a radical which may contain alkyd, epoxy, acryl, etc., groups.
  • paint ingredients are reticulating agents, pigments, solvents and additives, which are added to the resin prior to its solubilization in water.
  • Reticulants normally consist of ammine resins or blocked isocyanates and are added in order to polymerize the paint ingredients.
  • Pigments are added to impart colour and covering power to the paint or to improve in general its characteristics.
  • Solvents give stability to the system and improve all the film characteristics. Additives improve and exalt all the film characteristics.
  • the protective paint may consist, as a non limiting example, of an acrylic thermoplastic carboxylated resin made water soluble by salification with bases such as ammonium hydroxide and/or amines, and of a dispersion of a wax having particular characteristics of hardness, melting point and average particle dimensions.
  • the paint maintains, after the application and drying (at 180°C), a thermoplastic structure such as to be easily removed by an alkaline wash.
  • the dried paint film has a friction coefficient of between 0.04 and 0.08 which allows the forming of the sheet without breakage of the film, and a lowering of the "stickiness" of the cut and stacked sheets.
  • the protective film obtained with a paint of this type has a low resistance to arc discharge in a thickness interval comprised between 2.5 and 3.5 ⁇ m. Such thicknesses allow in fact a point welding with discharges of 6 V at 10,000 A, with a negligible formation of fumes and carbon depositions.
  • Our polymer is obtained by the copolymerisation of 4 monomers, has an average molecular weight (Mw) between 5,000 and 50,000, in particular between 8,000 and 15,000 and a mEq. value in the dry state of between 30 and 100, in particular between 50 and 60.
  • Mw average molecular weight
  • a paint thus obtained may be employed in traditional ways (dip-coating, flow-coating, coil-coating, spraying): however, the best results are obtained by the electrophoretic process according to the invention.
  • An acrylic polymer which may be used in the preparation of a protective paint is produced as follows.
  • Butylglycol, 165.2 parts and isopropyl alcohol, 10.11 parts (all parts by wt.) are charged in a reaction vessel equipped with stirrer, temperature control means, container for the addition of monomers, condenser and with a means apt to maintain the reagents in a nitrogen atmosphere.
  • the reaction vessel is equipped for direct recycling of the solvent.
  • the vessel is then heated, under stirring, in the nitrogen atmosphere, to 140°C.
  • a mixture of monomers A is prepared in the meantime, having the following composition by wt.: Ethyl acrylate 108.49 Butyl acrylate 95.92 Methyl methacrylate 114.64 Styrene 69.90 Methacrylic acid 76.81 Tertiary Dodecylmercaptane 0.93
  • the number of acidity is brought to 110-111 by adding methacrylic acid.
  • a paint for the temporary protection of metal coils utilizing the preceding resin is prepared as follows: to 730g of resin solution prepared as described, 50g of a polymeric wax dispersing with 18% active substance, melting point 93-99°C and average particle diameter 2-5 ⁇ m are added, stirring rapidly for 10'.
  • the newly conceived counter-electrode which is employed in the electrophoresis apparatus and relative process which are objects of the present invention consists in its preferred but not limitative embodiment, of a rectangular metal plate, generally of stainless AISI 316 steel, in which holes are punched.
  • cylinders may be used as counter-electrodes, obtained by rolling on themselves metal bands on which the holes and the points associated with them are located.
  • each hole at least one point is associated, protruding in the direction of the coil to be painted.
  • a thickening of the electric charges takes place which flow toward the point; the tension difference between the points on the counter-electrode and the coil thus provides a perfectly homogeneous electric field. This provides for a perfect paint deposition on the coil.
  • the points may also be more than one for each hole: a very advantageous embodiment of the invention provides points formed while punching the holes: by making cross-cuts in the locations where the holes are wished, four triangular sectors are obtained which are pushed outside to form the points.
  • a same inventive conception includes all electrodes providing for any plurality of points, with or without adjacent holes, which protrude from the main electrode surface thus creating a uniform electric field.
  • the present invention concers an apparatus and a related process for the electrophoretic painting of metal structure, in particular of metal sheet coils.
  • It consists of at least one electrode on which the structure is electrically charged, at least one tank containing the paint, at least two counter-electrodes having a polarity opposite to the one of the electrode dipped into the paint bath, at least one over-flow tank in which the metal structure is washed, at least one oven for the polymerization and at least one cooling system.
  • the apparatus and process are characterized in that said at least two counter electrodes consist of at least two metal elements situated on opposite sides with respect to the metal structure and that on each of the elements there is at least a series of holes associated with a series of metal points directed toward the metal structure in order to obtain on it a uniform electric field.
  • Fig. 1 shows, in a cross-section, the plant for the electrophoretic painting which is an object of the present invention.
  • anodic electrophoresis is considered; however, similar statements may be made in connection with cathodic electrophoresis.
  • Figs. 3 and 4 show one of the at least two counter-electrodes contained in Fig. 1.
  • FIGs. 1 and 2 as an illustrative, non limitative example, a plant for anaphoretic electrodeposition is shown.
  • 1 indicates the tank where the paint electrodeposition on the coil is carried out: it is normally made out of PVC coated steel.
  • tank 1 Next to tank 1 is an overflow tank 5 with circulation pumps 17 and an ultrafiltration station 6.
  • roller 4 To roller 4 a hole is connected, which in the case of anaphoresis (as in the figure) is positively charged (anode) and positively charges coil 19.
  • the electrically insulated roller 2 guides the coil 19 into the tank 1: the roller idles on the shaft and is cooled inside.
  • Counter-electrodes 3,20 which, in the case represented by the figure, are negatively charged (cathodes) dip into tank 1; in a preferred, non limitative, embodiment each of them consists of a plate 21 (Figs. 3 and 4), generally of AISI 316 stainless steel, on which holes 22 are bored; to each of the holes at least one point 23 corresponds which protrudes toward coil 19 to be painted.
  • Around holes 22 electric charges concentrate flowing toward points 23; in this way, a perfectly homogeneous electric field is created between negative counter-electrode 3,20 and coil 19.
  • the coil up to 2,000 mm wide, runs at the rate of 70 m/minute. This rather high speed requires a high "penetration" of the counter-electrodes in order that the coil be covered in a few seconds with a constant thickness (3 ⁇ 0.5 ⁇ m) of protective paint.
  • the washing operation is very important; in fact, the coil 19, covered by perfectly compact and adhering paint layer, drags out of the tank physically adherent, non-electrodeposited portions of the bath which must be removed.
  • the washing is made first with tap water, followed by rinsing with demineralized water or by ultrafiltration. Normally, ultrafiltration is employed which requires less water and allows to recover a considerable amount of paint, which otherwise would be lost.
  • a permeable membrane on a support is employed, through which the electrophoresis bath is passed, at a rate of 2-3 m/sec. under a 2 to 4 bar pressure, tangentially to one side of the membrane; the heavier paint particles adhere to the membrane, while water, neutralizing agents, soluble salts, solvents and fractions of resin go through and are returned to the rinsing nozzles 14.
  • Tubular or plate ultrafilters may also be employed.
  • the plant further comprises dialysis cells 11 for controlling the neutralizing agent contents in the bath; the cells 11 consist of a semipermeable membrane placed in front of the counter-electrodes forming a cell; only the neutralizer ions go through, while colloidal resin particles present in the bath are stopped.
  • the neutralizer ions go by dialysis through the membrane and are then removed by a controlled flow of demineralized water which starts as the cell conductivity reaches a predetermined value.
  • the coil goes through a polymerisation furnace where in 5 sec. a temperature of 180°C is reached.
  • An infrared furnace is suitable for this purpose.
  • the plant is completed by a group 8 for the continuous refilling of the paint, a group 9 of paint tanks, a current rectifier group 12 and electric service and regulation boards 13.
  • the cathodic surface in the tank was reduced by 45%, thus obtaining a thickness increase from 3-8 ⁇ m to 15-22 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (21)

  1. Vorrichtung zur elektrophoretischen Lackierung von Metallstrukturen (19), insbesondere zur elektrophoretischen Lackierung von Metallblechrollen, mit mindestens einer Elektrode (4), an der die Struktur (19) elektrisch geladen wird, mindestens einem Tank (1), der ein Lackbad (18) enthält, mindestens zwei Gegenelektroden (3, 20), die in das Bad (18) eingetaucht sind und eine Polarität aufweisen, die derjenigen der mindestens einen Elektrode (4) entgegengesetzt ist, einem Überströmtank (5), in dem die Struktur (19) einer Wäsche unterzogen wird, einem Polymerisationsofen (15) und schließlich einer Kühleinrichtung (16), wobei die Vorrichtung dadurch gekennzeichnet ist, daß die mindestens zwei Gegenelektroden (3, 20) aus mindestens zwei Metallelementen (21) bestehen, die in bezug auf die Metallstruktur (19) auf entgegengesetzen Seiten angeordnet sind, und daß sich auf jedem der Elemente (21) mindestens eine erste Reihe von Löchern (22) befindet, die mindestens einer zweiten Reihe von Metallpunkten (23) zugeordnet ist, die zu der Struktur (19) hin gerichtet sind, um darauf ein gleichförmiges elektrisches Feld zu schaffen.
  2. Vorrichtung nach Anspruch 1,
    dadurch gekennzeichnet, daß
    die mindestens eine Elektrode (4) positiv geladen ist und daß die mindestens zwei Gegenelektroden (3, 20) negativ geladen sind.
  3. Vorrichtung nach Anspruch 1,
    dadurch gekennzeichnet, daß
    die mindestens eine Elektrode (4) negativ geladen ist und daß die mindestens zwei Gegenelektroden (3, 20) positiv geladen sind.
  4. Vorrichtung nach einem der Ansprüche 1 bis 3,
    dadurch gekennzeichnet, daß
    die Elemente (21) Platten sind.
  5. Vorrichtung nach einem der Ansprüche 1 bis 3,
    dadurch gekennzeichnet, daß
    die Elemente (21) Zylinder sind.
  6. Vorrichtung nach einem der Ansprüche 1 bis 5,
    dadurch gekennzeichnet, daß
    die Löcher (22) und die Punkte (23) durch Stanzen der Platten (21) erhalten werden.
  7. Vorrichtung nach Anspruch 1,
    dadurch gekennzeichnet, daß
    sie eine Einrichtung (2) umfaßt, die eingerichtet ist, um die Struktur (19) in das Bad (18) einzutauchen.
  8. Vorrichtung nach Anspruch 7,
    dadurch gekennzeichnet, daß
    die Einrichtung (2) zwischen der ersten Einrichtung (4) und der zweiten Einrichtung (3) angeordnet ist und aus einer beweglichen Walze besteht, die elektrisch isoliert und im Inneren gekühlt ist.
  9. Vorrichtung nach einem der Ansprüche 1 bis 8,
    dadurch gekennzeichnet, daß
    die Struktur (19) sich mit einer Geschwindigkeit von 70 m/min. vorwärtsbewegt.
  10. Vorrichtung nach einem der Ansprüche 1 bis 9,
    dadurch gekennzeichnet, daß
    der Polymerisationsofen (15) die Struktur in 5 sec. auf 180 °C aufheizt.
  11. Verfahren zur elektrophoretischen Lackierung von Metallstrukturen, insbesondere von Metallblechrollen,
    wobei die Struktur zuerst auf mindestens eine Elektrode geführt wird, an der sie elektrisch geladen wird, und gleich danach zwischen mindestens zwei Gegenelektroden hindurchgeführt wird, die in das Lackbad eingetaucht sind und eine Polarität aufweisen, die derjenigen der mindestens einen Elektrode entgegengesetzt ist; wobei die Struktur in einen Überströmtank geführt wird, wo sie einer Wäsche unterzogen wird; wobei die Struktur durch einen Polymeristionsofen hindurchläuft und schließlich durch eine Kühleinrichtung, wobei das Verfahren dadurch gekennzeichnet ist, daß die mindestens zwei Gegenelektroden aus mindestens zwei Metallelementen bestehen, die auf entgegengesetzten Seiten der Struktur angeordnet sind, und daß sich auf jedem der Elemente mindestens eine erste Reihe von Löchern befindet, denen mindestens eine Reihe von Metallpunkten zugeordnet ist, die zur Struktur hin gerichtet sind, um an dieser ein gleichförmiges elektrisches Feld zu realisieren.
  12. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    es ein Verfahren für anaphoretische Lackierung ist.
  13. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    es ein Verfahren für kathaphoretische Lackierung ist.
  14. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    die Elemente aus Platten bestehen.
  15. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    die Elemente aus Zylindern bestehen.
  16. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    es ein Lackbad verwendet, das folgendermaßen hergestellt wird:
    In einem Reaktionsgefäß, das mit einem Rührer, einer Temperatursteuereinrichtung, einem Behälter für die hinzuzufügenden Monomere, einem Rückflußkühler und einer Einrichtung zur Haltung der Reagenzien in einer Stickstoffatmosphäre ausgestattet ist, werden 165,2 Gewichtsteile Butylglycol und 10,11 Gewichtsteile Isopropylalkohol eingefüllt, wobei das Gefäß für eine direkte Rückführung des Lösungsmittels eingerichtet ist; das Gefäß wird im Rückstrom auf 140 °C erhitzt, unter Rühren und in einer Stickstoffatmosphäre; in der Zwischenzeit wird eine Mischung von Monomeren A folgendermaßen vorbereitet (Gewichtsteile) : Ethylacrylat 108,49 Butylacrylat 95,92 Methylmathacrylat 114,64 Styrol 69,90 Methacrylsäure 76,81 Tertiäres Dodecylmercaptan 0,93;
    die Säurezahl wird gesteuert und durch Hinzufügen von Metacrylsäure auf 110-111 eingestellt; in einem anderen Behälter wird eine Mischung B vorbereitet, die aus folgendem besteht: Butylglycol 65,21 nach Gewicht tertiäres Butylperbenzoat 6,47;
    dann werden 46 Gewichtsteile der Mischung A in das Reaktionsgefäß eingeführt und die Temperatur wird auf 135 °C gebracht; dann wird der Rest der Mischung A zugefügt, immer mit direkter Umwälzung, und zwar unter Hinzufügung von 55 Gewichtsteilen der Mischung B; dieser Vorgang sollte in 6 Stunden vollendet werden; dann wird der Rest der Mischung B in einer Stunde Zeit hinzugefügt, wobei die Temperatur auf 135 °C gehalten wird; diese Temperatur wird für eine weitere Stunde bei 135 °C - 137 °C gehalten; dann werden unter Vakuum ungefähr 75 Gewichtsteile des Lösungsmittels ausdestilliert; nach einer Kühlung auf 95 - 100 °C werden 270,13 Gewichtsteile Butylglycol hinzugefügt, und bei 50 °C werden dann 16 - 18 Gewichtsteile von 28 Bé Ammoniak weiter zur Mischung hinzugefügt; diese Temperatur wird unter Rühren für 3 Stunden aufrechterhalten, und dann werden die vorgeschriebenen Daten kontrolliert, die folgendermaßen sein sollten: Trockener Rückstand: 50 ± 1 (30' bis 180 °C) mEq.: 58 - 60 auf die Feststoffe Viskosität: 300 - 500 mPa·s (Brookfield) Na.: 95 - 110 auf den Feststoff MPW nach Gewicht: ca. 10.000;
    auf 730 g der so zubereiteten Harzlösung werden 50 g einer Dispersion von Polymerwachs mit 18 % Wirkstoff mit einem Schmelzpunkt von 93 - 99 °C und einem durchschnittlichen Teilchendurchmesser von 2 - 5 µm zugesetzt, wobei für 10 min. schnell umgerührt wird; unter Rühren werden 100 g Butylglycol und 100 g entmineralisiertes Wasser zugefügt, dann unter geringem Mischen Di-Isopropylamin bis auf einen pH-Wert von 8.
  17. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    die Metallstruktur mit der Rate von 70 m/min. durch das Lackbad läuft.
  18. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    der Polymerisationsofen die Metallstruktur innerhalb 5 sec. auf 180 °C erhitzt.
  19. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    zwischen der mindestens einen Elektrode und den mindestens zwei Gegenelektroden eine Spannung von 150 V aufgebracht wird.
  20. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    zwischen der mindestens einen Elektrode und den mindestens zwei Gegenelektroden eine Spannung von 400 V aufgebracht wird.
  21. Verfahren nach Anspruch 11,
    dadurch gekennzeichnet, daß
    der elektroaufgebrachte Lackfilm eine Dicke von 3 ± 0,5 µm aufweist.
EP93108657A 1992-06-02 1993-05-28 Vorrichtung und Verfahren zum elektrophoretischen Lackieren von Metallstrukturen, insbesondere von gewickelten Metallblechen Expired - Lifetime EP0572941B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI921359A IT1260515B (it) 1992-06-02 1992-06-02 Apparecchiatura e processo relativo per la verniciatura elettroforetica di manufatti metallici in particolare per coil di lamiera metallica
ITMI921359 1992-06-02

Publications (2)

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EP0572941A1 EP0572941A1 (de) 1993-12-08
EP0572941B1 true EP0572941B1 (de) 1996-02-07

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EP (1) EP0572941B1 (de)
AT (1) ATE134001T1 (de)
DE (1) DE69301501T2 (de)
IT (1) IT1260515B (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE29612278U1 (de) * 1996-07-15 1996-10-10 Kever, Helmut, 86316 Friedberg Anodenzelle mit kreissegmentartigem Anodenquerschnitt für elektrophoretische Metallbeschichtungsbäder
CN108624938A (zh) * 2017-03-17 2018-10-09 天津金鹏铝材制造有限公司 一种电泳涂漆型材的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE505824C (de) * 1925-11-20 1930-08-28 Anode Rubber Co Ltd Verfahren zur Herstellung eines dichten gleichmaessigen Kautschukueberzeuges auf Metallen durch Elektrophorese
FR675754A (fr) * 1929-05-24 1930-02-14 Perfectionnements aux anodes pour chromage électrolytique et galvanoplastie générale
DE1989353U (de) * 1968-03-26 1968-07-11 Solvay Werke Gmbh VORRICHTUNG zUR ELEKTROPHORETISCHEN BESCHICHTUNG.
US3962060A (en) * 1974-10-23 1976-06-08 Aluminum Company Of America Continuous electrodeposition of coating material on metal sheet stock

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Publication number Publication date
DE69301501T2 (de) 1996-06-20
ITMI921359A0 (it) 1992-06-02
IT1260515B (it) 1996-04-09
ATE134001T1 (de) 1996-02-15
ITMI921359A1 (it) 1993-12-02
EP0572941A1 (de) 1993-12-08
DE69301501D1 (de) 1996-03-21

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