EP0754251B1 - Chrome-free process for the no-rinse treatment of aluminium and its alloys, plus solutions suitable for use in the process - Google Patents

Chrome-free process for the no-rinse treatment of aluminium and its alloys, plus solutions suitable for use in the process Download PDF

Info

Publication number
EP0754251B1
EP0754251B1 EP95915174A EP95915174A EP0754251B1 EP 0754251 B1 EP0754251 B1 EP 0754251B1 EP 95915174 A EP95915174 A EP 95915174A EP 95915174 A EP95915174 A EP 95915174A EP 0754251 B1 EP0754251 B1 EP 0754251B1
Authority
EP
European Patent Office
Prior art keywords
water
treatment
organic film
treatment solution
bis
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
EP95915174A
Other languages
German (de)
French (fr)
Other versions
EP0754251A1 (en
Inventor
Uwe Karmaschek
Raschad Mady
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0754251A1 publication Critical patent/EP0754251A1/en
Application granted granted Critical
Publication of EP0754251B1 publication Critical patent/EP0754251B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides containing also phosphates
    • C23C22/361—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 fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds

Definitions

  • the invention relates to the preparation of cleaned metal surfaces, especially of strips of aluminum or aluminum alloys for one subsequent coating with organic coatings, in particular on the manufacture of metal goods for architectural applications and for the food packaging sector is thought.
  • no-rinse processes are generally known today.
  • the metal surface is cleaned of oil, dirt and other residues. Any residues of chemicals from this first stage are removed by rinsing with water.
  • the clean metal surface is wetted with an aqueous bath solution, which is no longer rinsed off but dried in situ on the metal surface and converted there into a solid film of the bath components.
  • Such coatings can substantially improve the surface quality, particularly with regard to corrosion protection and adhesion of subsequently applied cover layers.
  • chrome-free conversion treatment of aluminum surfaces with fluorides boron, silicon, titanium or zirconium alone or in combination with organic polymers is to achieve permanent corrosion protection and to create a basis for subsequent painting known in principle:
  • DE-C-24 33 704 describes treatment baths for increasing paint adhesion and permanent corrosion protection on, inter alia, aluminum, the 0.1 to 5 g / l polyacrylic acid or its salts or esters and 0.1 to 3.5 g / l ammonium fluorozirconate, calculated as ZrO 2 .
  • the pH values of these baths can fluctuate over a wide range. The best results are generally obtained when the pH is 6-8.
  • WO 92/07973 teaches a chromium- free treatment process for aluminum, the essential components in acidic aqueous solution being 0.01 to about 18% by weight of H 2 ZrF 6 and 0.01 to about 10% by weight of a 3- (NC 1 -4 alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer used.
  • German patent application DE-A-43 17 217 describes a process for the pretreatment of surfaces made of aluminum or its alloys before a second, permanently corrosion-protective conversion treatment, in which the surfaces are brought into contact with acidic aqueous treatment solutions, the complex fluorides of the elements boron, Contain silicon, titanium, zircon or hafnium individually or in a mixture with one another in concentrations of the fluoro anions of between 100 and 4000, preferably 200 to 2000, mg / l and a pH between 0.3 and 3.5, preferably between 1 and 3.
  • the treatment solutions can additionally contain polymers of the type of the polyacrylates and / or the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines in concentrations below 500 mg / l, preferably below 200 mg / l.
  • Phosphoric acid is another optional component of these baths.
  • US-A-4 136 073 claims a chromium-free treatment process for aluminum surfaces, in which the surfaces are brought into contact with acidic (pH 1.2 to 5.5) aqueous solutions containing an organic film former and a soluble titanium compound in the weight ratio polymer: titanium contained between 100: 1 and 1:10.
  • the preferred titanium concentration is between 0.01 and 5% by weight.
  • the present invention is based on the object of a chrome-free “no-rinse” method of the type described at the beginning or suitable for this
  • a chrome-free “no-rinse” method of the type described at the beginning or suitable for this
  • To create treatment agents for architectural applications and in particular suitable for use in the food packaging sector are.
  • those for food applications typical requirements such as sterilizability from the treated material manufactured packaging and avoiding peeling the coating when opening cans ("feathering").
  • a uniform, visually appealing finish layer can be created on the metal surface, which, for example, in the subsequent overcoats with clear coats meets the aesthetic requirements, particularly in the field of food packaging.
  • Such treatment solutions best meet the different requirements for the behavior of the coating which contain both Ti (IV) and Zr (IV), a weight ratio Ti: Zr in the range 3: 1 to 1: 3 being particularly preferred.
  • the pH of the solutions should preferably be between 1.5 and 2.5.
  • the fluoride is preferably used as a complex-bound fluoride, for example as TiF 6 2- or ZrF 6 2- .
  • the organic film former is advantageously a synthetic polymer with a sufficient content of free carboxyl groups, its Water solubility or homogeneous dispersibility in water in the process Ensure pH range.
  • Polymers are particularly suitable of acrylic acid and / or methacrylic acid, which may also be restricted Amounts of copolymers and the corresponding esters, nitriles and / or may contain amides.
  • Preferred organic film formers are clear soluble polyacrylic acids, especially in the pH range of aqueous treatment baths retain their clear solubility. In general it is about are polyacrylic acids of a not too high molecular weight, for example those with molecular weights from 20,000 to about 150,000, preferably from 40,000 to about 100,000.
  • aqueous treatment solutions according to the invention can be pre-cleaned
  • Metal tapes can be applied in any type of application is suitable, a uniformly defined liquid film in the specified Generate quantity ranges on the metal surface.
  • Roller application process with two or three rollers ("Chemcoater"), but also wetting the tape by spraying or dipping with subsequent squeezing of the excess liquid film through, for example, plastic-coated leveling rollers or adjustable ones Air knife is applicable.
  • the temperature of the treatment solution can vary between 15 and 50 ° C are. The temperature is preferably chosen between 20 and 35 ° C.
  • the applied liquid film is allowed to act on the metal surface for a reaction time of about 1 to 40 seconds, whereupon the film is dried and thermally treated at an elevated temperature.
  • a deformable water-insoluble solid film with a mass per unit area of about 50 to 350 mg / m 2 , preferably of about 100 to 250 mg / m 2 remains on the metal surface.
  • the drying and / or the thermal treatment of the applied liquid film or the chemicals applied with it can take place in the temperature range from approximately 50 to 125 ° C., the range between 50 and 80 ° C. being preferred.
  • Both acidic and alkaline cleaners are suitable.
  • the layers obtained with the aqueous treatment solution according to the invention deliver an even finish without discoloration of the base material. she meet in combination with suitable organic applied below Coatings meet the requirements for the food packaging sector.
  • the invention further relates to the aqueous suitable for this process Treatment solution concentrates.
  • the concentrates so that they are for use in the invention Process with 2 to 50 parts by weight of water per part by weight of concentrate be diluted.
  • Table 1 contains bath compositions according to the invention, Table 3 comparative examples in which either the phosphate or the polymer component was omitted. Test results for this are summarized in Table 4.
  • Bath compositions Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ti 4+ - 7.1 g / l 3.6 g / l 7.1 g / l 3.6 g / l Zr 4+ 10.8 g / l - 5.4 g / l 5.4 g / l 10.8 g / l PO 4 -3 12.0 g / l 12.0 g / l 12.0 g / l 12.0 g / l 12.0 g / l 12.0 g / l 12.0 g / l F - 13.5 g / l 16.9 g / l 15.2 g / l 23.7 g / l 22.0 g / l OP 0.7 g / l 0.7

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)

Description

Die Erfindung betrifft die Vorbereitung gereinigter Metalloberflächen, insbesondere von Bändern aus Aluminium oder Aluminiumlegierungen für eine nachfolgende Beschichtung mit organischen Überzügen, wobei insbesondere an die Fertigung von Metallwaren für Architekturanwendungen und für den Lebensmittel-Verpackungsbereich gedacht ist.The invention relates to the preparation of cleaned metal surfaces, especially of strips of aluminum or aluminum alloys for one subsequent coating with organic coatings, in particular on the manufacture of metal goods for architectural applications and for the food packaging sector is thought.

Im Rahmen der chemischen Behandlung von Metalloberflächen, beispielsweise für den nachfolgenden Auftrag von Lacken, Klebern und/oder Kunststoffen, sind heute sogenannte "No-Rinse"-Verfahren allgemein bekannt. Hierzu wird in einer ersten Stufe die Metalloberfläche von Öl, Schmutz und anderen Rückständen gereinigt. Eventuelle Rückstände von Chemikalien aus dieser ersten Stufe werden durch Spülen mit Wasser beseitigt. In der jetzt nachfolgenden Verfahrensstufe wird die saubere Metalloberfläche mit einer wäßrigen Badlösung benetzt, die nicht mehr abgespült, sondern in situ auf der Metalloberfläche getrocknet und dort zu einem Feststoffilm der Badbestandteile umgewandelt wird. Durch solche Überzüge kann die Oberflächenbeschaffenheit, insbesondere bezüglich Korrosionsschutz und Haftung nachfolgend aufgebrachter Abdeckschichten substantiell verbessert werden. In dem umfangreichen einschlägigen druckschriftlichen Stand der Technik sind ursprünglich häufig Behandlungslösungen vorgeschlagen worden, die 6-wertiges Chrom enthalten ("Gelbchromatierung"). Wegen des toxischen Charakters von Cr(VI) benötigen diese Verfahren bzw. dabei anfallende Spülwässer eine aufwendige Abwasseraufbereitung. Auch Verfahren, die Chrom ausschließlich in der dreiwertigen Stufe einsetzen (DE-A-32 47 729), können wegen der zunehmenden Forderungen nach völliger Chromfreiheit nicht völlig befriedigen. In the context of the chemical treatment of metal surfaces, for example for the subsequent application of lacquers, adhesives and / or plastics, so-called "no-rinse" processes are generally known today. In a first step, the metal surface is cleaned of oil, dirt and other residues. Any residues of chemicals from this first stage are removed by rinsing with water. In the subsequent process step, the clean metal surface is wetted with an aqueous bath solution, which is no longer rinsed off but dried in situ on the metal surface and converted there into a solid film of the bath components. Such coatings can substantially improve the surface quality, particularly with regard to corrosion protection and adhesion of subsequently applied cover layers. Treatment solutions containing hexavalent chromium ("yellow chromating") were originally often proposed in the extensive relevant prior art. Because of the toxic nature of Cr (VI), these processes and the rinsing water that they require require elaborate wastewater treatment. Even processes that only use chromium in the trivalent stage ( DE-A-32 47 729 ) cannot be completely satisfied because of the increasing demands for complete freedom from chromium.

Die chromfreie Konversionsbehandlung von Aluminiumoberflächen mit Fluoriden von Bor, Silicium, Titan oder Zirkonium allein oder in Verbindung mit organischen Polymeren ist zur Erzielung eines permanenten Korrosionsschutzes und zur Erzeugung einer Grundlage für eine anschließende Lackierung prinzipiell bekannt:The chrome-free conversion treatment of aluminum surfaces with fluorides boron, silicon, titanium or zirconium alone or in combination with organic polymers is to achieve permanent corrosion protection and to create a basis for subsequent painting known in principle:

Die US-A-5 129 967 und US-A-4 921 552 offenbaren Behandlungsbäder für eine No-Rinse-Behandlung (dort als "dried in place conversion coating" bezeichnet) von Aluminium, enthaltend

  • a) 10 bis 16 g/l Polyacrylsäure oder deren Homopolymere,
  • b) 12 bis 19 g/l Hexafluorozirkonsäure,
  • c) 0,17 bis 0,3 g/l Fluorwasserstoffsäure und
  • d) bis zu 0,6 g/l Hexafluorotitansäure.
    • US-A-5 129 967 and US-A-4 921 552 disclose treatment baths for a no-rinse treatment (referred to there as "dried in place conversion coating") containing aluminum
  • a) 10 to 16 g / l polyacrylic acid or its homopolymers,
  • b) 12 to 19 g / l hexafluorozirconic acid,
  • c) 0.17 to 0.3 g / l hydrofluoric acid and
  • d) up to 0.6 g / l hexafluorotitanic acid.

    • EP-B-8 942 offenbart Behandlungslösungen, vorzugsweise für Aluminiumdosen, enthaltend

  • a) 0,5 bis 10 g/l Polyacrylsäure oder eines Esters davon und
  • b) 0,2 bis 8 g /1 an mindestens einer der Verbindungen H2ZrF6, H2TiF6 und H2SiF6, wobei der pH-Wert der Lösung unterhalb von 3,5 liegt,
    • sowie ein wäßriges Konzentrat zum Wiederauffrischen der Behandlungslösung enthaltend
  • a) 25 bis 100 g/l Polyacrylsäure oder eines Esters davon,
  • b) 25 bis 100 g/l von mindestens einer der Verbindungen H2ZrF6, H2TiF6 und H2SiF6, und
  • c) einer Quelle freier Fluoridionen, die 17 bis 120 g/l freies Fluorid liefert.
    •  EP-B-8 942 discloses treatment solutions, preferably containing aluminum cans
  • a) 0.5 to 10 g / l polyacrylic acid or an ester thereof and
  • b) 0.2 to 8 g / l of at least one of the compounds H 2 ZrF 6 , H 2 TiF 6 and H 2 SiF 6 , the pH of the solution being below 3.5,
    • and containing an aqueous concentrate for replenishing the treatment solution
  • a) 25 to 100 g / l polyacrylic acid or an ester thereof,
  • b) 25 to 100 g / l of at least one of the compounds H 2 ZrF 6 , H 2 TiF 6 and H 2 SiF 6 , and
  • c) a source of free fluoride ions which provides 17 to 120 g / l of free fluoride.

    • DE-C-24 33 704 beschreibt Behandlungsbäder zur Erhöhung der Lackhaftung und des permanenten Korrosionsschutzes auf u.a. Aluminium, die 0,1 bis 5 g/l Polyacrylsäure oder deren Salze oder Ester sowie 0,1 bis 3,5 g/l Ammoniumfluorozirkonat, berechnet als ZrO2, enthalten können. Die pH-Werte dieser Bäder können über einen weiten Bereich schwanken. Die besten Ergebnisse werden im allgemeinen erhalten, wenn der pH bei 6 - 8 liegt. DE-C-24 33 704 describes treatment baths for increasing paint adhesion and permanent corrosion protection on, inter alia, aluminum, the 0.1 to 5 g / l polyacrylic acid or its salts or esters and 0.1 to 3.5 g / l ammonium fluorozirconate, calculated as ZrO 2 . The pH values of these baths can fluctuate over a wide range. The best results are generally obtained when the pH is 6-8.

    US-A-4 992 116 beschreibt Behandlungsbäder für die Konversionsbehandlung von Aluminium mit pH-Werten zwischen etwa 2,5 und 5, die mindestens drei Komponenten enthalten:

  • a) Phosphationen im Konzentrationsbereich zwischen 1,1x10-5 bis 5,3x10-3 mol/l entsprechend 1 bis 500 mg/l,
  • b) 1,1x10-5 bis 1,3x10-3 mol/l einer Fluorosäure eines Elements der Gruppe Zr, Ti, Hf und Si (entsprechend je nach Element 1,6 bis 380 mg/l) und
  • c) 0,26 bis 20 g/l einer Polyphenolverbindung, erhältlich durch Umsetzung von Poly(vinylphenol) mit Aldehyden und organischen Aminen.
    • US-A-4 992 116 describes treatment baths for the conversion treatment of aluminum with pH values between about 2.5 and 5, which contain at least three components:
  • a) phosphate ions in the concentration range between 1.1x10 -5 to 5.3x10 -3 mol / l corresponding to 1 to 500 mg / l,
  • b) 1.1x10 -5 to 1.3x10 -3 mol / l of a fluoric acid of an element from the group Zr, Ti, Hf and Si (corresponding to 1.6 to 380 mg / l depending on the element) and
  • c) 0.26 to 20 g / l of a polyphenol compound, obtainable by reacting poly (vinylphenol) with aldehydes and organic amines.

    • WO 92/07973 lehrt ein chromfreies Behandlungsverfahren für Aluminium, das als wesentliche Komponenten in saurer wäßriger Lösung 0,01 bis etwa 18 Gew.-% H2ZrF6 und 0,01 bis etwa 10 Gew.-% eines 3-(N-C1-4alkyl-N-2-hydroxyethylaminomethyl)-4-hydroxystyrol-Polymers verwendet. WO 92/07973 teaches a chromium- free treatment process for aluminum, the essential components in acidic aqueous solution being 0.01 to about 18% by weight of H 2 ZrF 6 and 0.01 to about 10% by weight of a 3- (NC 1 -4 alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer used.

    Die Deutsche Patentanmeldung DE-A-43 17 217 beschreibt ein Verfahren zur Vorbehandlung von Oberflächen aus Aluminium oder seinen Legierungen vor einer zweiten, permanent korrosionsschützenden Konversionsbehandlung, bei dem man die Oberflächen mit sauren wäßrigen Behandlungslösungen in Kontakt bringt, die komplexe Fluoride der Elemente Bor, Silicium, Titan, Zirkon oder Hafnium einzeln oder im Gemisch miteinander in Konzentrationen der Fluoro-Anionen von insgesamt zwischen 100 und 4000, vorzugsweise 200 bis 2000, mg/l enthalten und einen pH-Wert zwischen 0,3 und 3,5, vorzugsweise zwischen 1 und 3, aufweisen. Dabei können die Behandlungslösungen zusätzlich Polymere vom Typ der Polyacrylate und/oder der Umsetzungsprodukte von Poly(vinylphenol) mit Aldehyden und organischen Hydroxylgruppen-haltigen Aminen in Konzentrationen unter 500 mg/l, vorzugsweise unter 200 mg/l enthalten. Phosphorsäure ist ein weiterer fakultativer Bestandteil dieser Bäder.German patent application DE-A-43 17 217 describes a process for the pretreatment of surfaces made of aluminum or its alloys before a second, permanently corrosion-protective conversion treatment, in which the surfaces are brought into contact with acidic aqueous treatment solutions, the complex fluorides of the elements boron, Contain silicon, titanium, zircon or hafnium individually or in a mixture with one another in concentrations of the fluoro anions of between 100 and 4000, preferably 200 to 2000, mg / l and a pH between 0.3 and 3.5, preferably between 1 and 3. The treatment solutions can additionally contain polymers of the type of the polyacrylates and / or the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines in concentrations below 500 mg / l, preferably below 200 mg / l. Phosphoric acid is another optional component of these baths.

    US-A-4 136 073 beansprucht ein chromfreies Behandlungsverfahren für Aluminiumoberflächen, bei dem man die Oberflächen mit sauren (pH 1,2 bis 5,5) wäßrigen Lösungen in Berührung bringt, die einen organischen Filmbildner und eine lösliche Titanverbindung im Gewichtsverhältnis Polymer:Titan zwischen 100:1 und 1:10 enthalten. Die bevorzugte Titankonzentration beträgt zwischen 0,01 und 5 Gew.-%. US-A-4 136 073 claims a chromium-free treatment process for aluminum surfaces, in which the surfaces are brought into contact with acidic (pH 1.2 to 5.5) aqueous solutions containing an organic film former and a soluble titanium compound in the weight ratio polymer: titanium contained between 100: 1 and 1:10. The preferred titanium concentration is between 0.01 and 5% by weight.

    Die vorliegende Erfindung geht von der Aufgabe aus, ein chromfreies "No-Rinse"-Verfahren der eingangs geschilderten Art bzw. hierfür geeignete Behandlungsmittel zu schaffen, die für Architekturanwendungen und insbesondere für die Anwendung auf dem Sektor der Lebensmittelverpackung geeignet sind. Hierbei sind insbesondere die für Lebensmittel anwendungen typischen Anforderungen wie beispielsweise Sterilisierbarkeit der aus dem behandelten Material hergestellten Verpackung und die Vermeidung des Abziehens der Beschichtung beim Öffnen von Dosen ("Feathering") zu erfüllen. Gleichzeitig soll durch das erfindungsgemäße Verfahren eine gleichmäßige, optisch ansprechende Finish-Lage auf der Metalloberfläche erzeugt werden, die beispielsweise bei den nachfolgenden Überschichtungen mit Klarlacken den ästhetischen Anforderungen genügt, die insbesondere auf dem Bereich der Verpackung von Lebensmitteln gewünscht werden.The present invention is based on the object of a chrome-free “no-rinse” method of the type described at the beginning or suitable for this To create treatment agents for architectural applications and in particular suitable for use in the food packaging sector are. Here are in particular those for food applications typical requirements such as sterilizability from the treated material manufactured packaging and avoiding peeling the coating when opening cans ("feathering"). At the same time, a uniform, visually appealing finish layer can be created on the metal surface, which, for example, in the subsequent overcoats with clear coats meets the aesthetic requirements, particularly in the field of food packaging.

    Gegenstand der Erfindung ist dementsprechend ein Verfahren zur Erzeugung von chromfreien Konversionsschichten auf Oberflächen von Aluminium und seinen Legierungen im No-Rinse-Verfahren durch Behandeln mit wäßrigen Lösungen mit einem pH-Wert zwischen 1 und 3,5, die Titan und/oder Zirkon sowie organische Filmbildner enthalten, dadurch gekennzeichnet, daß man die Oberflächen mit Lösungen in Kontakt bringt, die im wesentlichen aus:

  • a) 2,2 bis 22,0 g/l Zr(IV) und/oder 1,4 bis 14,0 g/l Ti(IV),
  • b) 2,4 bis 24,0 g/l Orthophosphat,
  • c) 3,0 bis 30,0 g/l Fluorid,
  • d) 0,15 bis 1,5 g/l eines wasserlöslichen oder in Wasser homogen dispergierbaren organischen Filmbildners und
  • e) Wasser
    • bestehen, und die Lösungen nach einer Einwirkungszeit zwischen einer und 40 Sekunden ohne Spülung bei Temperaturen zwischen 50 und 125 °C auf der Oberfläche eintrocknet. The invention accordingly relates to a process for producing chromium-free conversion layers on surfaces of aluminum and its alloys in the no-rinse process by treatment with aqueous solutions with a pH between 1 and 3.5, the titanium and / or zirconium and organic Contain film formers, characterized in that the surfaces are brought into contact with solutions consisting essentially of:
  • a) 2.2 to 22.0 g / l Zr (IV) and / or 1.4 to 14.0 g / l Ti (IV),
  • b) 2.4 to 24.0 g / l orthophosphate,
  • c) 3.0 to 30.0 g / l fluoride,
  • d) 0.15 to 1.5 g / l of a water-soluble or homogeneously dispersible organic film former and
  • e) water
    • exist, and the solutions dry after an exposure time between one and 40 seconds without rinsing at temperatures between 50 and 125 ° C on the surface.

    Vorzugsweise enthalten die Behandlungslösungen

  • a) 4,3 bis 13,0 g/l Zr(IV) und/oder 2,8 bis 8,5 g/l Ti(IV),
  • b) 4,8 bis 14,3 g/l Orthophosphat,
  • c) 6,0 bis 18,2 g/l Fluorid,
  • d) 0,28 bis 0,82 g/l eines wasserlöslichen oder in Wasser homogen dispergierbaren organischen Filmbildners.
    • The treatment solutions preferably contain
  • a) 4.3 to 13.0 g / l Zr (IV) and / or 2.8 to 8.5 g / l Ti (IV),
  • b) 4.8 to 14.3 g / l orthophosphate,
  • c) 6.0 to 18.2 g / l fluoride,
  • d) 0.28 to 0.82 g / l of a water-soluble or homogeneously dispersible organic film former.

    • Dabei erfüllen solche Behandlungslösungen die unterschiedlichen Anforderungen an das Verhalten der Beschichtung am besten, die sowohl Ti(IV) als auch Zr(IV) enthalten, wobei ein Gewichtsverhältnis Ti:Zr im Bereich 3:1 bis 1:3 besonders bevorzugt ist. Der pH-Wert der Lösungen soll vorzugsweise zwischen 1,5 und 2,5 liegen. Das Fluorid setzt man vorzugsweise als komplexgebundenes Fluorid, beispielsweise als TiF6 2- oder ZrF6 2- ein.Such treatment solutions best meet the different requirements for the behavior of the coating which contain both Ti (IV) and Zr (IV), a weight ratio Ti: Zr in the range 3: 1 to 1: 3 being particularly preferred. The pH of the solutions should preferably be between 1.5 and 2.5. The fluoride is preferably used as a complex-bound fluoride, for example as TiF 6 2- or ZrF 6 2- .

    Der organische Filmbildner ist zweckmäßigerweise ein synthetisches Polymeres mit einem hinreichenden Gehalt an freien Carboxylgruppen, die seine Wasserlöslichkeit bzw. homogene Dispergierbarkeit in Wasser im verfahrensgemäßen pH-Wertbereich sicherstellen. Geeignet sind insbesondere Polymere von Acrylsäure und/oder Methacrylsäure, die gegebenenfalls auch beschränkte Mengen an Copolymeren sowie den entsprechenden Estern, Nitrilen und/ oder Amiden enthalten können. Bevorzugte organische Filmbildner sind klar lösliche Polyacrylsäuren, die insbesondere im pH-Bereich der wäßrigen Behandlungsbäder ihre Klarlöslichkeit behalten. Im allgemeinen handelt es sich dabei um Polyacrylsäuren eines nicht zu hohen Molekulargewichtes, beispielsweise solche mit Molekulargewichten von 20 000 bis etwa 150 000, vorzugsweise von 40 000 bis etwa 100 000.The organic film former is advantageously a synthetic polymer with a sufficient content of free carboxyl groups, its Water solubility or homogeneous dispersibility in water in the process Ensure pH range. Polymers are particularly suitable of acrylic acid and / or methacrylic acid, which may also be restricted Amounts of copolymers and the corresponding esters, nitriles and / or may contain amides. Preferred organic film formers are clear soluble polyacrylic acids, especially in the pH range of aqueous treatment baths retain their clear solubility. In general it is about are polyacrylic acids of a not too high molecular weight, for example those with molecular weights from 20,000 to about 150,000, preferably from 40,000 to about 100,000.

    Im erfindungsgemäßen Verfahren wird eine konventionell gereinigte und gespülte Metalloberfläche nach Spülen mit vollentsalztem Wasser und Trocknung und/oder nach Abquetschen des Wasserfilmes in an sich beliebiger Weise mit der wäßrigen Behandlungslösung derart benetzt, daß zweckmäßigerweise pro Quadratmeter der Fläche etwa 3 bis 10 ml, vorzugsweise etwa 4 bis 8 ml der wäßrigen Behandlungslösung aufgetragen werden.In the method according to the invention, a conventionally cleaned and rinsed Metal surface after rinsing with deionized water and drying and / or after squeezing the water film in any way per se wetted with the aqueous treatment solution in such a way that expediently about 3 to 10 ml, preferably about 4 to 8, per square meter of the area ml of the aqueous treatment solution are applied.

    Die erfindungsgemäßen wäßrigen Behandlungslösungen können auf die vorgereinigten Metallbänder in jeder Applikationsart aufgebracht werden, die geeignet ist, einen gleichmäßigen definierten Flüssigfilm in den angegebenen Mengenbereichen auf der Metalloberfläche zu erzeugen. Bewährt haben sich insbesondere das Walzenauftragsverfahren mit zwei oder drei Walzen ("Chemcoater"), aber auch ein Benetzen des Bandes durch Sprühen oder Tauchen mit anschließendem Abquetschen des überschüssigen Flüssigkeitsfilmes durch beispielsweise Kunststoff-beschichtete Egalisierwalzen oder regelbare Luftrakel ist anwendbar. Die Temperatur der Behandlungslösung kann zwischen 15 und 50 °C liegen. Vorzugsweise wählt man die Temperatur zwischen 20 und 35 °C.The aqueous treatment solutions according to the invention can be pre-cleaned Metal tapes can be applied in any type of application is suitable, a uniformly defined liquid film in the specified Generate quantity ranges on the metal surface. Have proven especially the roller application process with two or three rollers ("Chemcoater"), but also wetting the tape by spraying or dipping with subsequent squeezing of the excess liquid film through, for example, plastic-coated leveling rollers or adjustable ones Air knife is applicable. The temperature of the treatment solution can vary between 15 and 50 ° C are. The temperature is preferably chosen between 20 and 35 ° C.

    Man läßt den aufgetragenen Flüssigfilm für eine Reaktionsdauer von etwa 1 bis 40 Sekunden auf die Metalloberfläche einwirken, woraufhin der Film getrocknet und bei erhöhter Temperatur thermisch behandelt wird. Die Verfahrensstufen des Einwirkens auf die Metalloberfläche und der Trocknung können allerdings auch zusammengefaßt werden. Nach dem Trocknen verbleibt auf der Metalloberfläche ein verformungsfähiger wasserunlöslicher Feststoffilm mit einer flächenbezogenen Masse von etwa 50 bis 350 mg/m2, vorzugsweise von etwa 100 bis 250 mg/m2. Die Trocknung und/ oder die thermische Behandlung des aufgebrachten Flüssigkeitsfilms bzw. der damit aufgetragenen Chemikalien kann im Temperaturbereich von etwa 50 bis 125 °C erfolgen, wobei der Bereich zwischen 50 und 80 °C bevorzugt ist.The applied liquid film is allowed to act on the metal surface for a reaction time of about 1 to 40 seconds, whereupon the film is dried and thermally treated at an elevated temperature. However, the process steps of acting on the metal surface and drying can also be summarized. After drying, a deformable water-insoluble solid film with a mass per unit area of about 50 to 350 mg / m 2 , preferably of about 100 to 250 mg / m 2, remains on the metal surface. The drying and / or the thermal treatment of the applied liquid film or the chemicals applied with it can take place in the temperature range from approximately 50 to 125 ° C., the range between 50 and 80 ° C. being preferred.

    Für die reinigende Vorbehandlung der erfindungsgemäß zu benetzenden Metalloberflächen sind sowohl saure wie alkalische Reiniger geeignet. Die mit der erfindungsgemäßen wäßrigen Behandlungslösung erzielten Schichten liefern ein gleichmäßiges Finish ohne Verfärbungen des Grundmaterials. Sie erfüllen in Kombination mit nachfolgend aufgebrachten geeigneten organischen Beschichtungen die Forderungen für den Sektor der Lebensmittelverpackungen.For the cleaning pretreatment of the metal surfaces to be wetted according to the invention Both acidic and alkaline cleaners are suitable. The layers obtained with the aqueous treatment solution according to the invention deliver an even finish without discoloration of the base material. she meet in combination with suitable organic applied below Coatings meet the requirements for the food packaging sector.

    Die Erfindung betrifft weiterhin die für dieses Verfahren geeigneten wäßrigen Konzentrate der Behandlungslösungen. Vorteilhafterweise stellt man die Konzentrate so ein, daß sie zur Anwendung in dem erfindungsgemäßen Verfahren mit 2 bis 50 Gewichtsteilen Wasser pro Gewichtsteil Konzentrat verdünnt werden. The invention further relates to the aqueous suitable for this process Treatment solution concentrates. Advantageously, one poses the concentrates so that they are for use in the invention Process with 2 to 50 parts by weight of water per part by weight of concentrate be diluted.

    Somit betrifft die vorliegende Erfindung in einer weiteren Ausführungsform ein wäßriges Konzentrat, das durch Verdünnen mit 2 bis 50 Gewichtsteilen Wasser pro Gewichtsteil Konzentrat eine anwendungsfertige Behandlungslösung ergibt, welche im wesentlichen aus:

  • a) 2,2 bis 22,0 g/l Zr(IV) und/oder 1,4 bis 14,0 g/l Ti(IV),
  • b) 2,4 bis 24,0 g/l Orthophosphat,
  • c) 3,0 bis 30,0 g/l Fluorid,
  • d) 0,15 bis 1,5 g/l eines wasserlöslichen oder in Wasser homogen dispergierbaren organischen Filmbildners und
  • e) Wasser
    • besteht und zur Verwendung im Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 8 dient. Thus, in a further embodiment, the present invention relates to an aqueous concentrate which, by dilution with 2 to 50 parts by weight of water per part by weight of concentrate, gives a ready-to-use treatment solution which essentially consists of:
  • a) 2.2 to 22.0 g / l Zr (IV) and / or 1.4 to 14.0 g / l Ti (IV),
  • b) 2.4 to 24.0 g / l orthophosphate,
  • c) 3.0 to 30.0 g / l fluoride,
  • d) 0.15 to 1.5 g / l of a water-soluble or homogeneously dispersible organic film former and
  • e) water
    • exists and serves for use in the method according to one or more of claims 1 to 8.

    BeispieleExamples

    Innerhalb der üblichen Prozeßfolge für "No-Rinse-Produkte" mit den Stufen

  • 1. Reinigung und Entfettung Verwendung von tensidhaltigen alkalischen oder sauren Reinigungsmitteln (z.b. RIDOLINER C 72 oder RIDOLINER 124/120 E) im Spritzverfahren bei einer Behandlungstemperatur von 50-65 °C und Behandlungszeiten von 8 - 20 s.
  • 2. Spülen mit Betriebswasser
  • 3. Spülen mit VE-Wasser
  • 4. Trocknung
  • 5. Applikation der Vorbehandlung in der "No-Rinse-Technologie" Laborapplikation mit einer "Lackschleuder" mittels Zentrifugalkraft; 5 Sekunden schleudern mit 550 Umdrehungen/Minute, Badtemperatur 30 °C. Badzusammensetzung siehe Tab. 1. pH-Wert der Bäder: 2,0.
  • 6. Trocknung: Umlufttrockenschrank, 70 °C
  • 7. Lackierung
    erfolgte die eigentliche Oberflächenvorbehandlung gemäß Pkt. 5 mit Varianten in nachfolgenden Tabellen.
    • Within the usual process sequence for "no-rinse products" with the stages
  • 1. Cleaning and degreasing Use of alkaline or acidic cleaning agents containing surfactants (eg RIDOLINE R C 72 or RIDOLINE R 124/120 E) in a spray process at a treatment temperature of 50-65 ° C and treatment times of 8 - 20 s.
  • 2. Rinse with process water
  • 3. Rinse with demineralized water
  • 4. Drying
  • 5. Application of the pretreatment in the "no-rinse technology" laboratory application with a "paint spinner" using centrifugal force; Spin for 5 seconds at 550 revolutions / minute, bath temperature 30 ° C. For the bath composition, see Table 1. Bath pH: 2.0.
  • 6. Drying: circulating air drying cabinet, 70 ° C
  • 7. Painting
    The actual surface pretreatment was carried out according to point 5 with variants in the following tables.

    • Tabelle 1 enthält erfindungsgemäße Badzusammensetzungen, Tabelle 3 Vergleichsbeispiele, in denen entweder die Phosphat- oder die Polymerkomponente weggelassen wurde. Prüfergebnisse hierzu sind in Tabelle 4 zusammengefaßt. Badzusammensetzungen Beisp. 1 Beisp. 2 Beisp. 3 Beisp. 4 Beisp. 5 Ti4+ - 7,1 g/l 3,6 g/l 7,1 g/l 3,6 g/l Zr4+ 10,8 g/l - 5,4 g/l 5,4 g/l 10,8 g/l PO4 -3 12,0 g/l 12,0 g/l 12,0 g/l 12,0 g/l 12,0 g/l F- 13,5 g/l 16,9 g/l 15,2 g/l 23,7 g/l 22,0 g/l O.P. 0,7 g/l 0,7 g/l 0,7 g/l 0,7 g/l 0,7 g/l F.F. 6 ml/m2 6 ml/m2 6 ml/m2 6 ml/m2 6 ml/m2 Table 1 contains bath compositions according to the invention, Table 3 comparative examples in which either the phosphate or the polymer component was omitted. Test results for this are summarized in Table 4. Bath compositions Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ti 4+ - 7.1 g / l 3.6 g / l 7.1 g / l 3.6 g / l Zr 4+ 10.8 g / l - 5.4 g / l 5.4 g / l 10.8 g / l PO 4 -3 12.0 g / l 12.0 g / l 12.0 g / l 12.0 g / l 12.0 g / l F - 13.5 g / l 16.9 g / l 15.2 g / l 23.7 g / l 22.0 g / l OP 0.7 g / l 0.7 g / l 0.7 g / l 0.7 g / l 0.7 g / l FF 6 ml / m 2 6 ml / m 2 6 ml / m 2 6 ml / m 2 6 ml / m 2

    Mit den oben genannten Varianten wurden folgende Metall- bzw. Gesamtschichtauflagen erzielt, nachdem der Flüssigfilm bei 70 °C eingetrocknet wurde (Tabelle 2): Schichtauflagen Beisp. 1 Beisp. 2 Beisp. 3 Beisp. 4 Beisp. 5 Ti - 43 mg/m2 22 mg/m2 43 mg/m2 22 mg/m2 Zr 65 mg/m2 - 33 mg/m2 32 mg/m2 65 mg/m2 G.S. 222 mg/m2 220 mg/m2 220 mg/m2 293 mg/m2 295 mg/m2 With the above-mentioned variants, the following metal or total layer coatings were achieved after the liquid film had been dried at 70 ° C (Table 2): Layer pads Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ti - 43 mg / m 2 22 mg / m 2 43 mg / m 2 22 mg / m 2 Zr 65 mg / m 2 - 33 mg / m 2 32 mg / m 2 65 mg / m 2 GS 222 mg / m 2 220 mg / m 2 220 mg / m 2 293 mg / m 2 295 mg / m 2

    TestergebnisseTest results 1. Architekturbereich 1. Architectural area

    Legierung:Alloy:
    Al 99,5
    AlMn1Mg0,5    Al 99.5
    AlMn1Mg0.5
    Lacksystem:Paint system:
    1-Schicht-Polyester "PE-25" Fa. Bollig & Kemper1-layer polyester "PE-25" from Bollig & Kemper
  • a) T-Bend-Test
    (Biegung der Blechkante um 180° und Tesaband-Abriß)
  • 1 = sehr gut; kein Abriß
  • 5 = mangelhaft; völliger Abriß
    •  Al 99,5 AlMn1Mg0,5 Blech nur entfettet 5 5 Vergleich: Gelbchromatierung 4 4 (AlodineR 1200, Henkel KGaA) Beisp. 1 5 5 Beisp. 2 2 1 Beisp. 3 3 3 Beisp. 4 1 1 Beisp. 5 2 2 a) T-bend test
    (Bending of the sheet edge by 180 ° and tearing of the tape)
  • 1 = very good; no demolition
  • 5 = poor; complete demolition
    • Al 99.5 AlMn1Mg0.5 Sheet only degreased 5 5 Comparison: yellow chromating 4th 4th (Alodine R 1200, Henkel KGaA) Ex. 1 5 5 Ex. 2 2nd 1 Ex. 3 3rd 3rd Ex. 4 1 1 Ex. 5 2nd 2nd
  • b) Münztest
    (Mit der Kante einer Münze wird im Winkel von 45 ° der Lack kräftig abgekratzt)    b) coin test
    (With the edge of a coin, the lacquer is scraped off sharply at an angle of 45 °)
    • Beurteilung:Evaluation:

    1 =1 =
    Decklack wird abgekratzt, Primer bleibt unbeschädigt oder 1-Komponentenlack wird nicht beschädigtTop coat is scraped off, primer remains undamaged or 1-component paint will not be damaged
    2 =2 =
    Primerbeschädigung < 5 % oder 1-Komp.-Lackbeschädigung < 5 %Primer damage <5% or 1-component paint damage <5%
    3 =3 =
    Primerbeschädigung max. 30 % oder 1-Komp.-Lackbeschädigung max 30 %Primer damage max. 30% or 1-component paint damage max 30%
    4 =4 =
    Primerbeschädigung bis 75 % oder 1-Komp.-Lackbeschädigung bis 75 %Primer damage up to 75% or 1-component paint damage up to 75%
    5 =5 =
    Primerbeschädigung 100 % oder 1-Komp.-Lackbeschädigung 100Primer damage 100% or 1-component paint damage 100
    Al99,5Al99.5 AlMn1Mg0,5AlMn1Mg0.5 Blech nur entfettetSheet only degreased 55 55 Vergl: GelbchromatierungCompare: yellow chromating 33rd 55 (AlodineR 1200, Henkel KGaA)(Alodine R 1200, Henkel KGaA) NO-RINSE-VorbehandlungNO-RINSE pretreatment 11 11 (Cr6+-haltig, AlodineR NR 6012S,(Contains Cr 6+ , Alodine R NR 6012S, Henkel KGaA)Henkel KGaA) Beisp.1Ex. 1 55 55 Beisp.2Ex. 2 11 22nd Beisp.3Ex. 3 33rd 33rd Beisp.4Ex.4 11 11 Beisp.5Ex. 5 22nd 22nd 2. Lebensmittelsektor 2. Food sector FeatheringtestFeathering test

    Legierung:
    AlMg5
    Lacksystem:
    Dexter/Midland L3E 692 S
    Beurteilung:
    Nach dem Kochen eines lackierten Blechabschnittes in VE-Wasser wird das Aufreißen des Verschlusses einer Getränkedose simuliert.
    1 = sehr gut:
    sauberer Abriß; kein überstehender oder fehlender Lack
    5 = mangelhaft:
    ein ca. 1 mm oder größerer überstehender Lackfilm ist feststellbar.
    Abstufung:
    1 - 5
    AlMg5 Blech nur entfettet 4 - 5 Vergleich: No-Rinse-Vorbehandlung 1 (Cr(III)-haltig: AlodineR NR 6207 R, (Henkel KGaA) Beisp. 1 1 - 2 Beisp. 2 1 Beisp. 3 1 - 2 Beisp. 4 1 Beisp. 5 1
    Figure 00130001
    Alloy:
    AlMg5
    Paint system:
    Dexter / Midland L3E 692 S.
    Evaluation:
    After a lacquered sheet metal section has been boiled in demineralized water, the opening of a beverage can closure is simulated.
    1 = very good:
    clean demolition; no protruding or missing paint
    5 = poor:
    a paint film that protrudes approx. 1 mm or larger is detectable.
    Gradation:
    1 - 5
    AlMg5 Sheet only degreased 4 - 5 Comparison: no-rinse pretreatment 1 (Cr (III) -containing: Alodine R NR 6207 R, (Henkel KGaA) Ex. 1 1 - 2 Ex. 2 1 Ex. 3 1 - 2 Ex. 4 1 Ex. 5 1
    Figure 00130001

    Claims (9)

    1. A process for the production of chromium-free conversion coatings on surfaces of aluminium and its alloys on the no-rinse principle by treatment with aqueous solutions having a pH value of 1 to 3.5 and containing titanium and/or zirconium and organic film formers, characterized in that the surfaces are contacted with solutions essentially consisting of
      a) 2.2 to 22.0 g/l of Zr(lV) and/or 1.4 to 14.0 g/l of Ti(IV),
      b) 2.4 to 24.0 g/l of orthophosphate,
      c) 3.0 to 30.0 g/l of fluoride,
      d) 0.15 to 1.5 g/l of a water-soluble or homogeneously water-dispersible organic film former and
      e) water
      and the solutions are dried on the surface without rinsing after a contact time of 1 to 40 seconds at temperatures of 50 to 125°C.
    2. A process as claimed in claim 1, characterized in that the treatment solutions contain
      a) 4.3 to 13.0 g/l of Zr(IV) and/or 2.8 to 8.5 g/l of Ti(IV),
      b) 4.8 to 14.3 g/l of orthophosphate,
      c) 6.0 to 18.2 g/l of fluoride,
      d) 0.28 to 0.82 g/l of a water-soluble or homogeneously water-dispersible organic film former.
    3. A process as claimed in one or both of claims 1 and 2, characterized in that the treatment solution contains both titanium and zirconium, the ratio by weight of Ti to Zr preferably being 3:1 to 1:3.
    4. A process as claimed on one or more of claims 1 to 3, characterized in that the organic film former is a carboxyfunctional polymer, more especially a homopolymer and/or copolymer of acrylic and/or methacrylic acid, and has an average molecular weight of 20,000 to 150,000 and preferably in the range from 40,000 to 100,000.
    5. A process as claimed in one or more of claims 1 to 4, characterized in that the treatment solution has a temperature of 15 to 50°C and preferably in the range from 20 to 35°C.
    6. A process as claimed in one or more of claims 1 to 5, characterized in that the treatment solution has a pH value of 1.5 to 2.5.
    7. A process as claimed in one or more of claims 1 to 6, characterized in that the treatment solution is applied to the metal surface in the form of a liquid film in a quantity of 3 to 10 ml/m2 and, more particularly, in a quantity of 4 to 8 ml/m2.
    8. A process as claimed in one or more of claims 1 to 7, characterized in that the liquid film is dried at a temperature of 50 to 80°C.
    9. An aqueous concentrate which, by dilution with 2 to 50 parts by weight of water per part by weight of concentrate, gives a ready-to-use treatment solution essentially consisting of
      a) 2.2 to 22.0 g/l of Zr(IV) and/or 1.4 to 14.0 g/l of Ti(lV),
      b) 2.4 to 24.0 g/l of orthophosphate,
      c) 3.0 to 30.0 g/l of fluoride,
      d) 0.15 to 1.5 g/l of a water-soluble or homogeneously water-dispersible organic film former and
      e) water
      for use in the process claimed in one or more of claims 1 to 8.
    EP95915174A 1994-04-08 1995-03-31 Chrome-free process for the no-rinse treatment of aluminium and its alloys, plus solutions suitable for use in the process Expired - Lifetime EP0754251B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE4412138A DE4412138A1 (en) 1994-04-08 1994-04-08 Chromium-free process for no-rinse treatment of aluminum and its alloys as well as suitable aqueous bath solutions
    DE4412138 1994-04-08
    PCT/EP1995/001197 WO1995027807A1 (en) 1994-04-08 1995-03-31 Chrome-free process for the no-rinse treatment of aluminium and its alloys, plus solutions suitable for use in the process

    Publications (2)

    Publication Number Publication Date
    EP0754251A1 EP0754251A1 (en) 1997-01-22
    EP0754251B1 true EP0754251B1 (en) 1998-05-20

    Family

    ID=6514924

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP95915174A Expired - Lifetime EP0754251B1 (en) 1994-04-08 1995-03-31 Chrome-free process for the no-rinse treatment of aluminium and its alloys, plus solutions suitable for use in the process

    Country Status (7)

    Country Link
    US (1) US5868872A (en)
    EP (1) EP0754251B1 (en)
    JP (1) JP3662586B2 (en)
    CA (1) CA2187463A1 (en)
    DE (2) DE4412138A1 (en)
    ES (1) ES2117863T3 (en)
    WO (1) WO1995027807A1 (en)

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE102008019761B3 (en) * 2008-04-18 2009-06-04 Henkel Ag & Co. Kgaa Heat exchanger with expandable plastic tailpipes

    Families Citing this family (35)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    ATE302654T1 (en) * 1997-10-14 2005-09-15 Henkel Kgaa COMPOSITION AND METHOD FOR THE MULTIPURPOSE TREATMENT OF METAL SURFACES
    US6802913B1 (en) 1997-10-14 2004-10-12 Henkel Kommanditgesellschaft Aut Aktien Composition and process for multi-purpose treatment of metal surfaces
    EP0919877B1 (en) * 1997-12-01 2004-02-18 Canon Kabushiki Kaisha Process for producing electrophotographic photosensitive member
    DE19807688C2 (en) * 1998-02-25 2003-06-26 Daimler Chrysler Ag Use of a chromium-free conversion solution based on zirconium as protective film on light metal blanks of a cylinder liner to be inserted
    US6432603B1 (en) * 1998-11-27 2002-08-13 Canon Kabushiki Kaisha Process for producing electrophotographic photosensitive member
    JP2000162806A (en) 1998-11-30 2000-06-16 Canon Inc Electrophotographic photoreceptor, its production, process cartridge and electrophotographic device
    US6248490B1 (en) 1998-12-01 2001-06-19 Canon Kabushiki Kaisha Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus
    DE19921842A1 (en) 1999-05-11 2000-11-16 Metallgesellschaft Ag Pretreatment of aluminum surfaces with chrome-free solutions
    DE19923084A1 (en) * 1999-05-20 2000-11-23 Henkel Kgaa Chromium-free corrosion protection agent for coating metallic substrates contains hexafluoro anions, phosphoric acid, metal compound, film-forming organic polymer or copolymer and organophosphonic acid
    JP4099307B2 (en) * 2000-04-20 2008-06-11 日本ペイント株式会社 Non-chromium anti-rust treatment agent for aluminum, anti-rust treatment method and anti-rust treated aluminum products
    JP2001342578A (en) * 2000-05-31 2001-12-14 Honda Motor Co Ltd Surface treatment agent for metal
    JP5183837B2 (en) * 2001-05-07 2013-04-17 日本ペイント株式会社 Chemical conversion treatment agent and treatment method
    AU2003290716A1 (en) * 2002-11-15 2004-06-15 Henkel Kommanditgesellschaft Auf Aktien Passivation composition and process for zinciferous and aluminiferous surfaces
    DE10258291A1 (en) * 2002-12-13 2004-07-08 Henkel Kgaa Process for coating metal substrates with a free-radically polymerizable coating agent and coated substrates
    US6887308B2 (en) * 2003-01-21 2005-05-03 Johnsondiversey, Inc. Metal coating coupling composition
    GB0314901D0 (en) * 2003-06-26 2003-07-30 Natech Ltd Coating material
    US20050226975A1 (en) * 2004-04-13 2005-10-13 Greg Drouillard Foodstuff marking system
    US20060042726A1 (en) * 2004-09-02 2006-03-02 General Electric Company Non-chrome passivation of steel
    JP4784236B2 (en) * 2004-09-30 2011-10-05 住友電気工業株式会社 Non-aqueous electrolyte battery lead wire and non-aqueous electrolyte battery
    DE102005005858A1 (en) 2005-02-08 2006-08-17 Henkel Kgaa Process for coating metal sheet, in particular zinc sheet
    US7858162B2 (en) * 2006-04-06 2010-12-28 Ppg Industries Ohio, Inc. Food cans coated with a composition comprising an acrylic polymer
    DE102006039633A1 (en) * 2006-08-24 2008-03-13 Henkel Kgaa Chrome-free, thermally curable corrosion inhibitor
    US9428410B2 (en) 2007-09-28 2016-08-30 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate
    US8097093B2 (en) 2007-09-28 2012-01-17 Ppg Industries Ohio, Inc Methods for treating a ferrous metal substrate
    US20090188269A1 (en) * 2008-01-25 2009-07-30 Henkel Corporation High pressure connection systems and methods for their manufacture
    DE102008009371A1 (en) 2008-02-14 2009-08-20 Henkel Ag & Co. Kgaa Method for producing a heat exchanger
    DE102008023276A1 (en) * 2008-05-13 2009-11-19 Henkel Ag & Co. Kgaa Connecting pipes with thermosetting adhesives
    DE102008034105A1 (en) 2008-07-21 2010-01-28 Henkel Ag & Co. Kgaa Connecting pipes by means of a sleeve and a thermally expandable adhesive
    US9347134B2 (en) 2010-06-04 2016-05-24 Prc-Desoto International, Inc. Corrosion resistant metallate compositions
    EP2532769A1 (en) 2011-06-10 2012-12-12 Amcor Flexibles Kreuzlingen Ltd. Method of producing a chromium-free conversion coating on a surface of an aluminium or aluminium alloy strip
    US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
    JP6295832B2 (en) * 2014-05-28 2018-03-20 株式会社ブリヂストン Aluminum-rubber composite and method for producing the same
    US10886249B2 (en) 2018-01-31 2021-01-05 Ams International Ag Hybrid wafer-to-wafer bonding and methods of surface preparation for wafers comprising an aluminum metalization
    WO2020148412A1 (en) 2019-01-18 2020-07-23 Constellium Neuf-Brisach Continuous surface treatment for coils made of aluminum alloys sheets
    FR3091880B1 (en) * 2019-01-18 2022-08-12 Constellium Neuf Brisach Continuous surface treatment of coils made from aluminum alloy sheets

    Family Cites Families (18)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3912548A (en) * 1973-07-13 1975-10-14 Amchem Prod Method for treating metal surfaces with compositions comprising zirconium and a polymer
    JPS5315687B2 (en) * 1973-10-04 1978-05-26
    JPS5145604B2 (en) * 1973-12-21 1976-12-04
    JPS5173938A (en) * 1974-12-25 1976-06-26 Nippon Packaging Kk Aruminiumuoyobi sonogokinnohyomenshoriho
    US4063969A (en) * 1976-02-09 1977-12-20 Oxy Metal Industries Corporation Treating aluminum with tannin and lithium
    FR2417537A1 (en) * 1978-02-21 1979-09-14 Parker Ste Continentale COMPOSITION BASED ON HAFNIUM TO INHIBIT CORROSION OF METALS
    US4191596A (en) * 1978-09-06 1980-03-04 Union Carbide Corporation Method and compositions for coating aluminum
    DE3247729A1 (en) * 1982-12-23 1984-07-05 Gerhard Collardin GmbH, 5000 Köln METHOD FOR TREATING METAL SURFACES, ESPECIALLY SUCH OF ALUMINUM, ALUMINUM ALLOYS AND STEEL, AND AQUEOUS AQUEOUS BATH SOLUTIONS THEREFOR
    US4470853A (en) * 1983-10-03 1984-09-11 Coral Chemical Company Coating compositions and method for the treatment of metal surfaces
    US4978399A (en) * 1988-01-04 1990-12-18 Kao Corporation Metal surface treatment with an aqueous solution
    US5129967A (en) * 1988-05-03 1992-07-14 Betz Laboratories, Inc. Composition and method for non-chromate coating of aluminum
    US4921552A (en) * 1988-05-03 1990-05-01 Betz Laboratories, Inc. Composition and method for non-chromate coating of aluminum
    US4992116A (en) * 1989-04-21 1991-02-12 Henkel Corporation Method and composition for coating aluminum
    US5089064A (en) * 1990-11-02 1992-02-18 Henkel Corporation Process for corrosion resisting treatments for aluminum surfaces
    US5158622A (en) * 1991-02-12 1992-10-27 Betz Laboratories, Inc. Method and composition for treatment of aluminum
    DE4317217A1 (en) * 1993-05-24 1994-12-01 Henkel Kgaa Chrome-free conversion treatment of aluminum
    US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals
    US5441580A (en) * 1993-10-15 1995-08-15 Circle-Prosco, Inc. Hydrophilic coatings for aluminum

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE102008019761B3 (en) * 2008-04-18 2009-06-04 Henkel Ag & Co. Kgaa Heat exchanger with expandable plastic tailpipes

    Also Published As

    Publication number Publication date
    US5868872A (en) 1999-02-09
    DE4412138A1 (en) 1995-10-12
    JPH09511548A (en) 1997-11-18
    DE59502263D1 (en) 1998-06-25
    EP0754251A1 (en) 1997-01-22
    JP3662586B2 (en) 2005-06-22
    WO1995027807A1 (en) 1995-10-19
    CA2187463A1 (en) 1995-10-19
    ES2117863T3 (en) 1998-08-16

    Similar Documents

    Publication Publication Date Title
    EP0754251B1 (en) Chrome-free process for the no-rinse treatment of aluminium and its alloys, plus solutions suitable for use in the process
    DE2433704C3 (en) Use of aqueous dispersions containing zirconium compounds and polyacrylic acid for treating metal surfaces
    EP1254279B1 (en) Anti-corrosive agents and method for protecting metal surfaces against corrosion
    DE2428065C2 (en) Process for sealing zinc phosphate coatings on steel substrates
    EP3350357B1 (en) Pre-treating aluminum surfaces with zirconium- and molybdenum-containing compositions
    DE60114311T2 (en) Chrome-free coating compositions and painted metal sheets
    EP0774016B1 (en) No-rinse phosphatising process
    DE10010758A1 (en) Corrosion protection of zinc, aluminum and/or magnesium surfaces such as motor vehicle bodies, comprises passivation using complex fluorides of Ti, Zr, Hf, Si and/or B and organic polymers
    EP1402083B1 (en) Corrosion protection method for metal surfaces
    DE102009044821B4 (en) Treatment solution and method for coating metal surfaces
    EP0948666A1 (en) Method for treating metallic surfaces
    WO2000068458A1 (en) Pretreatment of aluminum surfaces with chrome-free solutions
    EP1751327A1 (en) Coloured conversion layers on metallic surfaces
    WO1996034995A1 (en) Chromium- and fluoride-free treatment of metallic surfaces
    EP0111897B1 (en) Process for the treatment of metal surfaces, especially aluminium, aluminium alloy and steel ones, and aqueous bath solutions suitable therefor
    DE3236247A1 (en) METHOD FOR SURFACE TREATMENT OF ALUMINUM
    EP1658392B1 (en) Colour conversion layers on metal surfaces
    EP0760870B1 (en) Iron phosphatisation using substituted monocarboxilic acids
    EP1029111B1 (en) Corrosion protection for galvanised and alloy galvanised steel strips
    DE4041091A1 (en) METHOD FOR REFILLING CONVERSION LAYERS
    DE10030462A1 (en) Adhesion promoter in conversion solutions
    WO1999020696A1 (en) Method for coating metals and metal coated using said method
    EP0121155B1 (en) Preparation of iron or steel surfaces for painting

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 19960930

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): BE CH DE ES FR GB IT LI NL SE

    17Q First examination report despatched

    Effective date: 19970319

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAG Despatch of communication of intention to grant

    Free format text: ORIGINAL CODE: EPIDOS AGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): BE CH DE ES FR GB IT LI NL SE

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    ET Fr: translation filed
    REF Corresponds to:

    Ref document number: 59502263

    Country of ref document: DE

    Date of ref document: 19980625

    ITF It: translation for a ep patent filed

    Owner name: STUDIO JAUMANN P. & C. S.N.C.

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2117863

    Country of ref document: ES

    Kind code of ref document: T3

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 19980723

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 19990401

    26N No opposition filed
    EUG Se: european patent has lapsed

    Ref document number: 95915174.7

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: BE

    Payment date: 20010515

    Year of fee payment: 7

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: IF02

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20020331

    BERE Be: lapsed

    Owner name: *HENKEL K.G.A.A.

    Effective date: 20020331

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: NL

    Payment date: 20030327

    Year of fee payment: 9

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20041001

    NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

    Effective date: 20041001

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

    Effective date: 20050331

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: CH

    Payment date: 20050331

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20050425

    Year of fee payment: 11

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20060331

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20060331

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20060401

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20060401

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20090325

    Year of fee payment: 15

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20090327

    Year of fee payment: 15

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20090316

    Year of fee payment: 15

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20100331

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20101130

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20100331

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20101001

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20100331