EP1060032B1 - Beschichtung von metallbändern - Google Patents

Beschichtung von metallbändern Download PDF

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Publication number
EP1060032B1
EP1060032B1 EP99937821A EP99937821A EP1060032B1 EP 1060032 B1 EP1060032 B1 EP 1060032B1 EP 99937821 A EP99937821 A EP 99937821A EP 99937821 A EP99937821 A EP 99937821A EP 1060032 B1 EP1060032 B1 EP 1060032B1
Authority
EP
European Patent Office
Prior art keywords
strip
process according
chemical
thermoplastic resin
chemically
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 - Lifetime
Application number
EP99937821A
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English (en)
French (fr)
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EP1060032A2 (de
Inventor
Brian John Bastable
Malcolm Robert Mallace
Ieuan Stephen Rees
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corus UK Ltd
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Corus UK Ltd
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Publication of EP1060032A2 publication Critical patent/EP1060032A2/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102—Pretreatment of metallic substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies

Definitions

  • This invention relates to laminated mild steel strip for use especially, but not exclusively, in the packaging industry and to methods of manufacturing such strip. More especially, the invention relates to a method of chemically treating mild steel strip prior to lamination with a thermoplastic material.
  • Organic-coated metal substrates for example thermoplastic resin-coated tinplate or blackplate
  • thermoplastic resin-coated tinplate or blackplate are used, inter alia, in the production of packaging materials, for example, food and beverage cans.
  • organic coatings so used are required to conform with strict performance criteria.
  • the coating must exhibit good stain resistance, corrosion resistance and resistance to delamination.
  • GB-A-2329608A discloses a process for producing thermoplastic resin-coated aluminium alloy plate in which the plate is treated sequentially with alkali and acid solutions to put the plate surfaces in such a condition that the increase rate of the specific surface area is 3 to 30%. The treated plate is then subjected to an anodic oxidation treatment prior to lamination with thermoplastic resin.
  • Organic coatings have traditionally comprised solvent or water-based lacquers. Recently however, the use of laminated polymer films and coatings, such as thermoplastic resins, has been recognised as a viable alternative.
  • organic coatings are not applied directly onto mild steel (otherwise known as blackplate), because for packaging applications the metal surface is too reactive and underfilm corrosion can spread rapidly.
  • metallic -coated mild steels such as tinplate or electrolytically chromium-coated steel (ECCS) as substrates for organic coatings.
  • a surface-treated mild steel strip may comprise a chrome/CrO x or tin layer electrochemically deposited so that the final substrate has either a metallic chromium layer of typically from 50 to 150 mg/m 2 and a chromium oxide/hydroxide layer of typically from 10 to 30 mg/m 2 , or a layer of metallic tin of typically between 5 and 10 g/m 2 .
  • tinplate is additionally subjected to chromate solution treatment, the amount of oxidisable chromium being between 1 and 10 mg/m 2 .
  • electro-plating pre-treatment is a costly and time consuming process. Not only are materials expensive, but the electro-plating process itself consumes large quantities of energy. In addition, this conventional pre-treatment adds an additional production step in the process line, which adds costs in terms of line-time, manpower and through yield.
  • any such pre-treatment should be capable of application under the present day metal strip coating and lamination line conditions.
  • non-metallic coatings refers to coatings which despite optionally including metal ions, differ from what is conventionally described as a metallic layer in that there is no native metal. Unlike a metal layer wherein metal atoms, through metallic bonding, solely form a crystalline structure, in the non-metallic coatings of the present invention, both metallic and non-metallic ions are distributed within an amorphous network.
  • the strip may be cold-rolled mild steel strip. Mild steel strip is conventionally referred to as blackplate.
  • the strip has a gauge of between 0.08 and 0.50mm.
  • a preferred gauge is 0.18mm.
  • the strip is cleaned to remove all traces of contamination which may be present as a result of previous cold rolling and annealing processes.
  • the strip is cleaned electrolytically using a caustic-based solution, although the nature of the cleaner does not influence the subsequent chemical treatment.
  • the strip may be rinsed with water to remove all traces of the cleaning solution.
  • the chemical coating may be applied to the strip using a conventional application method such as immersion, spraying, roller coating, or a combination thereof.
  • the chemical coating is applied by immersing the cleaned strip in chemical contained in one or more treatment vessels.
  • the strip is chemically treated for less than 60 seconds; in other embodiments, the chemical treatment times are less than 30 seconds or less than 15 seconds.
  • the strip is chemically treated for less than 10 seconds; typically, 5 seconds.
  • the strip is chemically treated at a temperature of less than 100°C, most preferably at less than 30°C.
  • the strip is chemically treated to form a chemical coating which prevents subsequent underfilm corrosion of the strip and promotes adhesion between the strip and thermoplastic resin.
  • the chemical coating may be referred to as a coupling agent since it forms a strong and durable chemical bridge at the interface between the metal substrate and the final organic resin coating.
  • the chemical bridge has a dual role; it interacts with receptive inorganic surfaces to form tenacious chemical bonds at the interface with the metal substrate and at the interface with the organic resin coating.
  • the oxyanion coating may comprise a phosphate, a chromate, an oxalate or an arsenate. Additionally, the coating may comprise yttrium, elements in the lanthanum series of the periodic table, silanes or azoles.
  • the surface of the metal develops a naturally occurring surface oxide layer.
  • the oxide layer on blackplate at ambient temperature will have an average thickness of between 2 and 20 mm.
  • the chemical coating may be applied to the metal oxide layer on the surface of the metal substrate.
  • the chemical treatment may comprise, for example zinc orthophosphates, manganese phosphates or iron phosphates, thereby producing crystalline phosphate coatings on the strip.
  • the strip is chemically coated with a composition comprising less than 5% atomic chromium.
  • the strip may be rinsed and/or dried, for example with hot air, prior to treatment with organic resin.
  • thermoplastic resin may be applied to one or both sides of the chemically-treated strip.
  • the layer or layers of thermoplastic resin may be melted and rapidly quenched to attain the required degree of crystalline structure.
  • thermoplastic resin may be co-extruded with the chemically-treated strip to form laminated strip.
  • the film of thermoplastic resin may be bonded to chemically-treated strip under conditions of elevated temperature and pressure.
  • the chemically-treated strip may be coated with a thermoplastic resin together with a bonding layer.
  • the bonding layer may comprise a polyester, or an acid or acid-anhydride polyolefin resin containing carboxyl or anhydride groups. Typically, the bonding layer is between 1 and 10 ⁇ m thick.
  • the chemically-treated strip may be extrusion coated with at least one thermoplastic resin.
  • thermoplastic resins comprise polypropylene (PP), polyethyleneteraphthalate (PET) or a combination thereof.
  • the thickness of the layer, or layers, of thermoplastic resin are between 3 and 50 ⁇ m.
  • the chemical treatment has two functions; firstly it provides corrosion protection and inhibits underfilm corrosion, and secondly, it promotes good adhesion between the organic resin coating and the strip. These properties combined with the barrier properties of the organic coating provide a laminated metal strip product which can be formed into components for a range of applications whilst maintaining adequate performance criteria with regard to corrosion resistance and inter layer adhesion during the lifetime of the products.
  • the invention provides a laminated strip produced by a process which comprises the steps of chemically treating the strip to form on at least one of its surfaces a non-metallic coating, and applying to that coated surface a coating of a thermoplastic resin to form a layer thereon.
  • a process line for producing laminated blackplate comprises a plurality of guide rollers for transporting a strip of blackplate continuously from a coiled roll to an exit coil via a multiplicity of vertical tanks. These tanks include a cleaning tank, rinsing tanks and a chemical treatment tank. The line speed is typically 10 to 100 metres per minute with a treatment dwell time of between 1 to 10 seconds.
  • organic polymeric resin e.g. a thermoplastic resin such as PET at elevated temperature and pressure.
  • the laminated strip is then rapidly quenched to produce an essentially amorphous organic outer coating.
  • chemicals A and B were evaluated as potential alternatives to the conventional electroplating step in the production of an organically coated mild steel strip.
  • Chemical A comprised a commercially available chemical treatment comprising chromium, silicon and organic active species.
  • Chemical B comprised a commercially available chemical treatment comprising a two component organic polymer i.e. an acrylic polymer and (NH 3 )Cr 2 O 6 .
  • blackplate of 0.08 to 0.50mm thickness was subjected to an electrolytic cleaning process using a commercial cleaning solution at a temperature not exceeding 100°C, by passing a current of 20A for 5 seconds. This treatment is considered to return current densities to approximately 10 Adm -2 .
  • the nature of the cleaner employed on the blackplate does not influence any subsequent chemical treatment. It is important that the strip is clean and free of contamination from prior processing. Before dipping in the chemical treatment vessels, the samples were washed in two ambient water rinse tanks. The concentrations of the cleaner and chemical treatments were those recommended by the respective suppliers. A batch of samples exposed only to electrolytic cleaning were also prepared as a control sample group, identified in Figures 1 and 2 as B-plate.
  • an ECCS control sample group was also laminated. Samples of both 15 ⁇ m PET and/or 40 ⁇ m PP were laminated at elevated temperature and pressure. The hot samples were plunged into cold water just as the current was switched off. Instant quenching of this nature has the effect of retaining the amorphous nature of the thermoplastic coating at ambient temperature. Table 1 illustrates the concentrations, dip times and treatment section temperatures for evaluated chemicals A and B.
  • 8oz cans (73 x 63mm) were filled with either rabbit cat food or cut green beans in salt brine under standard filling conditions. The cans were stored on their sides at an elevated temperature (37°C). Cans with scored ends were stored with the score running vertically so that it entered the head space area. Four cans of each variable were opened after 2, 5, and 15 weeks. Opened cans were evaluated for sulphide staining, delamination and corrosion (on and off the score line).
  • the can end performance was judged on three main criteria (sulphide staining, delamination and corrosion (on and off the score line)) using a points system. Three points were awarded if the defect was obviously present and two points if the defect was only minor. No points were allocated if the defect was absent. All points were totalled for each category of defect over the three openings, for both polymer film types and for each chemical pre-treatment. The results are illustrated in Figure 1 and Figure 2.
  • the trials show that chemical pre-treatment in accordance with the invention provides an effective alternative to metallic electroplated coatings prior to coating of strip with organic resins.
  • blackplate can undergo chemical pre-treatment "off-line" with transfer to the lamination line post treatment.
  • this is less cost effective due to the necessity for a separate coating facility and any associated transportation or storage costs.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Claims (28)

  1. Verfahren zur Herstellung eines beschichteten Flußstahlbandes, wobei das Verfahren die folgenden Schritte umfaßt:
    (a) Reinigung des Bandes;
    (b) eine chemische Vorbehandlung des gereinigten Bandes, um auf einer seiner Oberflächen oder auf beiden Oberflächen einen nicht-metallischen chemischen Überzug aus einem Oxyanion zu bilden, um einer Korrosion des darunterliegenden Flußstahlsubstrats zu widerstehen und um eine Adhäsion auf einer vorher aufgetragenen Schicht zu verbessern; und
    (c) es wird auf dem chemisch behandelten Band ein Überzug aus einem thermoplastischen Kunstharz aufgetragen, um eine Schutzschicht auf wenigstens einer Oberfläche des Bandes zu erzielen.
  2. Verfahren nach Anspruch 1, bei welchem das Flußstahlband kaltgewalzt ist.
  3. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das Band eine Dickenabmessung zwischen 0,08 und 0,50 mm besitzt.
  4. Verfahren nach Anspruch 3, bei welchem das Band eine Dickenabmessung von 0,18 mm besitzt.
  5. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das Band elektrolytisch gereinigt wird.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem der chemische Überzug auf das Band durch Eintauchen, durch Aufsprühen, durch Aufwalzen des Überzuges oder durch eine Kombination hiervon aufgetragen wird.
  7. Verfahren nach Anspruch 6, bei welchem der chemische Überzug dadurch aufgetragen wird, daß das Band in wenigstens einen chemischen Behandlungsbehälter eingetaucht wird.
  8. Verfahren nach Anspruch 7, bei welchem die Verweilzeit des Bandes in dem chemischen Behandlungsbehälter weniger als 60 Sekunden beträgt.
  9. Verfahren nach Anspruch 8, bei welchem die Verweilzeit des Bandes in dem chemischen Behandlungsbehälter weniger als 30 Sekunden beträgt.
  10. Verfahren nach Anspruch 9, bei welchem die Verweilzeit des Bandes in dem chemischen Behandlungsbehälter weniger als 15 Sekunden beträgt.
  11. Verfahren nach Anspruch 10, bei welchem die Verweilzeit des Bandes in dem chemischen Behandlungsbehälter weniger als 10 Sekunden beträgt.
  12. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das Band chemisch bei einer Temperatur von weniger als 100°C behandelt wird.
  13. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das Band chemisch behandelt wird, um einen chemischen Überzug zwischen dem Band und dem thermoplastischen Kunstharz zu erzeugen, welches anti-korrosiv ist und die Haftung verbessert.
  14. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem der Oxyanion-Überzug aus einem Phosphat, einem Chromat, einem Oxalat oder einem Arsenat besteht.
  15. Verfahren nach Anspruch 14, bei welchem der chemische Überzug ein organisches Zweikomponenten-Polymer enthält.
  16. Verfahren nach Anspruch 14, bei welchem der chemische Überzug Chrom, Silizium und ein organisch aktives Mittel enthält.
  17. Verfahren nach Anspruch 14, bei welchem der chemische Überzug aus einem Phosphat, beispielsweise Zink-Orthophosphat, Mangan-Phosphaten oder Eisen-Phosphaten besteht.
  18. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem der chemische Überzug weniger als 5 Atomprozent Chrom enthält.
  19. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das chemisch behandelte Band gespült und/oder getrocknet wird, bevor es mit dem organischen Kunstharz überzogen wird.
  20. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem eine oder mehrere Schichten des thermoplastischen Kunstharzes auf einer oder auf beiden Seiten des chemisch behandelten Bandes aufgetragen werden.
  21. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem die Schicht oder die Schichten aus thermoplastischem Kunstharz geschmolzen und schnell abgeschreckt werden, um das erforderliche Ausmaß einer kristallinen Struktur zu erreichen.
  22. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das chemisch behandelte Band durch Extrusion mit wenigstens einem thermoplastischen Kunstharz überzogen wird.
  23. Verfahren nach Anspruch 22, bei welchem der Film aus thermoplastischem Kunstharz auf dem chemisch behandelten Band unter Bedingungen einer erhöhten Temperatur und eines erhöhten Druckes verbunden wird.
  24. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das chemisch behandelte Band mit dem thermoplastischen Kunstharz zusammen mit einer Verbindungsschicht überzogen wird.
  25. Verfahren nach Anspruch 24, bei welchem die Verbindungsschicht aus einem Polyester oder einer Säure oder einem Säure-Anhydrid-Polyolefin-Kunstharz besteht, das Carboxyl-Gruppen oder Anhydrid-Gruppen aufweist.
  26. Verfahren nach Anspruch 24 oder 25, bei welchem die Dicke der Verbindungsschicht zwischen 1 und 10 µm beträgt.
  27. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem das thermoplastische Kunstharz Polypropylen (PP), Polyäthylenterephtalat (PET) oder eine Kombination hiervon ist.
  28. Verfahren nach einem der vorhergehenden Ansprüche, bei welchem die Dicke der Schicht oder der Schichten aus thermoplastischem Kunstharz zwischen 3 und 50 µm beträgt.
EP99937821A 1998-03-02 1999-03-02 Beschichtung von metallbändern Expired - Lifetime EP1060032B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9804297 1998-03-02
GB9804297A GB2334906A (en) 1998-03-02 1998-03-02 Laminated metal strip
PCT/GB1999/000567 WO1999044756A2 (en) 1998-03-02 1999-03-02 Coated metal strips

Publications (2)

Publication Number Publication Date
EP1060032A2 EP1060032A2 (de) 2000-12-20
EP1060032B1 true EP1060032B1 (de) 2002-06-12

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EP99937821A Expired - Lifetime EP1060032B1 (de) 1998-03-02 1999-03-02 Beschichtung von metallbändern

Country Status (14)

Country Link
EP (1) EP1060032B1 (de)
KR (1) KR20010041481A (de)
CN (1) CN1291918A (de)
AT (1) ATE218930T1 (de)
AU (1) AU741976B2 (de)
BR (1) BR9908396A (de)
CA (1) CA2322533A1 (de)
DE (1) DE69901797T2 (de)
ES (1) ES2178453T3 (de)
GB (1) GB2334906A (de)
ID (1) ID28089A (de)
PL (1) PL343020A1 (de)
RU (2) RU2220789C2 (de)
WO (1) WO1999044756A2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013107506A1 (de) * 2013-07-16 2015-01-22 Thyssenkrupp Rasselstein Gmbh Verfahren zur Passivierung von bandförmigem Schwarzblech

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DE19961411A1 (de) * 1999-12-17 2001-06-21 Chemetall Gmbh Verfahren zur Herstellung von beschichteten Metalloberflächen und deren Verwendung
EP1948851B1 (de) 2005-09-13 2012-11-14 Chemetall GmbH Verfahren zur herstellung von weissblech, danach hergestelltes weissblech und daraus hergestellte verpackung
DE102008059014A1 (de) * 2008-05-28 2009-12-03 Basf Coatings Ag Verfahren zur Beschichtung von Metallbändern
US8486538B2 (en) * 2009-01-27 2013-07-16 Ppg Industries Ohio, Inc Electrodepositable coating composition comprising silane and yttrium
RU2655984C1 (ru) * 2017-05-11 2018-05-30 Общество с ограниченной ответственностью "Компания Металл Профиль" Способ нанесения покрытия на стальной прокат
CN113929035A (zh) * 2021-07-28 2022-01-14 厦门保沣实业有限公司 易拉盖防爆舌、泄露加工工艺及其生产出的易拉盖
RU2767082C1 (ru) * 2021-12-24 2022-03-16 Роберт Владимирович Ли Сборный футерованный резервуар

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Also Published As

Publication number Publication date
CA2322533A1 (en) 1999-09-10
DE69901797T2 (de) 2003-03-06
EP1060032A2 (de) 2000-12-20
PL343020A1 (en) 2001-07-30
WO1999044756A3 (en) 1999-11-25
ID28089A (id) 2001-05-03
BR9908396A (pt) 2000-10-31
ES2178453T3 (es) 2002-12-16
WO1999044756A2 (en) 1999-09-10
CN1291918A (zh) 2001-04-18
GB9804297D0 (en) 1998-04-22
DE69901797D1 (de) 2002-07-18
RU2003124575A (ru) 2005-02-27
AU741976B2 (en) 2001-12-13
RU2220789C2 (ru) 2004-01-10
KR20010041481A (ko) 2001-05-25
GB2334906A (en) 1999-09-08
AU3259699A (en) 1999-09-20
ATE218930T1 (de) 2002-06-15

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