EP0111897B1 - Process for the treatment of metal surfaces, especially aluminium, aluminium alloy and steel ones, and aqueous bath solutions suitable therefor - Google Patents
Process for the treatment of metal surfaces, especially aluminium, aluminium alloy and steel ones, and aqueous bath solutions suitable therefor Download PDFInfo
- Publication number
- EP0111897B1 EP0111897B1 EP83112610A EP83112610A EP0111897B1 EP 0111897 B1 EP0111897 B1 EP 0111897B1 EP 83112610 A EP83112610 A EP 83112610A EP 83112610 A EP83112610 A EP 83112610A EP 0111897 B1 EP0111897 B1 EP 0111897B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- chromium
- iii
- aqueous bath
- metal surfaces
- 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
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 8
- 239000010959 steel Substances 0.000 title claims abstract description 8
- 239000004411 aluminium Substances 0.000 title claims description 4
- -1 fluoride ions Chemical class 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000470 constituent Substances 0.000 claims abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 239000008199 coating composition Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 229920001519 homopolymer Polymers 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 229910001430 chromium ion Inorganic materials 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000008237 rinsing water Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- UJRBOEBOIXOEQK-UHFFFAOYSA-N oxo(oxochromiooxy)chromium hydrate Chemical compound O.O=[Cr]O[Cr]=O UJRBOEBOIXOEQK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—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
-
- 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
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Definitions
- the invention relates to the preparation of cleaned metal surfaces, in particular of strips made of aluminum, aluminum alloys and cold-rolled steel - but also other metal surfaces - for a subsequent coating with organic coatings, in particular the manufacture of metal goods for the food packaging sector.
- Such coatings can substantially improve the surface quality, in particular with regard to corrosion protection and adhesion of subsequently applied cover layers.
- Treatment solutions containing hexavalent chromium were originally often proposed in the extensive relevant prior art. Because of the toxic nature of this compound, these processes and the rinsing water that they require require elaborate wastewater treatment.
- treatment solutions which contain hexavalent chromium and trivalent chromium salts together with film formers are described, for example, in DE-AS 1 769 582 and in DE-OS 2 903 311.
- alkali silicate is to be used as the inorganic film former.
- the second reference uses polyacrylic acid as an organic film former. Due to the content of 6-valent chromium in the aqueous bath fluids, these materials are not suitable for use in the food sector.
- DE-OS 2 711 431 describes a process for the surface treatment of metals, in particular iron, zinc and aluminum, in which the cleaned metal surface is to be wetted with an acidic aqueous solution, the chromium (III) ions; Contains phosphate ions and finely divided silica, it being possible for acetate ions, male ions, zinc ions and / or manganese ions to additionally be present in the treatment solution.
- the toxic chromium (VI) ion can be dispensed with here, but acidic dispersions containing silica and phosphate ions have the disadvantage of a limited pot life
- Japanese Patent Application 57-174,469 is referenced in “Patent Abstracts of Japan, unexamined applications •, Vol. 7, No. 19 (January 25, 1983), C Field, page 64 C 147. It was then known to use solutions containing Cr 2 O 3 , co-salts of inorganic acids, phosphoric acid, silica sol and suitable fluorides to form a chromate film on steel surfaces. After treating the surfaces with such solutions, the excess solution is removed and the steel surface is dried without rinsing.
- DE-A-3 038 699 describes aqueous acidic chromate coating solutions for the treatment of zinc, zinc alloy or cadmium surfaces which contain trivalent chromium ions as practically the only chromium ions, fluoride ions and an acid and by mixing a green trivalent chromium ion solution with a blue trivalent one Chromium ion solution can be prepared.
- the green solution containing trivalent chromium ions is obtained by reducing a solution containing hexavalent chromium.
- phosphoric acid is mentioned as a suitable acid.
- the present invention is based on the object of creating a “no-rinse” method of the type described at the outset or suitable treatment agents which do not have the disadvantages known hitherto for materials of this type and in particular for use in the food packaging sector are suitable.
- the process according to the invention is intended to produce a glossy, visually appealing finish layer on the metal surface which, for example in the subsequent overlays with clear lacquers, meets the aesthetic requirements which are particularly desired in the field of food packaging.
- the invention relates in a first embodiment to a method for treating metal surfaces, preferably aluminum, aluminum alloys and steel, in particular for a subsequent coating with coating compositions on an organic basis, the previously cleaned metal surfaces being wetted with an aqueous bath solution which contains chromium (III ) ions, fluoride ions and phosphate ions - but no chromium (VI) ions
- the method according to the invention is suitable for the surface treatment of all metals relevant here, in particular therefore ferrous metals, aluminum or aluminum alloys, zinc and / or magnesium.
- the invention is particularly suitable for the pretreatment of strips made of aluminum or aluminum alloys and cold-rolled steel for their subsequent use in the food packaging sector.
- a conventionally cleaned and rinsed metal surface for example the surface of strips of the aforementioned metals, is squeezed in any way with the aqueous treatment solution after squeezing off the water film in such a way that expediently about 2 to 20 ml per square meter of the area , preferably about 3 to 7 ml of the aqueous treatment solution.
- the content of the aforementioned active constituents of the aqueous treatment solution should continue to be within the following ranges per square meter of the metal surface: 5 to 100 mg of chromium (III) ions, 5.5 to 110 mg of fluoride ions and 6 to 125 mg of phosphate ions, and about 1 , 5 to 35 mg of the organic water-soluble or homogeneously water-dispersible film former.
- the applied liquid film is allowed to act on the metal surface for a reaction time of about 1 to 10 seconds, whereupon the film is dried and thermally treated at an elevated temperature.
- the process steps of acting on the metal surface and drying can also be summarized. After drying on the metal shell l Smile Friend a ver f ormungsstructer water-insoluble solid film with a basis weight of about 18 to 370 mg / m 2, preferably from about 50 to 250 mg / m 2 metal surface.
- the drying and / or the thermal treatment of the applied liquid film or the chemicals applied with it can take place in particular in the temperature range from approximately 50 to 300 ° C.
- Chromium (III) ions and fluoride ions are most easily introduced into the bath using chromium (III) fluoride, although the ratio of chromium (III) ions: fluoride ions is in the range from 1: 2.5 to 3.5 can fluctuate.
- the phosphate content is adjusted by adding phosphates or phosphoric acid with subsequent partial neutralization. It applies that the phosphate content based on 1 mol of chromium (III) ions is preferably in a molar ratio of 0.3 to 3.0.
- the organic film former is expediently a synthetic polymer with a sufficient content of free carboxyl groups, which is its water solubility. ensure homogeneous dispersibility in water.
- Preferred organic film formers are clearly soluble polyacrylic acids, which retain their clear solubility in particular in the pH range of the aqueous treatment baths - which is usually between 2 and 3.
- these are polyacrylic acids of a molecular weight which is not too high, for example those with molecular weights of up to about 150,000, preferably up to about 100,000.
- aqueous treatment solutions according to the invention can be applied to the pre-cleaned metal strips in any type of application which is suitable for producing a uniform, defined liquid film in the specified quantity ranges on the metal surface.
- the roller application process with two or three rollers has proven successful, but wetting of the strip by spraying or dipping with subsequent squeezing off of the excess liquid film by means of, for example, plastic-coated leveling rollers or adjustable air doctor blades can also be used.
- Both acidic and alkaline cleaners are suitable for the pretreatment of the metal surfaces to be wetted according to the invention.
- the layers obtained with the aqueous treatment solution according to the invention provide a uniform, glossy finish without discoloration of the base material.
- suitable organic coatings applied below they meet the requirements for the food packaging sector.
- Aluminum strip of the alloy AIMg 5 was first cleaned and degreased in a coil coating line. An acidic solution containing 1 g / IH 2 SO 4 , 0.2 g / l HF and 1 g / l surfactant combination was used for this. The cleaning was carried out at a temperature of 60 ° C., 8 seconds and at a spray pressure of 1.5 bar. The tape was then rinsed with warm demineralized water and the rinsing water squeezed out.
- a liquid film of 5 ml / m 2 surface was then applied with the solution according to the invention by means of roller application processes, whereby the surface per m 2 is covered with a liquid film containing 25 mg Cr 3+ , 27.5 mg F-, 31.3 mg PO 4 - and 8.75 mg of polyacrylic acid ("Acrylsol® A 1 - from Röhm & Haas, Philadelphia. USA) contains.
- the water contained in the liquid film was evaporated in a floating dryer with a circulating air temperature of 100 ° C. and a metal object temperature of approx. 50 ° C., and a water-insoluble film of 92.5 mg / m 2 was obtained on the metal surface.
- the speeds of rotation of the chemcoater rollers were set such that a liquid film of 8 ml / m 2 of belt surface was applied to a cleaned and water-rinsed aluminum belt at a belt speed of 100 m / minute by means of the application rollers of the chemcoater.
- the tape was wetted with a liquid film which contains 40 mg Cr 3+ , 44 mg F - , 50 mg PO 4 ---- and 14 mg polyacrylic acid 100% strength per m 2 of surface and, after drying, a mass per unit area of 148 mg / m 2 on the aluminum.
- the water portion of the liquid film was removed by means of a warm air dryer and then the tape was heated to an object temperature of 200 ° C. After cooling, the film obtained on the tape was wetted with 8 to 10 mg of dioctyl sebacate to improve the sliding property.
- the chemically pretreated aluminum surface thus obtained was coated with varnishes suitable for the food sector and tested for its resistance to filling goods and forming behavior. In all tests, technological values were found which, in comparison to conventional solutions and methods, achieved results which were at least equivalent, and in some cases even better, with the methods according to the invention.
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Coating With Molten Metal (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
Die Erfindung betrifft die Vorbereitung gereinigter Metalloberflächen, insbesondere von Bändern aus Aluminium, Aluminiumlegierungen sowie kaltgewalztem Stahl - aber auch anderen Metalloberflächen -, für eine nachfolgende Beschichtung mit organischen Überzügen, wobei insbesondere an die Fertigung von Metallwaren für den Lebensmittel-Verpackungsbereich gedacht ist.The invention relates to the preparation of cleaned metal surfaces, in particular of strips made of aluminum, aluminum alloys and cold-rolled steel - but also other metal surfaces - for a subsequent coating with organic coatings, in particular the manufacture of metal goods for the food packaging sector.
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 im Gegenteil in situ auf derIn the course 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. For this purpose, the metal surface is cleaned of oil, dirt and other residues in a first stage Any residues of chemicals from this first stage are removed by rinsing with water In the now subsequent process stage, the clean metal surface is wetted with an aqueous bath solution which is no longer rinsed off, but on the contrary in situ on the
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.Dried metal surface and there is converted into a solid film of the bath components. Such coatings can substantially improve the surface quality, in particular with regard to corrosion protection and adhesion of subsequently applied cover layers.
In dem umfangreichen einschlägigen druckschriftlichen Stand der Technik sind ursprünglich häufig Behandlungslösungen vorgeschlagen worden, die 6-wertiges Chrom enthalten. Wegen des toxischen Charakters dieser Verbindung benötigen diese Verfahren bzw. dabei anfallende Spülwässer eine aufwendige Abwasseraufbereitung.Treatment solutions containing hexavalent chromium were originally often proposed in the extensive relevant prior art. Because of the toxic nature of this compound, these processes and the rinsing water that they require require elaborate wastewater treatment.
Die Verwendung von Behandlungslösungen, die 6-wertige Chrom- und 3-wertige Chromsalze zusammen mit Filmbildnern enthalten sind beispielsweise in der DE-AS 1 769 582 und in der DE-OS 2 903 311 beschrieben. In der zuerst genannten Literaturstelle soll als anorganischer Filmbildner beispielsweise Alkalisilikat zum Einsatz kommen. Die zweite Literaturstelle verwendet Polyacrylsäure als organischen Filmbildner. Aufgrund des Gehaltes der wäßrigen Badflüssigkeiten an 6- wertigem Chrom sind diese Materialien für den Einsatz im Lebensmittelsektor nicht geeignet.The use of treatment solutions which contain hexavalent chromium and trivalent chromium salts together with film formers are described, for example, in DE-AS 1 769 582 and in DE-OS 2 903 311. In the first-mentioned literature reference, for example, alkali silicate is to be used as the inorganic film former. The second reference uses polyacrylic acid as an organic film former. Due to the content of 6-valent chromium in the aqueous bath fluids, these materials are not suitable for use in the food sector.
Die DE-OS 2 711 431 schildert ein Verfahren zur Oberflächenbehandlung von Metallen, insbesondere von Eisen, Zink und Aluminium, bei dem die gereinigte Metalloberfläche mit einer sauren wäßrigen Lösung benetzt werden soll, die Chrom (lII)-Ionen ; Phosphationen und fein verteilte Kieselsäure enthält, wobei zusätzlich Acetationen, Maleinationen, Zinkionen und/oder Manganionen in der Behandlungslösung vorliegen können. Zwar kann hier auf das giftige Chrom(VI)-lon verzichtet werden, saure Dispersionen mit einem Gehalt an Kieselsäure und Phosphationen haben jedoch den Nachteil einer nur begrenzten TopfzeitDE-OS 2 711 431 describes a process for the surface treatment of metals, in particular iron, zinc and aluminum, in which the cleaned metal surface is to be wetted with an acidic aqueous solution, the chromium (III) ions; Contains phosphate ions and finely divided silica, it being possible for acetate ions, male ions, zinc ions and / or manganese ions to additionally be present in the treatment solution. The toxic chromium (VI) ion can be dispensed with here, but acidic dispersions containing silica and phosphate ions have the disadvantage of a limited pot life
In « Patent Abstracts of Japan, unexamined applications •, Vol. 7, Nr. 19 (25.1.1983), C Field, Seite 64 C 147, wird die japanische Patentanmeldung 57-174 469 referiert. Hiernach war es bekannt, zur Bildung eines Chromatfilms auf Stahloberflächen Lösungen zu verwenden, die Cr2O3, Co-Salze anorganischer Säuren, Phosphorsäure, Silica-Sol und geeignete Fluoride enthalten. Nach Behandlung der Oberflächen mit derartigen Lösungen wird die überschüssige Lösung entfernt und die Stahloberfläche ohne Spülen getrocknet.Japanese Patent Application 57-174,469 is referenced in “Patent Abstracts of Japan, unexamined applications •, Vol. 7, No. 19 (January 25, 1983), C Field, page 64 C 147. It was then known to use solutions containing Cr 2 O 3 , co-salts of inorganic acids, phosphoric acid, silica sol and suitable fluorides to form a chromate film on steel surfaces. After treating the surfaces with such solutions, the excess solution is removed and the steel surface is dried without rinsing.
In der DE-A-3 038 699 werden wäßrige saure Chromatbeschichtungslösungen für die Behandlung von Zink-, Zinklegierungs- oder Cadmiumoberflächen beschrieben, die trivalente Chromionen als praktisch einzige Chromionen, Fluoridionen und eine Säure enthalten und durch Mischen einer grünen trivalenten Chromionenlösung mit einer blauen trivalenten Chromionenlösung hergestellt werden. Hierbei wird die grüne trivalente Chromionen enthaltene Lösung durch Reduktion einer hexavalentes Chrom enthaltenden Lösung gewonnen. Als geeignete Säure wird unter anderen auch Phosphorsäure erwähnt. Zur Erzeugung eines Chromüberzuges auf den oben genannten Metalloberflächen werden diese mit derartigen Lösungen in Kontakt gebracht, anschließend mit Wasser abgespült und dann getrocknet.DE-A-3 038 699 describes aqueous acidic chromate coating solutions for the treatment of zinc, zinc alloy or cadmium surfaces which contain trivalent chromium ions as practically the only chromium ions, fluoride ions and an acid and by mixing a green trivalent chromium ion solution with a blue trivalent one Chromium ion solution can be prepared. Here, the green solution containing trivalent chromium ions is obtained by reducing a solution containing hexavalent chromium. Among other things, phosphoric acid is mentioned as a suitable acid. To produce a chrome coating on the above-mentioned metal surfaces, these are brought into contact with such solutions, then rinsed with water and then dried.
Die vorliegende Erfindung geht von der Aufgabe aus, ein « No-Rinse »-Verfahren der eingangs geschilderten Art bzw. hierfür geeignete Behandlungsmittel zu schaffen, die die bisher für Materialien dieser Art bekannten Nachteile nicht besitzen und insbesondere für die Anwendung auf dem Sektor der Lebensmittelverpackung geeignet sind. Gleichzeitig soll durch das erfindungsgemäße Verfahren eine glänzende, 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 creating a “no-rinse” method of the type described at the outset or suitable treatment agents which do not have the disadvantages known hitherto for materials of this type and in particular for use in the food packaging sector are suitable. At the same time, the process according to the invention is intended to produce a glossy, visually appealing finish layer on the metal surface which, for example in the subsequent overlays with clear lacquers, meets the aesthetic requirements which are particularly desired in the field of food packaging.
Gegenstand der Erfindung ist dementsprechend in einer ersten Ausführungsform ein Verfahren zur Behandlung von Metalloberflächen, bevorzugt Aluminium, Aluminiumlegierungen und Stahl, insbesondere für eine nachfolgende Beschichtung mit Überzugsmassen auf organischer Basis, wobei man die zuvor gereinigten Metalloberflächen mit einer wäßrigen Badlösung benetzt, die Chrom(III)-lonen, Fluoridionen und Phosphationen - jedoch keine Chrom(VI)-lonenAccordingly, the invention relates in a first embodiment to a method for treating metal surfaces, preferably aluminum, aluminum alloys and steel, in particular for a subsequent coating with coating compositions on an organic basis, the previously cleaned metal surfaces being wetted with an aqueous bath solution which contains chromium (III ) ions, fluoride ions and phosphate ions - but no chromium (VI) ions
- enthält, anschließend das aufgebrachte Gut - ohne zwischengeschalteten Spülvorgang - trocknet und durch Erhitzen in einen wasserünlöslichen Film umwandelt, welches dadurch gekennzeichnet ist, daß die wäßrige klare Badlösung
- a) die folgende Bestandteile in den nachstehend genannten Mengenbereichen enthält :
- b) und wobei das molare Verhältnis von Chrom(III)-lonen : Fluoridionen : Phosphationen im Bereich von 1 : 2,5 bis 3,5 : 0,3 bis 3,0 liegt. In einer weiteren Ausführungsform betrifft die Erfindung die für dieses Verfahren geeigneten wäßrigen Behandlungslösungen, d. h. eine wäßrige Badlösung zur Behandlung von Metalloberflächen, insbesondere von Aluminium, Aluminiumlegierungen und/oder Stahl, enthaltend Chrom(III)-lonen, Fluoridionen und Phosphationen - jedoch keine Chrom(VI)-Ionen -, welche dadurch gekennzeichnet ist, daß die Badlösung bei einem pH-Wert von 2 bis 3
- a) die folgenden Bestandteile in den nachstehend genannten Mengenbereichen enthält :
- b) wobei das molare Verhältnis von Chrom(III)-lonen : Fluoridionen : Phosphationen im Bereich von 1 : 2,5 bis 3,5 : 0,3 bis 3,0 liegt.
- a) die folgenden Bestandteile in den nachstehend genannten Mengenbereichen enthält :
- (a) contains the following components in the quantitative ranges specified below:
- b) and the molar ratio of chromium (III) ions: fluoride ions: phosphate ions is in the range from 1: 2.5 to 3.5: 0.3 to 3.0. In a further embodiment, the invention relates to the aqueous treatment solutions suitable for this process, ie an aqueous bath solution for the treatment of metal surfaces, in particular aluminum, aluminum alloys and / or steel, containing chromium (III) ions, fluoride ions and phosphate ions - but no chromium ( VI) -Ions -, which is characterized in that the bath solution at a pH of 2 to 3
- (a) contains the following constituents in the quantitative ranges specified below:
- b) where the molar ratio of chromium (III) ions: fluoride ions: phosphate ions is in the range from 1: 2.5 to 3.5: 0.3 to 3.0.
- (a) contains the following constituents in the quantitative ranges specified below:
Das erfindungsgemäße Verfahren eignet sich für die Oberflächenbehandlung aller hier einschlägigen Metalle, insbesondere also Eisenmetalle, Aluminium bzw. Aluminiumlegierungen, Zink und/oder Magnesium. Besonders geeignet ist die Erfindung für die Vorbehandlung von Bändern aus Aluminium bzw. Aluminiumlegierungen und kaltgewalztem Stahl für deren nachfolgenden Einsatz im Lebensmittel-Verpackungsbereich.The method according to the invention is suitable for the surface treatment of all metals relevant here, in particular therefore ferrous metals, aluminum or aluminum alloys, zinc and / or magnesium. The invention is particularly suitable for the pretreatment of strips made of aluminum or aluminum alloys and cold-rolled steel for their subsequent use in the food packaging sector.
Im erfindungsgemäßen Verfahren wird eine konventionell gereinigte und gespülte Metalloberfläche, beispielsweise also die Oberfläche von Bändern aus den zuvor genannten Metallen, nach Abquetschen des Wasserfilmes in an sich beliebiger Weise mit der wäßrigen Behandlungslösung derart benetzt, daß zweckmäßigerweise pro Quadratmeter der Fläche etwa 2 bis 20 ml, vorzugsweise etwa 3 bis 7 ml der wäßrigen Behandlungslösung aufgetragen werden. Dabei soll weiterhin pro Quadratmeter der Metalloberfläche der Gehalt an den zuvor genannten Aktivbestandteilen der wäßrigen Behandlungslösung innerhalb der folgenden Bereiche liegen : 5 bis 100 mg Chrom(III)-lonen, 5,5 bis 110 mg Fluoridionen und 6 bis 125 mg Phosphationen sowie etwa 1,5 bis 35 mg des organischen wasserlöslichen bzw. homogen wasserdispergierbaren Filmbildners.In the method according to the invention, a conventionally cleaned and rinsed metal surface, for example the surface of strips of the aforementioned metals, is squeezed in any way with the aqueous treatment solution after squeezing off the water film in such a way that expediently about 2 to 20 ml per square meter of the area , preferably about 3 to 7 ml of the aqueous treatment solution. The content of the aforementioned active constituents of the aqueous treatment solution should continue to be within the following ranges per square meter of the metal surface: 5 to 100 mg of chromium (III) ions, 5.5 to 110 mg of fluoride ions and 6 to 125 mg of phosphate ions, and about 1 , 5 to 35 mg of the organic water-soluble or homogeneously water-dispersible film former.
In einer bevorzugten Ausführungsform läßt man den aufgetragenen Flüssigfilm für eine Reaktionsdauer von etwa 1 bis 10 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 Metalloberlläche ein verformungsfähiger wasserunlöslicher Feststoffilm mit einer flächenbezogenen Masse von etwa 18 bis 370 mg/m2, vorzugsweise von etwa 50 bis 250 mg/m2 Metalloberfläche. Die Trocknung und/oder die thermische Behandlung des aufgebrachten Flüssigkeitsfilms bzw. der damit aufgetragenen Chemikalien kann insbesondere im Temperaturbereich von etwa 50 bis 300 °C erfolgen.In a preferred embodiment, the applied liquid film is allowed to act on the metal surface for a reaction time of about 1 to 10 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 on the metal shell l Smile Friend a ver f ormungsfähiger water-insoluble solid film with a basis weight of about 18 to 370 mg / m 2, preferably from about 50 to 250 mg / m 2 metal surface. The drying and / or the thermal treatment of the applied liquid film or the chemicals applied with it can take place in particular in the temperature range from approximately 50 to 300 ° C.
Chrom(III)-lonen und Fluoridionen werden am einfachsten durch Einsatz von Chrom(III)-Fluorid in das Bad eingebracht, wobei allerdings das Verhältnis von Chrom (III)-lonen : Fluoridionen im Bereich von 1 : 2,5 bis 3,5 schwanken kann. Der Phosphatgehalt wird durch Zugabe von Phosphaten bzw. Phosphorsäure mit nachfolgender partieller Neutralisation eingestellt. Dabei gilt, daß der Phosphatgehalt bezogen auf 1 Mol Chrom(III)-lonen bevorzugt im molaren Verhältnis von 0,3 bis 3,0 liegt. Der organische Filmbildner ist zweckmäßigerweise ein synthetisches Polymeres mit einem hinreichenden Gehalt an freien Carboxylgruppen, die seine Wasserlöslichkeit. bzw. homogene Dispergierbarkeit in Wasser 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 - der üblicherweise zwischen 2 und 3 liegt - ihre Klarlöslichkeit behalten. Im allgemeinen handelt es sich dabei um Polyacrylsäuren eines nicht zu hohen Molekulargewichtes, beispielsweise solche mit Molekulargewichten bis etwa 150 000, vorzugsweise bis etwa 100 000.Chromium (III) ions and fluoride ions are most easily introduced into the bath using chromium (III) fluoride, although the ratio of chromium (III) ions: fluoride ions is in the range from 1: 2.5 to 3.5 can fluctuate. The phosphate content is adjusted by adding phosphates or phosphoric acid with subsequent partial neutralization. It applies that the phosphate content based on 1 mol of chromium (III) ions is preferably in a molar ratio of 0.3 to 3.0. The organic film former is expediently a synthetic polymer with a sufficient content of free carboxyl groups, which is its water solubility. ensure homogeneous dispersibility in water. Particularly suitable are polymers of acrylic acid and / or methacrylic acid, which may also contain limited amounts of copolymers and the corresponding esters, nitriles and / or amides. Preferred organic film formers are clearly soluble polyacrylic acids, which retain their clear solubility in particular in the pH range of the aqueous treatment baths - which is usually between 2 and 3. In general, these are polyacrylic acids of a molecular weight which is not too high, for example those with molecular weights of up to about 150,000, preferably up to about 100,000.
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, aber auch ein Benetzen des Bandes durch Sprühen oder Tauchen mit anschließendem Abquetschen des überschüssigen Flüssigkeitsfilmes durch beispielsweise Kunststoff-beschichtete Egalisierwalzen oder regelbare Luftrakel sind anwendbar.The aqueous treatment solutions according to the invention can be applied to the pre-cleaned metal strips in any type of application which is suitable for producing a uniform, defined liquid film in the specified quantity ranges on the metal surface. In particular, the roller application process with two or three rollers has proven successful, but wetting of the strip by spraying or dipping with subsequent squeezing off of the excess liquid film by means of, for example, plastic-coated leveling rollers or adjustable air doctor blades can also be used.
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 glänzendes Finish ohne Verfärbungen des Grundmaterials. Sie erfüllen in Kombination mit nachfolgend aufgebrachten geeigneten organischen Beschichtungen die Forderungen für den Sektor der Lebensmittelverpackungen.Both acidic and alkaline cleaners are suitable for the pretreatment of the metal surfaces to be wetted according to the invention. The layers obtained with the aqueous treatment solution according to the invention provide a uniform, glossy finish without discoloration of the base material. In combination with suitable organic coatings applied below, they meet the requirements for the food packaging sector.
In einer Bandbeschichtungslinie wurde Aluminiumband der Legierung AIMg 5 zunächst im Spritzverfahren gereinigt und entfettet. Hierzu wurde eine saure Lösung verwendet mit einem Gehalt von 1 g/I H2SO4, 0,2 g/l HF und 1 g/l Tensidkombination. Die Reinigung wurde bei einer Temperatur von 60°C, 8 Sekunden und bei einem Spritzdruck von 1,5 bar durchgeführt. Anschließend wurde das Band mit warmen entsalztem Wasser gespült und das Spülwasser abgequetscht. Danach wurde mittels Walzenauftragsverfahren ein Flüssigfilm von 5 ml/m2 Oberfläche mit der erfindungsgemäßen Lösung aufgebracht, wodurch die Oberfläche pro m2 mit einem Flüssigfilm bedeckt ist, welcher 25 mg Cr3+, 27,5 mg F-, 31,3 mg PO4― und 8,75 mg Polyacrylsäure (« Acrylsol® A 1 - der Firma Röhm & Haas, Philadelphia. USA) enthält.Aluminum strip of the alloy AIMg 5 was first cleaned and degreased in a coil coating line. An acidic solution containing 1 g / IH 2 SO 4 , 0.2 g / l HF and 1 g / l surfactant combination was used for this. The cleaning was carried out at a temperature of 60 ° C., 8 seconds and at a spray pressure of 1.5 bar. The tape was then rinsed with warm demineralized water and the rinsing water squeezed out. A liquid film of 5 ml / m 2 surface was then applied with the solution according to the invention by means of roller application processes, whereby the surface per m 2 is covered with a liquid film containing 25 mg Cr 3+ , 27.5 mg F-, 31.3 mg PO 4 - and 8.75 mg of polyacrylic acid ("Acrylsol® A 1 - from Röhm & Haas, Philadelphia. USA) contains.
Nach einer Reaktionszeit von 3 Sekunden wurde das im Flüssigfilm enthaltene Wasser in einem Schwebetrockner mit 100 °C Umlufttemperatur und einer Metall-Objekttemperatur von ca. 50 °C abgedunstet, und ein wasserunlöslicher Film von 92,5 mg/m2 auf der Metalloberfläche erhalten.After a reaction time of 3 seconds, the water contained in the liquid film was evaporated in a floating dryer with a circulating air temperature of 100 ° C. and a metal object temperature of approx. 50 ° C., and a water-insoluble film of 92.5 mg / m 2 was obtained on the metal surface.
Anschließend wurde das so vorbehandelte Band mit einem PVC-Lack No. 8510-E-14-M der Fa. Dexter Midland Co. beschichtet und bei 240 °C Metall-Objekttemperatur eingebrannt. Dieses mittels No-Rinse-Technik chemisch vorbehandelte und lackierte Band wurde zu Deckeln für Getränkedosen verarbeitet und im Vergleich mit Deckeln mit bisher üblichen Konversionsschichten den für Getränkedosen spezifischen Prüfungen unterzogen.Then the tape pretreated in this way was coated with PVC varnish no. 8510-E-14-M from Dexter Midland Co. coated and baked at 240 ° C metal object temperature. This tape, which had been chemically pretreated and painted using the no-rinse technique, was processed into lids for beverage cans and, in comparison with lids with conversion layers that were customary to date, was subjected to the tests specific to beverage cans.
Die Ergebnisse mit dem erfindungsgemäß vorbehandelten Band waren in allen Fällen gleich gut oder besser, verglichen mit konventionell vorbehandeltem Band.The results with the tape pretreated according to the invention were equally good or better in all cases compared to conventionally pretreated tape.
Zur Herstellung einer erfindungsgemäßen Behandlungslösung wurden 2640 g Chromoxidhydrat mit einem Gehalt von 25 % Cr203 in einem auf 60 °C erhitzten Gemisch von 4 710 g entsalztem Wasser, 1 300 g Fluorwasserstoffsäure 40 %ig und 750 g Phosphorsäure 75 %ig unter Rühren gelöst. Nach Abkühlung der Lösung auf 30 °C wurden wiederum unter Rühren 2640 g Polyacrylsäure Typ Acrysol® A 1 der Firma Röhm & Haas zugegeben. Die so erhaltene Lösung wurde dann mit 88,5 Liter entsalztem Wasser verdünnt und zur Füllung der Chemcoaterwannen verwendet.To prepare a treatment solution according to the invention, 2640 g of chromium oxide hydrate containing 25% Cr 2 O 3 in a mixture of 4,710 g of deionized water, 1,300 g of 40% strength hydrofluoric acid and 750 g of 75% strength phosphoric acid were heated while stirring to 60 ° C. solved. After the solution had been cooled to 30 ° C., 2640 g of Acrysol® A 1 polyacrylic acid from Röhm & Haas were again added with stirring. The solution thus obtained was then diluted with 88.5 liters of deionized water and used to fill the chemcoater tubs.
Die Umdrehungsgeschwindigkeiten der Chemcoaterwalzen wurden so eingestellt, daß auf einem gereinigten und mit Wasser gespülten Aluminiumband bei einer Bandgeschwindigkeit von 100 m/Minute vermittels der Auftragswalzen des Chemcoaters ein Flüssigfilm von 8 ml/m2 Bandoberfläche aufgebracht wurde. Durch diese Applikation wurde das Band mit einem Flüssigkeitsfilm benetzt, welcher pro m2 Oberfläche 40 mg Cr3+, 44 mg F-, 50 mg PO4----und 14 mg Polyacrylsäure 100 %ig enthält und nach dem Trocknen eine flächenbezogene Masse von 148 mg/m2 auf dem Aluminium aufweist.The speeds of rotation of the chemcoater rollers were set such that a liquid film of 8 ml / m 2 of belt surface was applied to a cleaned and water-rinsed aluminum belt at a belt speed of 100 m / minute by means of the application rollers of the chemcoater. As a result of this application, the tape was wetted with a liquid film which contains 40 mg Cr 3+ , 44 mg F - , 50 mg PO 4 ---- and 14 mg polyacrylic acid 100% strength per m 2 of surface and, after drying, a mass per unit area of 148 mg / m 2 on the aluminum.
Nach einer Reaktionszeit von 3 Sekunden wurde der Wasseranteil des Flüssigfilmes mittels Warmlufttrockner entzogen und anschließend das Band auf eine Objekttemperatur von 200 °C erhitzt. Nach Abkühlung wurde der auf dem Band erhaltene Film mit 8 bis 10 mg Dioctylsebacat zur Verbesserung der Gleiteigenschaft benetzt. Die so erhaltene chemisch vorbehandelte Aluminiumoberfläche wurde mit für den Lebensmittelbereich geeigneten Lacken beschichtet und hinsichtlich ihrer Beständigkeit gegen Füllgüter und Umformverhalten geprüft. Es wurden bei allen Prüfungen technologische Werte gefunden, die im Vergleich zu Lösungen und Verfahren konventioneller Art mindestens gleichwertige, zum Teil sogar bessere Ergebnisse mit den erfindungsgemäßen Verfahren erzielten.After a reaction time of 3 seconds, the water portion of the liquid film was removed by means of a warm air dryer and then the tape was heated to an object temperature of 200 ° C. After cooling, the film obtained on the tape was wetted with 8 to 10 mg of dioctyl sebacate to improve the sliding property. The chemically pretreated aluminum surface thus obtained was coated with varnishes suitable for the food sector and tested for its resistance to filling goods and forming behavior. In all tests, technological values were found which, in comparison to conventional solutions and methods, achieved results which were at least equivalent, and in some cases even better, with the methods according to the invention.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83112610T ATE23573T1 (en) | 1982-12-23 | 1983-12-15 | PROCESSES FOR THE TREATMENT OF METAL SURFACES, ESPECIALLY THOSE OF ALUMINUM, ALUMINUM ALLOYS AND STEEL, AS WELL AS SUITABLE WATER BATH SOLUTIONS FOR THESE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19823247729 DE3247729A1 (en) | 1982-12-23 | 1982-12-23 | METHOD FOR TREATING METAL SURFACES, ESPECIALLY SUCH OF ALUMINUM, ALUMINUM ALLOYS AND STEEL, AND AQUEOUS AQUEOUS BATH SOLUTIONS THEREFOR |
| DE3247729 | 1982-12-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0111897A1 EP0111897A1 (en) | 1984-06-27 |
| EP0111897B1 true EP0111897B1 (en) | 1986-11-12 |
Family
ID=6181576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83112610A Expired EP0111897B1 (en) | 1982-12-23 | 1983-12-15 | Process for the treatment of metal surfaces, especially aluminium, aluminium alloy and steel ones, and aqueous bath solutions suitable therefor |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4761189A (en) |
| EP (1) | EP0111897B1 (en) |
| JP (1) | JPH076071B2 (en) |
| AT (1) | ATE23573T1 (en) |
| AU (1) | AU557724B2 (en) |
| BR (1) | BR8306981A (en) |
| CA (1) | CA1219790A (en) |
| DE (2) | DE3247729A1 (en) |
| ES (1) | ES8406563A1 (en) |
| GR (1) | GR79449B (en) |
| MX (1) | MX7298E (en) |
| NO (1) | NO162623C (en) |
| ZA (1) | ZA839574B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6096772A (en) * | 1983-10-31 | 1985-05-30 | Nippon Parkerizing Co Ltd | Pretreatment in chemical formation of aluminum alloy |
| JPS61136685A (en) * | 1984-12-07 | 1986-06-24 | Nippon Light Metal Co Ltd | Formation of hydrophilic and corrosion resistant film |
| NO168953C (en) * | 1986-08-27 | 1992-04-22 | Elektro Brite Gmbh | ACID CHROME PASSIVATOR FOR ZINC OR CADMIUM SURFACES |
| JP3239312B2 (en) * | 1994-03-31 | 2001-12-17 | 川崎製鉄株式会社 | Electrical steel sheet with electrical insulation coating with excellent corrosion resistance |
| DE4412138A1 (en) * | 1994-04-08 | 1995-10-12 | Henkel Kgaa | Chromium-free process for no-rinse treatment of aluminum and its alloys as well as suitable aqueous bath solutions |
| ES2102313B1 (en) * | 1994-07-29 | 1998-04-01 | Procoat S L | ANTICORROSIVE COMPOSITION FREE OF HEXAVALENT CHROME. |
| DE4443882A1 (en) * | 1994-12-09 | 1996-06-13 | Metallgesellschaft Ag | Process for applying phosphate coatings on metal surfaces |
| US6224657B1 (en) | 1998-10-13 | 2001-05-01 | Sermatech International, Inc. | Hexavalent chromium-free phosphate-bonded coatings |
| JP2003147544A (en) * | 2001-11-07 | 2003-05-21 | Nippon Parkerizing Co Ltd | Surface treatment film of zinc plated film, surface treatment solution for zinc plated film, and surface treatment method |
| CN101384751B (en) * | 2006-02-14 | 2013-01-02 | 汉高股份及两合公司 | Composition and processes of a dry-in-place trivalent chromium corrosion-resistant coating for use on metal surfaces |
| KR20090018067A (en) * | 2006-05-10 | 2009-02-19 | 헨켈 아게 운트 코. 카게아아 | Improved trivalent chromium-containing composition for use in corrosion resistant coating on metal surfaces |
| US10156016B2 (en) | 2013-03-15 | 2018-12-18 | Henkel Ag & Co. Kgaa | Trivalent chromium-containing composition for aluminum and aluminum alloys |
| DE102014222024A1 (en) | 2014-10-29 | 2016-06-16 | MTU Aero Engines AG | Slip and method of making an oxidation and corrosion resistant diffusion layer |
| NL2017398B1 (en) * | 2016-08-31 | 2018-03-08 | Ad Productions B V | Method of treating metal surfaces with an aqueous composition and aqueous composition |
| EP3659716A1 (en) * | 2018-11-27 | 2020-06-03 | Rhodia Operations | Polymers for metal surface treatment |
| WO2021233715A1 (en) * | 2020-05-19 | 2021-11-25 | Rhodia Operations | Polymers for metal surface treatment |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1769582C3 (en) * | 1967-06-14 | 1979-12-13 | British Chrome & Chemicals Ltd., Stockton-On-Tees (Grossbritannien) | Surface treatment agents for metals, processes for their production and their use for producing corrosion-resistant and electrically resistant coatings |
| JPS5145604A (en) * | 1974-10-17 | 1976-04-19 | Nippon Steel Corp | Seikorono uchibarihoshuji niokeru ronaikankihoho |
| US3989550A (en) * | 1975-04-21 | 1976-11-02 | Amchem Products, Inc. | Method of forming a hydrophilic coating on an aluminum surface |
| JPS5337550A (en) * | 1976-09-20 | 1978-04-06 | Nippon Paint Co Ltd | Surface treating agents for aluminum or aluminum alloy and surface treating process |
| ES452499A1 (en) * | 1976-10-05 | 1978-04-01 | Brugarolas Sa | Process for sealing anodic oxidation layers on aluminium surfaces and its alloys |
| US4183772A (en) * | 1978-01-30 | 1980-01-15 | Union Carbide Corporation | Composition and method for coating metal surfaces |
| US4131489A (en) * | 1978-03-31 | 1978-12-26 | Amchem Products, Inc. | Chromate conversion composition and method for coating aluminum using low concentrations of chromate, phosphate and fluoride ions |
| US4171231A (en) * | 1978-04-27 | 1979-10-16 | R. O. Hull & Company, Inc. | Coating solutions of trivalent chromium for coating zinc surfaces |
| US4191596A (en) * | 1978-09-06 | 1980-03-04 | Union Carbide Corporation | Method and compositions for coating aluminum |
| US4263059A (en) * | 1979-12-21 | 1981-04-21 | Rohco, Inc. | Coating solutions of trivalent chromium for coating zinc and cadmium surfaces |
| US4349392A (en) * | 1981-05-20 | 1982-09-14 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process |
| US4359345A (en) * | 1981-04-16 | 1982-11-16 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process |
-
1982
- 1982-12-23 DE DE19823247729 patent/DE3247729A1/en not_active Withdrawn
-
1983
- 1983-11-18 NO NO834243A patent/NO162623C/en unknown
- 1983-11-29 CA CA000442149A patent/CA1219790A/en not_active Expired
- 1983-12-15 EP EP83112610A patent/EP0111897B1/en not_active Expired
- 1983-12-15 AT AT83112610T patent/ATE23573T1/en active
- 1983-12-15 DE DE8383112610T patent/DE3367629D1/en not_active Expired
- 1983-12-19 GR GR73277A patent/GR79449B/el unknown
- 1983-12-20 BR BR8306981A patent/BR8306981A/en not_active IP Right Cessation
- 1983-12-21 AU AU22729/83A patent/AU557724B2/en not_active Ceased
- 1983-12-21 MX MX8310946U patent/MX7298E/en unknown
- 1983-12-22 ZA ZA839574A patent/ZA839574B/en unknown
- 1983-12-23 JP JP58252417A patent/JPH076071B2/en not_active Expired - Lifetime
- 1983-12-23 ES ES528361A patent/ES8406563A1/en not_active Expired
-
1987
- 1987-05-20 US US07/053,598 patent/US4761189A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN, unexamined applications, C Field, Vol. 5, No. 180, 19. November 1981 THE PATENT OFFICE JAPANESE GOVERNMENT, Seite 130 C 79,Kokai-No. 56-105 486 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ES528361A0 (en) | 1984-08-01 |
| ZA839574B (en) | 1984-08-29 |
| NO834243L (en) | 1984-06-25 |
| AU2272983A (en) | 1984-06-28 |
| AU557724B2 (en) | 1987-01-08 |
| NO162623C (en) | 1990-01-24 |
| NO162623B (en) | 1989-10-16 |
| ES8406563A1 (en) | 1984-08-01 |
| JPH076071B2 (en) | 1995-01-25 |
| CA1219790A (en) | 1987-03-31 |
| JPS59133373A (en) | 1984-07-31 |
| DE3367629D1 (en) | 1987-01-02 |
| DE3247729A1 (en) | 1984-07-05 |
| MX7298E (en) | 1988-04-26 |
| GR79449B (en) | 1984-10-30 |
| EP0111897A1 (en) | 1984-06-27 |
| US4761189A (en) | 1988-08-02 |
| ATE23573T1 (en) | 1986-11-15 |
| BR8306981A (en) | 1984-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0111897B1 (en) | Process for the treatment of metal surfaces, especially aluminium, aluminium alloy and steel ones, and aqueous bath solutions suitable therefor | |
| DE2433704C3 (en) | Use of aqueous dispersions containing zirconium compounds and polyacrylic acid for treating metal surfaces | |
| EP0754251B1 (en) | Chrome-free process for the no-rinse treatment of aluminium and its alloys, plus solutions suitable for use in the process | |
| DE69330138T3 (en) | METHOD AND COMPOSITIONS FOR TREATING METAL SURFACES | |
| EP0015020B2 (en) | Process for the surface treatment of metals and its use for the treatment of aluminium surfaces | |
| DE2715292C2 (en) | ||
| DE2428065C2 (en) | Process for sealing zinc phosphate coatings on steel substrates | |
| EP0774016B1 (en) | No-rinse phosphatising process | |
| DE69731731T2 (en) | PASSIVATION COMPOSITION AND METHOD OF COATING | |
| WO2000068458A1 (en) | Pretreatment of aluminum surfaces with chrome-free solutions | |
| EP1751327A1 (en) | Coloured conversion layers on metallic surfaces | |
| WO2001059181A2 (en) | Anti-corrosive agents and method for protecting metal surfaces against corrosion | |
| DE831632C (en) | Process for the production of coatings on aluminum and its alloys as well as means for carrying out the process | |
| DE2912759C2 (en) | Aqueous, acidic solution for producing a coating on surfaces made of aluminum or aluminum alloys | |
| DE3236247A1 (en) | METHOD FOR SURFACE TREATMENT OF ALUMINUM | |
| DE1521880B1 (en) | Process for the treatment of chemically applied coatings on metals with chromium-containing solutions | |
| WO1996034995A1 (en) | Chromium- and fluoride-free treatment of metallic surfaces | |
| EP0410497B1 (en) | Process for the passivate rinsing of phosphate coatings | |
| DE974713C (en) | Process for the production of coatings on metals | |
| WO1999024638A1 (en) | Corrosion protection for galvanised and alloy galvanised steel strips | |
| WO1996016205A1 (en) | Anticorrosive and friction-reducing treatment of metallic surfaces | |
| DE1112371B (en) | Process for applying coatings to aluminum and aluminum alloys | |
| DE1088309B (en) | Process for the treatment of iron surfaces for the purpose of increasing the corrosion resistance and improving the adhesive strength for organic coatings | |
| DE60127793T2 (en) | Chemically processed steel sheet with excellent corrosion resistance | |
| EP0055881A1 (en) | Method for the treatment of metal surfaces |
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 |
|
| AK | Designated contracting states |
Designated state(s): AT BE DE FR GB IT NL SE |
|
| 17P | Request for examination filed |
Effective date: 19841110 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE FR GB IT NL SE |
|
| REF | Corresponds to: |
Ref document number: 23573 Country of ref document: AT Date of ref document: 19861115 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 3367629 Country of ref document: DE Date of ref document: 19870102 |
|
| ET | Fr: translation filed | ||
| ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
| 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 |
|
| 26N | No opposition filed | ||
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19941205 Year of fee payment: 12 |
|
| EAL | Se: european patent in force in sweden |
Ref document number: 83112610.7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19951206 Year of fee payment: 13 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19951215 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19951215 Year of fee payment: 13 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19951230 Year of fee payment: 13 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19961215 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19961216 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19970701 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19961215 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19970701 |
|
| EUG | Se: european patent has lapsed |
Ref document number: 83112610.7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20011212 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20020215 Year of fee payment: 19 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20021219 Year of fee payment: 20 |
|
| 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: 20021231 |
|
| BERE | Be: lapsed |
Owner name: *GERHARD COLLARDIN G.M.B.H. Effective date: 20021231 |
|
| 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: 20030901 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |