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EP0793738B1 - Anticorrosive and friction-reducing treatment of metallic surfaces - Google Patents

Anticorrosive and friction-reducing treatment of metallic surfaces Download PDF

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Publication number
EP0793738B1
EP0793738B1 EP95940171A EP95940171A EP0793738B1 EP 0793738 B1 EP0793738 B1 EP 0793738B1 EP 95940171 A EP95940171 A EP 95940171A EP 95940171 A EP95940171 A EP 95940171A EP 0793738 B1 EP0793738 B1 EP 0793738B1
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EP
European Patent Office
Prior art keywords
acid
aqueous solution
component
carbon atoms
cans
Prior art date
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EP95940171A
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German (de)
French (fr)
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EP0793738A1 (en
Inventor
Henry Rossmaier
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0793738A1 publication Critical patent/EP0793738A1/en
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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

Definitions

  • the invention is in the field of surface treatment of molded Metal parts made of aluminum or aluminum alloys as well as tinned Steel (tinplate). It particularly affects beverage and food cans from these materials.
  • the invention pursues the goal in the process of Can manufacturing the can surfaces with a paintable, anti-corrosion To provide a layer that facilitates the drainage of water and which leads in particular to the fact that the coefficient of friction reduced between touching cans and thus the transport of Cans on conveyor belts are lightened, while maintaining porosity a later painting is reduced.
  • Tins made of tinned steel (tinplate) and aluminum (or aluminum alloys, which in the following for simplicity under "aluminum” are summarized) are for storing food and in particular of beverages widely used.
  • these are usually washed after shaping, for example acidic or alkaline cleaners are commercially available.
  • This Cleaner solutions must have sufficient solvent power for those concerned Contain metals to effectively remove metal debris from the cans.
  • the can surface itself can be roughened by the metal attack be, which increases the friction between touching cans elevated. This will reduce the speed of the can transport Conveyor belts are reduced and especially in places where there is separation If the cans build up a can backlog, the can can be transported completely be blocked. Because this increases the capacity of the production plant reduced, one tries to condition the can surfaces in such a way that the friction between touching cans is as low as possible becomes.
  • chrome-free methods for surface treatment are in the prior art known from aluminum, which is usually inorganic acids, especially phosphoric acid, hydrofluoric acid or other sources of fluoride and / or use complex fluorides with or without additional Use organic polymers.
  • inorganic acids especially phosphoric acid, hydrofluoric acid or other sources of fluoride and / or use complex fluorides with or without additional Use organic polymers.
  • US-A-4,992,116 an aqueous acid treatment solution, the phosphate, a fluoric acid of Zr, Ti, Hf or Si and a polyphenol compound contains a Mannich adduct of a substituted amine with a polyalkylene phenol or represents a tannin.
  • EP-B-8942 discloses treatment solutions preferably for aluminum cans containing a) 0.5 to 10 g / l polyacrylic acid or an ester here from and b) 0.2 to 8 g / l at least one of the compounds hexafluorozirconic acid, hexafluorotitanic acid or hexafluorosilicic acid.
  • Conversion solutions for aluminum are known from US Pat. No. 4,470,853 among others 10 to 150 ppm zircon, 20 to 250 ppm fluoride, 15 to 100 ppm of phosphate and 30 to 125 ppm of tannin. Your pH is in the Range 2.3 to 2.95.
  • the use of tannin in surface treatment of aluminum is also taught in DE-A-24 46 492, according to which one Aluminum is treated with an acidic, phosphate-containing solution, the one Contains metal salt of tannin in amounts between 0.1 and 10 g / l.
  • W091 / 14014 describes an aqueous solution containing ions of Fe, Zr, Sn, Al or Ce, metal etching acids such as hydrofluoric acid, alkoxylated phosphoric acid esters and a combination of alkoxylated alcohols and alkoxylated alkylphenols.
  • the W094 / 01517 describes a Process for the friction-reducing conversion treatment of metal cans, in which, in addition to inorganic metal compounds, alkoxylated or not alkoxylated castor oil triglycerides, hydrogenated castor oil derivatives, alkoxylated or non-alkoxylated amine salts of fatty acids, alkoxylated or non-alkoxylated amino fatty acids, alkoxylated or non-alkoxylated Fatty amine N-oxides, alkoxylated or non-alkoxylated quaternary ammonium salts or water-soluble organic polymers are used.
  • EP-A-612 833 proposes a surface treatment to reduce friction with an ester between a polyglycerin and fatty acids in front.
  • An effective surface treatment for tinplate or aluminum cans is intended on the one hand to meet the different requirements with regard to corrosion protection as well as freedom from pores and adhesion of a subsequent painting, each according to different requirements according to different Criteria are checked, sufficient and, on the other hand, the most effective Ensure a reduction in friction.
  • Systems known to date compromises between the different requirements and do not fully satisfy all points.
  • the task of The present invention is a solution for surface treatment of metal cans to provide an improved range of services with regard to the different requirements.
  • the alkyl radicals R 1 can represent radicals with a certain chain length and a certain number of double bonds. For economic reasons, however, it is preferable to use amine oxides or ammonium salts derived from oleochemical raw materials. In these cases, the R 1 radicals have a distribution of chain lengths and double bonds as are characteristic of the fatty acids in vegetable or animal fats and oils. Preference is given to using those compounds of the general formula (I) in which R 1 represents a mixture of alkyl groups, such as in those fatty acid mixtures which can be obtained by hydrolysis of coconut oil, palm kernel oil or animal tallow.
  • Suitable amine oxides of the general formula (I) are: bis (2-hydroxyethyl) cocoalkylamine oxide (Aromox R C / 12), bis (2-hydroxyethyl) tallow alkylamine oxide (Aromox R T / 12), dimethyl cocoalkylamine oxide (Aromox R DMC), hydrogenated dimethyl tallow alkylamine oxide (Aromox R DMHT) and dimethylhexadecylamine oxide (Aromox R DM-16), all of which are available from Akzo Chemicals Inc.
  • quaternary ammonium salts of the general formula (I) are: dodecyltrimethylammonium chloride (Arquad R 12-37W), octadecyltrimethylammonium chloride (Arquad R 18-50), dimethylbenzyl- (C 12-18 ) alkylammonium chloride (Arquad R B-100), Tris ( 2-hydroxyethyl) tallow alkyl ammonium acetate (Ethoquad R T / 13) and methyl bis (2-hydroxy-2-methylethyl) ammonium methyl sulfate (Propoquad R T / 12), all of which are also available from Akzo Chemicals Inc.
  • Preferred alkylamine oxides or quaternary ammonium salts of the general formula (I) are those which carry radicals R 2 , R 3 and, in the case of the quaternary ammonium salts, also R 4 , which form when the alkylamines are reacted with ethylene oxide, propylene oxide or butylene oxide. Examples include 2-hydroxyethyl groups and 2-hydroxy-2-methylethyl groups. As is customary in alkoxylation reactions, radicals R 2 , R 3 and R 4 can also be formed in which several alkoxy groups are linked to one another via ether bonds. Such polyether residues with up to 8 carbon atoms are also within the scope of the invention. However, particular preference is given to those compounds of the general formula (I) which bear 2-hydroxyethyl groups as radicals R 2 , R 3 and optionally R 4 .
  • the components of the Group a) represents the active ingredients which reduce friction the effect of the components of group b) is one-, two- or three-base Hydroxycarboxylic acids with 4 to 7 carbon atoms in the molecule, the sum of hydroxyl and carboxyl groups is at least 3, primarily in that a later applied varnish has a reduced porosity and thus has an increased corrosion resistance.
  • the porosity value referred to in the Anglo-Saxon literature as "Metal Exposure Value", MEV, can be determined and determined by an electrochemical measurement one of the quality requirements of the beverage industry for coated beverage cans
  • This measured variable can, for example, with an "Enamel Rater MK “from Manfred Kunke, Berlin (Germany) or with a “Enamel Rater” from Wilkens-Anderson Co, Chicaco, Illinois become.
  • the measurement is based on the fact that the beverage can is painted on the inside with an electrolytic solution (50.6 g of common salt and 1.19 g of dioctyl sodium sulfosuccinate in 5 liters of deionized water) and fill the can as an electrode switches.
  • a counter electrode is immersed in the electrolyte solution and after switching on the voltage and a waiting time of 4 sec. the flowing Current read in mA. With a perfect coating of the can there is none Current flow expected. Increasing current flow in mA, the "Metal Exposure Value "shows an increasing permeability of the coating for ions that can be interpreted as porosity. For one later filling with soft drinks is required, for example, that the average MEV is below 5 mA at a test voltage of 6.3 V should lie.
  • Suitable hydroxycarboxylic acids are malic acid, tartaric acid, citric acid and in particular those carboxylic acids which can be obtained by oxidation of pentose and hexose type sugars.
  • suitable carboxylic acids are gluconic acid, sugar acid, mannosugar acid, mucic acid and glucuronic acid. Gluconic acid is particularly preferred.
  • These acids can be used as such or in the form of their water-soluble salts, in particular their sodium salts.
  • the hydroxycarboxylic acids are, depending on their pK partly as such and partly in the form of their anions.
  • the other main components of the treatment solution according to the invention, c) and d), are in solutions for the conversion treatment of aluminum surfaces well known.
  • the use of hexafluorozirconate is preferred. It is immaterial whether the complex fluorides as water-soluble salts, for example as sodium or ammonium salts, or used as free acids.
  • the complex fluorine compounds so with the mineral acids of the Group d) or their acidic or neutral salts are combined in such a way that the treatment solution according to the invention has a pH in the effective range from 2.3 to 3.3. At pH values outside this range, the Training the desired corrosion-protecting and friction-reducing Layer the more unsatisfactory the further you go from the specified Area removed.
  • component d) 10 to 100 wt .-% of phosphoric acid or whose anions exist. If not phosphoric acid as the only acid of the Group d) is used, the concomitant use of nitric acid or their anions advantageous.
  • tannin in the concentration range 50 to 500 mg / l increases the Effect of group b) hydroxycarboxylic acids on the reduction the "metal exposure value" of a subsequent coating. Accordingly, it is preferred that the treatment solution according to the invention additionally Contains tannin. Tannins (compare, for example, Römpp Chemie Lexicon 9th edition 1992, keyword “Tannin”) stands as a group name for a number of natural polyphenols of very diverse compositions, which can be derived from gallic acid. Here are the gallic acid derivatives often esterified with glucose before. In the form of herbal extracts The tannins of different origins represent a well-known group of active ingredients for leather tanning.
  • the treatment solution contains, by means of the components of group a), surface-active components which tend to foam, it may be necessary to add defoamers to the treatment baths in the case of strong bath movements, such as for spray systems. Amounts in the range of 50 to 500 mg / l should generally be sufficient.
  • suitable defoamers are alkyl polyalkoxy esters. A suitable polyalkoxy ester of this type is available under the trade name Foamaster R C14 from Henkel KGaA, Düsseldorf (Germany).
  • a further improvement of the coating, especially with regard to their paintability can be achieved by using the treatment solution additionally water-soluble or water-dispersible organic Add polymers in concentrations from about 100 to about 1000 mg / l.
  • these polymers can be selected from h) homopolymers or heteropolymers of ethylene oxide, propylene oxide and / or butylene oxide, i) homopolymers or heteropolymers of acrylic acid, maleic acid and / or derivatives thereof, k) homo- or heteropolymers of vinylphenol and / or vinylphenol derivatives, 1) Homopolymers or heteropolymers of vinyl alcohol and / or vinyl alcohol derivatives. Polymers of the type mentioned are commercially available.
  • the polyvinylphenol derivatives of group k) are obtainable by a Mannich reaction from Polyvinylphenol with aldehydes with alkylamines.
  • a reaction product of poly (4-vinylphenol) with formaldehyde and 2-alkylamino-1-ethanol is contained in W092 / 07973.
  • compositions of the invention have become ready for use Treatment solutions described. It is of course possible to do this Baths by mixing together the individual components in the specified Prepare concentration areas directly on site. For the user such treatment solutions, however, it is cheaper, from a manufacturer to obtain aqueous concentrates of the treatment solutions and these on site by diluting with water to the concentration ranges of the application solutions adjust. Accordingly, the invention also includes aqueous Concentrates of the treatment solutions, which are diluted with water Treatment solutions according to the invention result. It is technical and economically most attractive to adjust the concentrates so that them by diluting them with water in a volume ratio between 1:50 and 1:200 the ready-to-use treatment solutions are obtained can. For example, the concentrate can be adjusted so that it to prepare the ready-to-use treatment solution with water in proportion Must be diluted 1: 100.
  • the treatment solution according to the invention preferably comes in one process for the production of cans, in particular beverage cans made of aluminum alloys, for use.
  • the preformed cans in the Usually subjected to one or two-stage acidic or alkaline cleaning, which is usually followed by a rinse with tap water.
  • the doses are brought in with the treatment solution according to the invention Touch, for example by immersing the cans in the solution or can be done by spraying the cans with the solution.
  • the temperature of the treatment solution is between 30 and 60 ° C and in particular 40 to 45 ° C.
  • the duration of treatment should be 10 do not fall below sec.
  • a treatment duration of more than 120 sec. brings no technical advantage. For example, it is convenient to have one Treatment duration of about 30 seconds to choose.
  • the invention encompasses also a method of producing an anti-corrosion, anti-friction and the protective layer on surfaces which improves the paintability made of aluminum or tin and their alloys, characterized in that that the surfaces with an aqueous solution after a or more of claims 1 to 8, which have a temperature in the range of 30 up to 60 ° C, for a period between 10 and 120 seconds in contact brings, which one preferably for the treatment of cans made of aluminum or uses aluminum alloys.
  • the invention was tested on aluminum beverage cans with a volume between 330 and 350 ml, as are customary for soft drinks.
  • the preformed cans were first cleaned (acidic cleaner Ridoline R 124, Henkel KGaA, Düsseldorf; 54 to 60 ° C, 1 minute) and then rinsed with tap water at room temperature. Thereafter, the surface treatment was carried out with treatment solutions according to the invention and with comparison solutions according to the table with pH values in the range between 2.45 and 2.93 at temperatures between 40 and 45 ° C. for a treatment period of 30 seconds in spraying. This was followed by rinsing with tap water, followed by rinsing with demineralized water, each at room temperature, after which the cans were dried at 150 ° C. for 5 minutes.
  • the well water resistance was determined in that the unpainted cans for 30 minutes in a 66 ° C solution of 0.2 g / l Sodium tetraborate decahydrate were dipped, then with fully desalinated Rinsed water and dried at 105 ° C in a drying oven. The can bottoms were then assessed visually for the degree of discoloration. No or a slight discoloration is considered acceptable, a dark or irregular discoloration as unacceptable. Either those with the method variants according to the invention as well as with comparison methods Doses treated according to the prior art passed these Corrosion resistance test.
  • the surface friction of the unpainted beverage cans was determined on a tilting table. For this, 3 doses are treated equally used. Two cans are placed side by side on the tilting table arranged so that its longitudinal axis is perpendicular to the tilt axis. A third can with its longitudinal axis is perpendicular to this pair of cans to the tilt axis so that it is about 0.5 cm is shifted in the direction of the tilt axis, whereby it is opposed to the lower cans are placed with the open side in the direction of the tilt axis. The tilting table is then automatically tilted at a constant speed and the angle of inclination ⁇ was found at which the upper box slipped while touching a switch.
  • the tangent of the angle of inclination ⁇ , in which the slipping takes place, is called the coefficient of friction.
  • 6 used the same treated doses, of which 3 each for an experiment to be chosen. 6 independent measurements with different ones are carried out Combinations of cans. The 6 measurements become the Average determined.
  • the treatment solutions according to the invention and the comparison solutions determined according to the prior art coefficient of friction showed no significant differences and were in the range from 0.476 to 0.514.
  • the cans connected as electrodes were filled with an electrolyte solution (50.6 g of sodium chloride and 1.19 g of dioctyl sodium sulfosuccinate in 5 l of completely deionized water), into which a metal bracket was immersed as a counter electrode. After applying the voltage, the current was measured in mA after 4 seconds and set as the MEV value. An upper MEV value of 5 mA is specified as the test criterion for beverage cans for soft drinks. The results obtained are entered in the table. The table also contains the number of doses that were measured per treatment solution, the mean MEV value, the maximum observed MEV value and the number of doses at which the specification was exceeded by a maximum MEV value of 5 mA.
  • Pretreatment Solutions and Metal Exposure Value (MEV) Basic recipe: 400 mg / l tris (2-hydroxyethyl) tallow ammonium acetate 145 mg / l hexafluorozirconic acid 66 mg / l phosphoric acid 266 mg / l nitric acid 32 mg / l hydrofluoric acid 200 mg / l defoamer (alkyl polyalkoxy ester, Foamaster R C14, Henkel KGaA, Düsseldorf) Additions of sodium gluconate and tannin Trial No.
  • MUV Metal Exposure Value

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  • 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)
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  • Application Of Or Painting With Fluid Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Description

Die Erfindung liegt auf dem Gebiet der Oberflächenbehandlung von geformten Metallteilen aus Aluminium oder Aluminiumlegierungen sowie aus verzinntem Stahl (Weißblech). Sie betrifft insbesondere Getränke- und Lebensmitteldosen aus diesen Materialien. Die Erfindung verfolgt das Ziel, im Prozeß der Dosenherstellung die Dosenoberflächen mit einer überlackierbaren, korrosionsschützenden Schicht zu versehen, die das Ablaufen von Wasser erleichtert und die insbesondere dazu führt, daß sich der Reibungskoeffizient zwischen einander berührenden Dosen verringert und damit der Transport der Dosen auf Transportbändern erleichtert wird, wobei gleichzeitig die Porosität einer späteren Lackierung verringert wird.The invention is in the field of surface treatment of molded Metal parts made of aluminum or aluminum alloys as well as tinned Steel (tinplate). It particularly affects beverage and food cans from these materials. The invention pursues the goal in the process of Can manufacturing the can surfaces with a paintable, anti-corrosion To provide a layer that facilitates the drainage of water and which leads in particular to the fact that the coefficient of friction reduced between touching cans and thus the transport of Cans on conveyor belts are lightened, while maintaining porosity a later painting is reduced.

Dosen aus verzinntem Stahl (Weißblech) sowie aus Aluminium (bzw. aus Aluminiumlegierungen, die im folgenden der Einfachheit wegen unter "Aluminium" zusammengefaßt werden) sind zum Aufbewahren von Lebensmitteln und insbesondere von Getränken weit verbreitet. Im Prozeß der Dosenherstellung werden diese nach der Formgebung üblicherweise gewaschen, wozu beispielsweise saure oder alkalische Reiniger kommerziell erhältlich sind. Diese Reinigerlösungen müssen ein ausreichendes Lösevermögen für die betreffenden Metalle aufweisen, um Metallabrieb aus den Dosen wirkungsvoll zu entfernen. Durch den Metallangriff kann dabei die Dosenoberfläche selbst aufgerauht werden, wodurch sich die Reibung zwischen sich berührenden Dosen erhöht. Hierdurch wird die Geschwindigkeit des Dosentransports auf den Transportbändern verringert und besonders an Stellen, wo sich durch Vereinzelung der Dosen ein Dosenrückstau bildet, kann der Dosentransport völlig blockiert werden. Da sich hierdurch die Kapazität der Produktionsanlage verringert, ist man bestrebt, die Dosenoberflächen so zu konditionieren, daß die Reibung zwischen sich berührenden Dosen möglichst gering wird. Tins made of tinned steel (tinplate) and aluminum (or aluminum alloys, which in the following for simplicity under "aluminum" are summarized) are for storing food and in particular of beverages widely used. In the process of making cans these are usually washed after shaping, for example acidic or alkaline cleaners are commercially available. This Cleaner solutions must have sufficient solvent power for those concerned Contain metals to effectively remove metal debris from the cans. The can surface itself can be roughened by the metal attack be, which increases the friction between touching cans elevated. This will reduce the speed of the can transport Conveyor belts are reduced and especially in places where there is separation If the cans build up a can backlog, the can can be transported completely be blocked. Because this increases the capacity of the production plant reduced, one tries to condition the can surfaces in such a way that the friction between touching cans is as low as possible becomes.

Das Aufbringen einer reibungsvermindernden Schicht darf jedoch nicht dazu führen, daß die Haftung von zum Korrosionsschutz und/oder aus dekorativen Gründen aufgebrachten Lackierungen, Beschriftungen oder sonstigen Beschichtungen leidet. Weiterhin muß die Beschichtung gewährleisten, daß die je nach Füllgut der Dosen unterschiedlichen Anforderungen hinsichtlich Korrosionsbeständigkeit erfüllt werden. Dabei sollen nur solche Wirkstoffe zum Einsatz kommen, die allgemein ökologisch und insbesondere lebensmitteltechnisch unbedenklich sind. Beispielsweise ist man aus Umweltaspekten bestrebt, auf chromhaltige Reagenzien zu verzichten.However, the application of a friction-reducing layer must not do this lead to the liability of corrosion protection and / or decorative Paintings, inscriptions or other coatings applied for reasons suffers. Furthermore, the coating must ensure that the Depending on the contents of the cans, different requirements regarding Corrosion resistance can be met. Only such active ingredients should be used are used, which are generally ecological and in particular food technology are harmless. For example, one is from environmental aspects endeavors to dispense with chrome-containing reagents.

Im Stand der Technik sind verschiedene chromfreie Verfahren zur Oberflächenbehandlung von Aluminium bekannt, die in der Regel anorganische Säuren, insbesondere Phosphorsäure, Flußsäure oder sonstige Quellen für Fluorid und/oder komplexe Fluoride einsetzen und die mit oder ohne zusätzlicher Verwendung organischer Polymere arbeiten. Beispielsweise beschreibt die US-A-4,992,116 eine wäßrige saure Behandlungslösung, die Phosphat, eine Fluorosäure von Zr, Ti, Hf oder Si sowie eine Polyphenolverbindung enthält, die ein Mannich-Addukt eines substituierten Amins an ein Polyalkylenphenol oder ein Tannin darstellt. Die EP-B-8942 offenbart Behandlungslösungen, vorzugsweise für Aluminiumdosen, enthaltend a) 0,5 bis 10 g/l Polyacrylsäure oder eines Esters hier von und b) 0,2 bis 8 g/l mindestens einer der Verbindungen Hexafluorozirkonsäure, Hexafluorotitansäure oder Hexafluorokieselsäure.Various chrome-free methods for surface treatment are in the prior art known from aluminum, which is usually inorganic acids, especially phosphoric acid, hydrofluoric acid or other sources of fluoride and / or use complex fluorides with or without additional Use organic polymers. For example, describes US-A-4,992,116 an aqueous acid treatment solution, the phosphate, a fluoric acid of Zr, Ti, Hf or Si and a polyphenol compound contains a Mannich adduct of a substituted amine with a polyalkylene phenol or represents a tannin. EP-B-8942 discloses treatment solutions preferably for aluminum cans containing a) 0.5 to 10 g / l polyacrylic acid or an ester here from and b) 0.2 to 8 g / l at least one of the compounds hexafluorozirconic acid, hexafluorotitanic acid or hexafluorosilicic acid.

Aus der US-A-4,470,853 sind Konversionslösungen für Aluminium bekannt, die unter anderem 10 bis 150 ppm Zirkon, 20 bis 250 ppm Fluorid, 15 bis 100 ppm Phosphat und 30 bis 125 ppm Tannin enthalten. Ihr pH-Wert liegt im Bereich 2,3 bis 2,95. Die Verwendung von Tannin bei der Oberflächenbehandlung von Aluminium wird auch in der DE-A-24 46 492 gelehrt, wonach man Aluminium mit einer sauren, phosphathaltigen Lösung behandelt, die ein Metallsalz von Tannin in Mengen zwischen 0,1 und 10 g/l enthält.Conversion solutions for aluminum are known from US Pat. No. 4,470,853 among others 10 to 150 ppm zircon, 20 to 250 ppm fluoride, 15 to 100 ppm of phosphate and 30 to 125 ppm of tannin. Your pH is in the Range 2.3 to 2.95. The use of tannin in surface treatment of aluminum is also taught in DE-A-24 46 492, according to which one Aluminum is treated with an acidic, phosphate-containing solution, the one Contains metal salt of tannin in amounts between 0.1 and 10 g / l.

Für die Verringerung der Reibung zwischen Aluminiumdosen beim Dosentransport wurden bereits unterschiedliche Lösungen vorgeschlagen. Beispielsweise beschreibt die W091/14014 eine wäßrige Lösung, die Ionen von Fe, Zr, Sn, Al oder Ce, metallätzende Säuren wie beispielsweise Flußsäure, alkoxylierte Phosphorsäureester sowie eine Kombination alkoxylierter Alkohole und alkoxylierter Alkylphenole enthält. Die W094/01517 beschreibt ein Verfahren zur reibungsvermindernden Konversionsbehandlung von Metalldosen, bei denen neben anorganischen Metallverbindungen alkoxylierte oder nicht alkoxylierte Castoröl-Triglyceride, hydrierte Castorölderivate, alkoxylierte oder nicht alkoxylierte Aminsalze von Fettsäuren, alkoxylierte oder nicht alkoxylierte Aminofettsäuren, alkoxylierte oder nicht alkoxylierte Fettamin-N-oxide, alkoxylierte oder nicht alkoxylierte quartäre Ammoniumsalze oder wasserlösliche organische Polymere zum Einsatz kommen. Dabei werden solche Aminoxide oder quartäre Ammoniumsalze eingesetzt, bei denen mindestens ein Alkylrest bis zu 20 Kohlenstoffatome enthält. Aminverbindungen dieses Typs kommen auch im Rahmen der vorliegenden Erfindung zum Einsatz. Die EP-A-612 833 schlägt zur Reibungsverminderung eine Oberflächenbehandlung mit einem Ester zwischen einem Polyglycerin und Fettsäuren vor.For reducing the friction between aluminum cans when transporting cans Different solutions have already been proposed. For example W091 / 14014 describes an aqueous solution containing ions of Fe, Zr, Sn, Al or Ce, metal etching acids such as hydrofluoric acid, alkoxylated phosphoric acid esters and a combination of alkoxylated alcohols and alkoxylated alkylphenols. The W094 / 01517 describes a Process for the friction-reducing conversion treatment of metal cans, in which, in addition to inorganic metal compounds, alkoxylated or not alkoxylated castor oil triglycerides, hydrogenated castor oil derivatives, alkoxylated or non-alkoxylated amine salts of fatty acids, alkoxylated or non-alkoxylated amino fatty acids, alkoxylated or non-alkoxylated Fatty amine N-oxides, alkoxylated or non-alkoxylated quaternary ammonium salts or water-soluble organic polymers are used. Here amine oxides or quaternary ammonium salts are used in which contains at least one alkyl radical up to 20 carbon atoms. Amine compounds this type also come within the scope of the present invention Commitment. EP-A-612 833 proposes a surface treatment to reduce friction with an ester between a polyglycerin and fatty acids in front.

Eine wirkungsvolle Oberflächenbehandlung von Weißblech- oder Aluminiumdosen soll einerseits den unterschiedlichen Anforderungen hinsichtlich Korrosionsschutz sowie Porenfreiheit und Haftung einer anschließenden Lackierung, die jeweils nach unterschiedlichen Anforderungen nach verschiedenen Kriterien geprüft werden, genügen und andererseits eine möglichst effektive Reibungsverminderung gewährleisten. Bisher bekannte Systeme stellen jeweils Kompromisse zwischen den unterschiedlichen Anforderungen dar und befriedigen nicht in jeweils allen Punkten vollständig. Die Aufgabe der vorliegenden Erfindung besteht darin, eine Lösung zur Oberflächenbehandlung von Metalldosen zur Verfügung zu stellen, die ein verbessertes Leistungsspektrum hinsichtlich der unterschiedlichen Anforderungen aufweist. Insbesondere hat sich gezeigt, daß bei Verfahren zur Konversionsbehandlung und Reibungsverminderung gemäß der W094/01517, bei denen als reibungsvermindernde Wirkstoffe Fettamin-N-oxide oder quartäre Fettalkylammoniumsalze zum Einsatz kommen, die Porosität einer nachfolgenden Lackierung den Anforderungen speziell der Getränkeindustrie nicht zuverlässig genügt.An effective surface treatment for tinplate or aluminum cans is intended on the one hand to meet the different requirements with regard to corrosion protection as well as freedom from pores and adhesion of a subsequent painting, each according to different requirements according to different Criteria are checked, sufficient and, on the other hand, the most effective Ensure a reduction in friction. Systems known to date compromises between the different requirements and do not fully satisfy all points. The task of The present invention is a solution for surface treatment of metal cans to provide an improved range of services with regard to the different requirements. In particular, it has been shown that in processes for conversion treatment and friction reduction according to W094 / 01517, in which as a friction reducing Active ingredients fatty amine N-oxides or quaternary fatty alkyl ammonium salts are used, the porosity of a subsequent painting meets the requirements especially the beverage industry is not reliably sufficient.

Die Aufgabe wird gelöst durch eine wäßrige Lösung zum Behandeln von Oberflächen aus Aluminium oder Zinn sowie jeweils deren Legierungen, die einen pH-Wert im Bereich 2,3 bis 3,3 aufweist und zumindest die folgenden Komponenten enthält:

  • a) 0,14 bis 2,25 mMol/l einer Komponenten ausgewählt aus oberflächenaktiven quartären Ammoniumsalzen oder Aminoxiden der allgemeinen Formel (I)
    Figure 00040001
    wobei R1 ein gesättigter oder ein- oder mehrfach ungesättigter Alkylrest mit 8 bis 22 C-Atomen, R2 und R3 unabhängig voneinander ein Alkyl- oder Hydroxyalkylrest mit 1 bis 8 C-Atomen oder ein Aryl- oder Alkylarylrest mit 6 bis 10 C-Atomen, R4 ein Rest des Typs R2 oder R3 oder ein -0--Rest und X- ein einwertiges Anion oder ein einwertiges Äquivalent eines mehrwertigen Anions bedeuten und a dann = 0 ist, wenn R4 ein -0-- Rest bedeutet, und ansonsten a = 1 ist,
  • b) 0,25 bis 1,5 mMol/l einer oder mehrerer ein- zwei- oder dreibasischer Hydroxycarbonsäuren mit 4 bis 7 C-Atomen im Molekül, wobei die Summe aus Hydroxyl- und Carboxylgruppen mindestens 3 beträgt, oder jeweils deren Anionen,
  • c) 0,4 bis 2 mMol/l eines oder mehrerer komplexer Fluoride und
  • d) 20 bis 500 mg/l Mineralsäuren, ausgewählt aus Phosphorsäure, Salpetersäure und Schwefelsäure, oder jeweils deren Anionen.
    • The object is achieved by an aqueous solution for treating surfaces made of aluminum or tin and their alloys in each case, which has a pH in the range from 2.3 to 3.3 and contains at least the following components:
  • a) 0.14 to 2.25 mmol / l of a component selected from surface-active quaternary ammonium salts or amine oxides of the general formula (I)
    Figure 00040001
    where R 1 is a saturated or mono- or polyunsaturated alkyl radical with 8 to 22 C atoms, R 2 and R 3 independently of one another an alkyl or hydroxyalkyl radical with 1 to 8 C atoms or an aryl or alkylaryl radical with 6 to 10 C -Atoms, R 4 is a radical of the type R 2 or R 3 or a -0 - radical and X - is a monovalent anion or a monovalent equivalent of a polyvalent anion and a is = 0 if R 4 is a -0 - - Rest means, and otherwise a = 1,
  • b) 0.25 to 1.5 mmol / l of one or more mono- or di-basic hydroxycarboxylic acids having 4 to 7 carbon atoms in the molecule, the sum of hydroxyl and carboxyl groups being at least 3, or their anions,
  • c) 0.4 to 2 mmol / l of one or more complex fluorides and
  • d) 20 to 500 mg / l mineral acids, selected from phosphoric acid, nitric acid and sulfuric acid, or their anions in each case.

    • Dabei können die Alkylreste R1 Reste mit einer bestimmten Kettenlänge und einer bestimmten Anzahl von Doppelbindungen darstellen. Aus ökonomischen Gründen ist es jedoch vorzuziehen, Aminoxide oder Ammoniumsalze einzusetzen, die aus fettchemischen Rohstoffen abgeleitet sind. In diesen Fällen weisen die Reste R1 eine Verteilung von Kettenlängen und Doppelbindungen auf, wie sie für die Fettsäuren in pflanzlichen oder tierischen Fetten und Ölen charakteristisch sind. Mit Vorzug werden solche Verbindungen der allgemeinen Formel (I) eingesetzt, in denen R1 für ein Gemisch von Alkylgruppen wie in denjenigen Fettsäuregemischen steht, die man durch Hydrolyse von Kokosöl, Palmkernöl oder von tierischem Talg erhalten kann.The alkyl radicals R 1 can represent radicals with a certain chain length and a certain number of double bonds. For economic reasons, however, it is preferable to use amine oxides or ammonium salts derived from oleochemical raw materials. In these cases, the R 1 radicals have a distribution of chain lengths and double bonds as are characteristic of the fatty acids in vegetable or animal fats and oils. Preference is given to using those compounds of the general formula (I) in which R 1 represents a mixture of alkyl groups, such as in those fatty acid mixtures which can be obtained by hydrolysis of coconut oil, palm kernel oil or animal tallow.

    Beispiele geeigneter Aminoxide der allgemeinen Formel (I) sind: Bis(2-hydroxyethyl)kokosalkylaminoxid (AromoxR C/12), Bis(2-hydroxyethyl)talgalkylaminoxid (AromoxR T/12), Dimethylkokosalkylaminoxid (AromoxR DMC), hydriertes Dimethyltalgalkylaminoxid (AromoxR DMHT) und Dimethylhexadecylaminoxid (AromoxR DM-16), die alle bei Akzo Chemicals Inc. erhältlich sind.Examples of suitable amine oxides of the general formula (I) are: bis (2-hydroxyethyl) cocoalkylamine oxide (Aromox R C / 12), bis (2-hydroxyethyl) tallow alkylamine oxide (Aromox R T / 12), dimethyl cocoalkylamine oxide (Aromox R DMC), hydrogenated dimethyl tallow alkylamine oxide (Aromox R DMHT) and dimethylhexadecylamine oxide (Aromox R DM-16), all of which are available from Akzo Chemicals Inc.

    Beispiele geeigneter quartärer Ammoniumsalze der allgemeinen Formel (I) sind: Dodecyltrimethylammoniumchlorid (ArquadR 12-37W), Octadecyltrimethylammoniumchlorid (ArquadR 18-50), Dimethylbenzyl-(C12-18)-alkylammoniumchlorid (ArquadR B-100), Tris(2-hydroxyethyl)talgalkylammoniumacetat (EthoquadR T/13) und Methylbis(2-hydroxy-2-methylethyl)ammoniummethylsulfat (PropoquadR T/12), die alle ebenfalls bei Akzo Chemicals Inc. erhältlich sind.Examples of suitable quaternary ammonium salts of the general formula (I) are: dodecyltrimethylammonium chloride (Arquad R 12-37W), octadecyltrimethylammonium chloride (Arquad R 18-50), dimethylbenzyl- (C 12-18 ) alkylammonium chloride (Arquad R B-100), Tris ( 2-hydroxyethyl) tallow alkyl ammonium acetate (Ethoquad R T / 13) and methyl bis (2-hydroxy-2-methylethyl) ammonium methyl sulfate (Propoquad R T / 12), all of which are also available from Akzo Chemicals Inc.

    Dabei werden solche Alkylaminoxide oder quartäre Ammoniumsalze der allgemeinen Formel (I) bevorzugt, die Reste R2, R3 und im Falle der quartären Ammoniumsalze auch R4 tragen, die sich bei der Umsetzung der Alkylamine mit Ethylenoxid, Propylenoxid oder Butylenoxid bilden. Beispiele hierfür sind 2-Hydroxyethylgruppen und 2-Hydroxy-2-methylethylgruppen. Wie bei Alkoxylierungsreaktionen üblich, können hierbei auch Reste R2, R3 und R4 entstehen, in denen jeweils mehrere Alkoxygruppen über Etherbindungen miteinander verknüpft sind. Derartige Polyetherreste mit bis zu 8 C-Atomen liegen ebenfalls im Rahmen der Erfindung. Besonders bevorzugt sind jedoch solche Verbindungen der allgemeinen Formel (I), die als Reste R2, R3 und gegebenenfalls R4 2-Hydroxyethylgruppen tragen. Preferred alkylamine oxides or quaternary ammonium salts of the general formula (I) are those which carry radicals R 2 , R 3 and, in the case of the quaternary ammonium salts, also R 4 , which form when the alkylamines are reacted with ethylene oxide, propylene oxide or butylene oxide. Examples include 2-hydroxyethyl groups and 2-hydroxy-2-methylethyl groups. As is customary in alkoxylation reactions, radicals R 2 , R 3 and R 4 can also be formed in which several alkoxy groups are linked to one another via ether bonds. Such polyether residues with up to 8 carbon atoms are also within the scope of the invention. However, particular preference is given to those compounds of the general formula (I) which bear 2-hydroxyethyl groups as radicals R 2 , R 3 and optionally R 4 .

    In den erfindungsgemäßen Behandlungslösungen stellen die Komponenten der Gruppe a) die reibungsvermindernd wirkenden Wirkstoffe dar. Demgegenüber liegt der Effekt der Komponenten der Gruppe b), eins-, zwei- oder dreibasische Hydroxycarbonsäuren mit 4 bis 7 C-Atomen im Molekül, wobei die Summe aus Hydroxyl- und Carboxylgruppen mindestens 3 beträgt, vornehmlich darin, daß ein später aufgebrachter Lack eine verringerte Porosität und damit eine erhöhte Korrosionsbeständigkeit aufweist. Der Porositätswert, in der angelsächsischen Literatur als "Metal Exposure Value", MEV, bezeichnet, ist durch eine elektrochemische Messung bestimmbar und stellt eine der Qualitätsanforderungen der Getränkeindustrie an lackierte Getränkedosen dar. Diese Meßgröße kann beispielsweise mit einem "Enamel Rater MK" der Firma Manfred Kunke, Berlin (Deutschland) oder mit einem "Enamel Rater" der Firma Wilkens-Anderson Co, Chicaco, Illinois bestimmt werden. Die Meßung beruht darauf, daß man die innen lackierte Getränkedose mit einer Elektrolytlösung (50,6 g Kochsalz und 1,19 g Dioctyl-Natrium-Sulfosuccinat in 5 1 vollentsalztem Wasser) füllt und die Dose als Elektrode schaltet. In die Elektrolytlösung wird eine Gegenelektrode getaucht und nach Einschalten der Spannung und einer Wartezeit von 4 sec. der fließende Strom in mA abgelesen. Bei perfekter Beschichtung der Dose ist kein Stromfluß zu erwarten. Zunehmender Stromfluß in mA, der den "Metal Exposure Value" darstellt, zeigt eine zunehmende Durchlässigkeit der Beschichtung für Ionen an, die als Porosität interpretiert werden kann. Für eine spätere Befüllung mit Erfrischungsgetränken wird beispielsweise gefordert, daß der durchschnittliche MEV unter 5 mA bei einer Prüfspannung von 6,3 V liegen soll.In the treatment solutions according to the invention, the components of the Group a) represents the active ingredients which reduce friction the effect of the components of group b) is one-, two- or three-base Hydroxycarboxylic acids with 4 to 7 carbon atoms in the molecule, the sum of hydroxyl and carboxyl groups is at least 3, primarily in that a later applied varnish has a reduced porosity and thus has an increased corrosion resistance. The porosity value, referred to in the Anglo-Saxon literature as "Metal Exposure Value", MEV, can be determined and determined by an electrochemical measurement one of the quality requirements of the beverage industry for coated beverage cans This measured variable can, for example, with an "Enamel Rater MK "from Manfred Kunke, Berlin (Germany) or with a "Enamel Rater" from Wilkens-Anderson Co, Chicaco, Illinois become. The measurement is based on the fact that the beverage can is painted on the inside with an electrolytic solution (50.6 g of common salt and 1.19 g of dioctyl sodium sulfosuccinate in 5 liters of deionized water) and fill the can as an electrode switches. A counter electrode is immersed in the electrolyte solution and after switching on the voltage and a waiting time of 4 sec. the flowing Current read in mA. With a perfect coating of the can there is none Current flow expected. Increasing current flow in mA, the "Metal Exposure Value "shows an increasing permeability of the coating for ions that can be interpreted as porosity. For one later filling with soft drinks is required, for example, that the average MEV is below 5 mA at a test voltage of 6.3 V should lie.

    Der Kern der vorliegenden Erfindung besteht darin, daß die Komponenten b) in der Behandlungslösung den MEV signifikant absenken, ohne die übrigen Eigenschaften wie Reibungsverminderung und Korrosionsschutz, die im wesentlichen auf die Komponenten a), c) und d) der Behandlungslösung zurückzuführen sind, negativ zu beeinflussen.The essence of the present invention is that components b) significantly lower the MEV in the treatment solution without the others Properties such as friction reduction and corrosion protection, which are essentially attributed to components a), c) and d) of the treatment solution are influencing negatively.

    Beispiele geeigneter Hydroxycarbonsäuren sind Äpfelsäure, Weinsäure, Citronensäure und insbesondere solche Carbonsäuren, die sich durch Oxidation von Zuckern vom Typ der Pentosen und der Hexosen erhalten lassen. Beispiele derartiger Säuren sind Gluconsäure, Zuckersäure, Mannozuckersäure, Schleimsäure und Glucuronsäure. Gluconsäure ist besonders bevorzugt. Diese Säuren können als solche oder in Form ihrer wasserlöslichen Salze, insbesondere ihrer Natriumsalze, eingesetzt werden. Bei dem pH-Wert der erfindungsgemäßen Behandlungslösungen im Bereich 2,3 bis 3,3 liegen die Hydroxycarbonsäuren je nach ihrem pKs-Wert teilweise als solche und teilweise in Form ihrer Anionen vor. Die Mitverwendung derartiger Carbonsäuren, insbesondere der Gluconsäure, bei der Oberflächenbehandlung von Aluminium, beispielsweise bei der alkalischen Beize, ist prinzipiell bekannt. Unerwartet ist jedoch der Effekt, daß die Hydroxycarbonsäuren der Gruppe b) die Wirkung der übrigen Komponenten der erfindungsgemäßen Behandlungslösung dahingehend ergänzt, daß der "Metal Exposure Value" einer aufgebrachten Lackierung verringert wird.Examples of suitable hydroxycarboxylic acids are malic acid, tartaric acid, citric acid and in particular those carboxylic acids which can be obtained by oxidation of pentose and hexose type sugars. Examples of such acids are gluconic acid, sugar acid, mannosugar acid, mucic acid and glucuronic acid. Gluconic acid is particularly preferred. These acids can be used as such or in the form of their water-soluble salts, in particular their sodium salts. At the pH value of the treatment solutions of the invention in the range 2.3 to 3.3, the hydroxycarboxylic acids are, depending on their pK partly as such and partly in the form of their anions. The use of such carboxylic acids, in particular gluconic acid, in the surface treatment of aluminum, for example in the case of alkaline pickling, is known in principle. However, the effect is unexpected that the hydroxycarboxylic acids of group b) supplement the effect of the other components of the treatment solution according to the invention in such a way that the "metal exposure value" of an applied coating is reduced.

    Die weiteren Hauptkomponenten der erfindungsgemäßen Behandlungslösung, c) und d), sind in Lösungen zur Konversionsbehandlung von Aluminiumoberflächen gut bekannt. Als komplexe Fluoride der Gruppe c) kommen beispielsweise Hexafluorotitanat, Hexafluorozirkonat, Hexafluorohafnat, Hexafluorosilicat oder Tetrafluoroborat in Betracht. Die Verwendung von Hexafluorozirkonat ist bevorzugt. Dabei ist es unwesentlich, ob die komplexen Fluoride als wasserlösliche Salze, beispielsweise als Natrium- oder Ammoniumsalze, oder als freie Säuren eingesetzt werden. Es muß lediglich darauf geachtet werden, daß die komplexen Fluoroverbindungen so mit den Mineralsäuren der Gruppe d) bzw. deren sauren oder neutralen Salzen kombiniert werden, daß die erfindungsgemäße Behandlungslösung einen pH-Wert im wirksamen Bereich von 2,3 bis 3,3 aufweist. Bei pH-Werten außerhalb dieses Bereichs wird die Ausbildung der angestrebten korrosionsschützenden und reibungsvermindernden Schicht um so unbefriedigender, je weiter man sich von dem angegebenen Bereich entfernt.The other main components of the treatment solution according to the invention, c) and d), are in solutions for the conversion treatment of aluminum surfaces well known. Examples of complex fluorides of group c) Hexafluorotitanate, hexafluorozirconate, hexafluorohafnate, hexafluorosilicate or tetrafluoroborate. The use of hexafluorozirconate is preferred. It is immaterial whether the complex fluorides as water-soluble salts, for example as sodium or ammonium salts, or used as free acids. You just have to pay attention be that the complex fluorine compounds so with the mineral acids of the Group d) or their acidic or neutral salts are combined in such a way that the treatment solution according to the invention has a pH in the effective range from 2.3 to 3.3. At pH values outside this range, the Training the desired corrosion-protecting and friction-reducing Layer the more unsatisfactory the further you go from the specified Area removed.

    Da der Phosphorsäure oder deren Anionen aufgrund der Bildung schwerlöslicher und auf der Metalloberfläche fest haftender Metallphosphate eine besondere korrosionsschützende Wirkung zukommt, ist es besonders vorzuziehen, daß die Komponente d) zu 10 bis 100 Gew.-% aus Phosphorsäure oder deren Anionen besteht. Falls nicht Phosphorsäure als einzige Säure der Gruppe d) eingesetzt wird, ist die Mitverwendung von Salpetersäure oder deren Anionen vorteilhaft. Because of phosphoric acid or its anions due to the formation of poorly soluble and a special metal phosphate firmly adhering to the metal surface corrosion protection effect, it is particularly preferable that component d) 10 to 100 wt .-% of phosphoric acid or whose anions exist. If not phosphoric acid as the only acid of the Group d) is used, the concomitant use of nitric acid or their anions advantageous.

    Die Wirkung der vorstehend beschriebenen Stoffkombination kann durch Zusatz weiterer Wirkstoffe aus dem Stand der Technik verstärkt werden:The effect of the combination of substances described above can be added further active ingredients from the prior art are reinforced:

    Ein Zusatz von Tannin im Konzentrationsbereich 50 bis 500 mg/l erhöht die Wirkung der Hydroxycarbonsäuren der Gruppe b) hinsichtlich der Reduktion des "Metal Exposure Value" einer anschließend aufgebrachten Lackierung. Demnach ist es bevorzugt, daß die erfindungsgemäße Behandlungslösung zusätzlich Tannin enthält. Tannine (vergleiche beispielsweise Römpp Chemie Lexikon 9. Auflage 1992, Stichwort "Tannin") steht als Gruppenname für eine Reihe von natürlichen Polyphenolen sehr vielfältiger Zusammensetzung, die sich von der Gallussäure ableiten lassen. Dabei liegen die Gallussäurederivate häufig mit Glucose verestert vor. In Form pflanzlicher Extrakte unterschiedlicher Herkunft stellen die Tannine eine bekannte Wirstoffgruppe für die Ledergerbung dar. In diesem Zusammenhang werden Strukturen und Herkunft der Tannine näher diskutiert in: Kirk-Othmer "Encyclopedia of Chemical Technology", 2. Auflage, Band XII (1967), SS. 303-341. Wie aus den Dokumenten US-A-4,470,853 und DE-A-24 46 492 hervorgeht, wurde die Verwendung von Tanninen bei der Oberflächenbehandlung von Aluminium bereits vorgeschlagen.An addition of tannin in the concentration range 50 to 500 mg / l increases the Effect of group b) hydroxycarboxylic acids on the reduction the "metal exposure value" of a subsequent coating. Accordingly, it is preferred that the treatment solution according to the invention additionally Contains tannin. Tannins (compare, for example, Römpp Chemie Lexicon 9th edition 1992, keyword "Tannin") stands as a group name for a number of natural polyphenols of very diverse compositions, which can be derived from gallic acid. Here are the gallic acid derivatives often esterified with glucose before. In the form of herbal extracts The tannins of different origins represent a well-known group of active ingredients for leather tanning. In this context, structures and Origin of the tannins discussed in more detail in: Kirk-Othmer "Encyclopedia of Chemical Technology ", 2nd edition, Volume XII (1967), pp. 303-341. As from documents US-A-4,470,853 and DE-A-24 46 492, the Use of tannins in the surface treatment of aluminum already suggested.

    Bei der Erzeugung von Konversionsschichten auf Aluminiumoberflächen wirkt sich erfahrungsgemäß die Anwesenheit von freien Fluoridionen günstig aus. Aus den vorstehend unter der Gruppe c) angeführten komplexen Fluoriden können durch Hydrolysereaktionen in der Behandlungslösung freie Fluoridionen entstehen, die bei dem pH-Wert der Behandlungslösung zumindest teilweise in Form von undissoziierter Flußsäure vorliegen. Die mit den erfindungsgemäßen Behandlungslösungen erzielte Schichtbildung kann, besonders in der Einfahrphase der Bäder, unterstützt werden, wenn die Behandlungslösungen zusätzlich 10 bis 100 mg/l Fluoridionen enthält, die als Flußsäure oder als lösliche neutrale oder saure Fluoride zugegeben werden können. Beispiele hierfür sind NaF, KF, KHF2 oder (NH4)HF2. Die Fluoridkomponente ist so zu wählen, daß der erforderlich pH-Bereich von 2,3 bis 3,3 nicht verlassen wird.Experience has shown that the presence of free fluoride ions has a favorable effect on the production of conversion layers on aluminum surfaces. From the complex fluorides listed above under group c), hydrolysis reactions in the treatment solution can result in free fluoride ions which are at least partially present in the form of undissociated hydrofluoric acid at the pH of the treatment solution. The layer formation achieved with the treatment solutions according to the invention can be supported, especially in the running-in phase of the baths, if the treatment solutions additionally contain 10 to 100 mg / l fluoride ions, which can be added as hydrofluoric acid or as soluble neutral or acid fluorides. Examples include NaF, KF, KHF 2 or (NH 4 ) HF 2 . The fluoride component should be selected so that the required pH range of 2.3 to 3.3 is not left.

    Da die Behandlungslösung durch die Komponenten der Gruppe a) zur Schaumbildung neigende oberflächenaktive Komponenten enthält, kann es bei starker Badbewegung wie beispielsweise für Spritzanlagen erforderlich sein, den Behandlungsbädern Entschäumer zuzusetzen. Mengen im Bereich von 50 bis 500 mg/l sollten in der Regel ausreichend sein. Als Entschäumer sind beispielsweise Alkylpolyalkoxyester geeignet. Ein geeigneter Polyalkoxyester dieses Typs ist unter dem Handelsnamen FoamasterR C14 von der Henkel KGaA, Düsseldorf (Deutschland) erhältlich.Since the treatment solution contains, by means of the components of group a), surface-active components which tend to foam, it may be necessary to add defoamers to the treatment baths in the case of strong bath movements, such as for spray systems. Amounts in the range of 50 to 500 mg / l should generally be sufficient. Examples of suitable defoamers are alkyl polyalkoxy esters. A suitable polyalkoxy ester of this type is available under the trade name Foamaster R C14 from Henkel KGaA, Düsseldorf (Germany).

    Alle vorstehend angegebenen Bereiche für wirksame Konzentrationen und pH-Wert sind so zu verstehen, daß innerhalb dieser Parameterbereiche die erwünschte Wirkung zuverlässig eintritt. Bei Unterschreitung der angegebenen Mindestkonzentrationen läßt in der Regel die erwünschte kombinierte reibungsvermindernde, korrosionsschützende und die Porosität einer nachfolgenden Lackierung verringernde Wirkung der Schutzschicht nach. Überschreitungen der maximalen Konzentrationen nach oben sind zumindest unökonomisch, können aber auch zu Nachteilen in der Schichtausbildung führen. Eine den Ansprüchen voll genügende Beschichtung wird besonders zuverlässig erhalten, wenn die Komponente a) in Konzentrationen von 0,5 bis 1,1 mMol/l und/oder die Komponente b) in Konzentrationen von 0,3 bis 1,15 mMol/l in der Behandlungslösung vorliegt. Das vorzugsweise mitverwendete Tannin setzt man bevorzugt in Konzentrationen von 100 bis 400 mg/l ein.All ranges given above for effective concentrations and pH are to be understood in such a way that within these parameter ranges the desired Effect occurs reliably. When falling below the specified As a rule, minimum concentrations leave the desired combined friction-reducing, anti-corrosive and the porosity of a subsequent Paint reducing effect of the protective layer after. Exceedances the maximum concentrations upwards are at least uneconomical, but can also lead to disadvantages in layer formation. A coating that fully meets the requirements becomes particularly reliable obtained when component a) in concentrations of 0.5 to 1.1 mmol / l and / or component b) in concentrations of 0.3 to 1.15 mmol / l in the treatment solution is available. The preferred tannin used is preferably used in concentrations of 100 to 400 mg / l.

    Eine weitere Verbesserung der Beschichtung, insbesondere hinsichtlich ihrer Lackierbarkeit, kann dadurch erreicht werden, daß man der Behandlungslösung zusätzlich wasserlösliche oder wasserdispergierbare organische Polymere in Konzentrationen von etwa 100 bis etwa 1000 mg/l zusetzt. Dabei können diese Polymere ausgewählt sein aus h) Homo- oder Heteropolymeren von Ethylenoxid, Propylenoxid und/oder Butylenoxid, i) Homo- oder Heteropolymeren von Acrylsäure, Maleinsäure und/oder Derivaten hiervon, k) Homo- oder Heteropolymeren von Vinylphenol und/oder Vinylphenolderivaten, 1) Homo- oder Heteropolymeren von Vinylakohol und/oder Vinylakoholderivaten. Polymere der genannten Art sind kommerziell erhältlich. Die Polyvinylphenolderivate der Gruppe k) sind erhältlich durch eine Mannich-Reaktion von Polyvinylphenol mit Aldehyden mit Alkylaminen. Beispielsweise genannt sei ein Umsetzungsprodukt von Poly(4-vinylphenol) mit Formaldehyd und 2-Alkylamino-1-ethanol. Nähere Angaben über dieses Polymer und seine Verwendung bei der Oberflächenbehandlung von Aluminium sind in der W092/07973 enthalten. A further improvement of the coating, especially with regard to their paintability can be achieved by using the treatment solution additionally water-soluble or water-dispersible organic Add polymers in concentrations from about 100 to about 1000 mg / l. Here these polymers can be selected from h) homopolymers or heteropolymers of ethylene oxide, propylene oxide and / or butylene oxide, i) homopolymers or heteropolymers of acrylic acid, maleic acid and / or derivatives thereof, k) homo- or heteropolymers of vinylphenol and / or vinylphenol derivatives, 1) Homopolymers or heteropolymers of vinyl alcohol and / or vinyl alcohol derivatives. Polymers of the type mentioned are commercially available. The polyvinylphenol derivatives of group k) are obtainable by a Mannich reaction from Polyvinylphenol with aldehydes with alkylamines. For example a reaction product of poly (4-vinylphenol) with formaldehyde and 2-alkylamino-1-ethanol. Details of this polymer and its use for the surface treatment of aluminum are contained in W092 / 07973.

    Vorstehend wurden Zusammensetzungen erfindungsgemäßer einsatzbereiter Behandlungslösungen beschrieben. Es ist selbstverständlich möglich, diese Bäder durch Zusammenmischen der einzelnen Komponenten in den angegebenen Konzentrationsbereichen am Einsatzort direkt zuzubereiten. Für den Anwender solcher Behandlungslösungen ist es jedoch günstiger, von einem Hersteller wäßrige Konzentrate der Behandlungslösungen zu beziehen und diese vor Ort durch Verdünnen mit Wasser auf die Konzentrationsbereiche der Anwendungslösungen einzustellen. Demnach umfaßt die Erfindung auch wäßrige Konzentrate der Behandlungslösungen, die durch Verdünnen mit Wasser die erfindungsgemäßen Behandlungslösungen ergeben. Dabei ist es technisch und wirtschaftlich am attraktivsten, die Konzentrate so einzustellen, daß aus ihnen durch Verdünnen mit Wasser in einem Volumenverhältnis zwischen 1 : 50 und 1 : 200 die anwendungsfertigen Behandlunglösungen erhalten werden können. Beispielsweise kann das Konzentrat so eingestellt sein, daß es zum Bereiten der anwendungsfertigen Behandlungslösung mit Wasser im Verhältnis 1 : 100 verdünnt werden muß.Above, compositions of the invention have become ready for use Treatment solutions described. It is of course possible to do this Baths by mixing together the individual components in the specified Prepare concentration areas directly on site. For the user such treatment solutions, however, it is cheaper, from a manufacturer to obtain aqueous concentrates of the treatment solutions and these on site by diluting with water to the concentration ranges of the application solutions adjust. Accordingly, the invention also includes aqueous Concentrates of the treatment solutions, which are diluted with water Treatment solutions according to the invention result. It is technical and economically most attractive to adjust the concentrates so that them by diluting them with water in a volume ratio between 1:50 and 1:200 the ready-to-use treatment solutions are obtained can. For example, the concentrate can be adjusted so that it to prepare the ready-to-use treatment solution with water in proportion Must be diluted 1: 100.

    Die erfindungsgemäße Behandlungslösung kommt vorzugsweise in einem Verfahren zur Herstellung von Dosen, insbesondere von Getränkedosen aus Aluminiumlegierungen, zum Einsatz. Hierbei werden die vorgeformten Dosen in der Regel einer ein- oder zweistufigen sauren oder alkalischen Reinigung unterzogen, worauf üblicherweise eine Spülung mit Leitungswasser erfolgt. Danach bringt man die Dosen mit der erfindungsgemäßen Behandlungslösung in Berührung, was beispielsweise durch Eintauchen der Dosen in die Lösung oder durch Besprühen der Dosen mit der Lösung erfolgen kann. Dabei soll die Temperatur der Behandlungslösung im Bereich zwischen 30 bis 60 °C liegen und insbesondere 40 bis 45 °C betragen. Die Behandlungsdauer soll 10 sec. nicht unterschreiten. Eine Behandlungsdauer von mehr als 120 sec. bringt keinen technischen Vorteil. Beispielsweise ist es günstig, eine Behandlungsdauer von etwa 30 sec. zu wählen. Danach werden die Dosen mit Leitungswasser und anschließend mit vollentsalztem Wasser gespült, wonach sie getrocknet und lackiert werden können. Demnach umfaßt die Erfindung auch ein Verfahren zum Erzeugen einer korrosionsschützenden, reibungsvermindernden und die Lackierbarkeit verbessernden Schutzschicht auf Oberflächen aus Aluminium oder Zinn sowie jeweils deren Legierungen, dadurch gekennzeichnet, daß man die Oberflächen mit einer wäßrigen Lösung nach einem oder mehreren der Ansprüche 1 bis 8, die eine Temperatur im Bereich von 30 bis 60 °C aufweist, für einen Zeitraum zwischen 10 und 120 Sekunden in Berührung bringt, das man vorzugsweise zur Behandlung von Dosen aus Aluminium oder Aluminiumlegierungen einsetzt.The treatment solution according to the invention preferably comes in one process for the production of cans, in particular beverage cans made of aluminum alloys, for use. Here, the preformed cans in the Usually subjected to one or two-stage acidic or alkaline cleaning, which is usually followed by a rinse with tap water. Then the doses are brought in with the treatment solution according to the invention Touch, for example by immersing the cans in the solution or can be done by spraying the cans with the solution. In doing so the temperature of the treatment solution is between 30 and 60 ° C and in particular 40 to 45 ° C. The duration of treatment should be 10 do not fall below sec. A treatment duration of more than 120 sec. brings no technical advantage. For example, it is convenient to have one Treatment duration of about 30 seconds to choose. After that, the cans come with Tap water and then rinsed with deionized water, after which they can be dried and painted. Accordingly, the invention encompasses also a method of producing an anti-corrosion, anti-friction and the protective layer on surfaces which improves the paintability made of aluminum or tin and their alloys, characterized in that that the surfaces with an aqueous solution after a or more of claims 1 to 8, which have a temperature in the range of 30 up to 60 ° C, for a period between 10 and 120 seconds in contact brings, which one preferably for the treatment of cans made of aluminum or uses aluminum alloys.

    Die Erfindung wurde an Aluminium-Getränkedosen mit einem Volumen zwischen 330 und 350 ml, wie sie für Erfrischungsgetränke üblich sind, erprobt. Die vorgeformten Dosen wurden zunächst gereinigt (saurer Reiniger RidolineR 124, Henkel KGaA, Düsseldorf; 54 bis 60 °C, 1 Minute) und anschließend mit Leitungswasser von Raumtemperatur gespült. Danach erfolgte die Oberflächenbehandlung mit erfindungsgemäßen Behandlungslösungen sowie mit Vergleichslösungen gemäß Tabelle mit pH-Werten im Bereich zwischen 2,45 und 2,93 bei Temperaturen zwischen 40 und 45 °C für eine Behandlungsdauer von 30 sec. im Spritzen. Anschließend erfolgte ein Spülung mit Leitungswasser, gefolgt von einer Spülung mit vollentsalztem Wasser, jeweils bei Raumtemperatur, wonach die Dosen für 5 Minuten bei 150 °C getrocknet wurden.The invention was tested on aluminum beverage cans with a volume between 330 and 350 ml, as are customary for soft drinks. The preformed cans were first cleaned (acidic cleaner Ridoline R 124, Henkel KGaA, Düsseldorf; 54 to 60 ° C, 1 minute) and then rinsed with tap water at room temperature. Thereafter, the surface treatment was carried out with treatment solutions according to the invention and with comparison solutions according to the table with pH values in the range between 2.45 and 2.93 at temperatures between 40 and 45 ° C. for a treatment period of 30 seconds in spraying. This was followed by rinsing with tap water, followed by rinsing with demineralized water, each at room temperature, after which the cans were dried at 150 ° C. for 5 minutes.

    Die Bestimmung der Brunnenwasserbeständigkeit nach Standardmethoden, die ein Maß für den Korrosionsschutz der behandelten Dosen liefert, erfolgte an den unlackierten Dosen. Unlackierte Dosen wurden auch für die nachstehende Bestimmung des Reibungskoeffizienten verwendet. Für die Bestimmung der Lackporosität, ausgedrückt als "Metal Exposure Value", wurden die Doseninnenseiten mit einem handelsüblichen Lack (Dexter Ecodex 4020) mit einem Lackauftrag von 120 bis 130 mg/Dose lackiert.The determination of the well water resistance according to standard methods, the provides a measure of the corrosion protection of the treated cans on the unpainted cans. Unpainted cans were also used for the following Determination of the coefficient of friction used. For the determination of the paint porosity, expressed as "metal exposure value", became the inside of the can with a standard paint (Dexter Ecodex 4020) a varnish application of 120 to 130 mg / can varnished.

    Die Bestimmung der Brunnenwasserbeständigkeit erfolgte dadurch, daß die unlackierten Dosen für 30 Minuten in eine 66 °C heiße Lösung von 0,2 g/l Natriumtetraboratdecahydrat getaucht wurden, anschließend mit vollentsalztem Wasser gespült und bei 105 °C in einem Trockenofen getrocknet wurden. Danach wurden die Dosenböden visuell nach dem Grad ihrer Verfärbung beurteilt. Dabei wird keine oder eine leichte Verfärbung als akzeptabel angesehen, eine dunkle oder unregelmäßige Verfärbung als unakzeptabel. Sowohl die mit den erfindungsgemäßen Verfahrensvarianten als auch mit Vergleichsverfahren nach dem Stand der Technik behandelten Dosen bestanden diesen Test auf Korrosionsbeständigkeit. The well water resistance was determined in that the unpainted cans for 30 minutes in a 66 ° C solution of 0.2 g / l Sodium tetraborate decahydrate were dipped, then with fully desalinated Rinsed water and dried at 105 ° C in a drying oven. The can bottoms were then assessed visually for the degree of discoloration. No or a slight discoloration is considered acceptable, a dark or irregular discoloration as unacceptable. Either those with the method variants according to the invention as well as with comparison methods Doses treated according to the prior art passed these Corrosion resistance test.

    Die Bestimmung der Oberflächenreibung der unlackierten Getränkedosen erfolgte auf einem Kipptisch. Hierzu werden jeweils 3 gleich behandelte Dosen verwendet. Zwei Dosen werden parallel aneinanderliegend auf dem Kipptisch so angeordnet, daß ihre Längsachse senkrecht zur Kippachse liegt. Auf dieses Dosenpaar wird eine dritte Dose mit ihrer Längsachse senkrecht zur Kippachse so gelegt, daß sie gegenüber den unteren Dosen um etwa 0,5 cm in Richtung der Kippachse verschoben ist, wobei sie entgegensetzt zu den unteren Dosen mit der offenen Seite in Richtung Kippachse gelegt wird. Danach wird der Kipptisch automatisch mit konstanter Geschwindigkeit gekippt und der Neigungswinkel α festgestellt, bei dem die obere Dose verrutscht und dabei einen Ausschalter berührt. Der Tangens des Neigungswinkels α, bei dem das Verrutschen erfolgt, wird als Reibungskoeffizient bezeichnet. Um statistisch gesicherte Aussagen zu erhalten, werden jeweils 6 gleich behandelte Dosen verwendet, aus denen jeweils 3 für einen Versuch ausgewählt werden. Man führt 6 voneinander unabhängige Messungen mit unterschiedlichen Dosenkombinationen durch. Aus den 6 Messungen wird der Mittelwert bestimmt. Die mit den erfindungsgemäßen Behandlungslösungen und den Vergleichslösungen nach dem Stand der Technik ermittelten Reibungskoeffizienten wiesen keine signifikanten Unterschiede auf und lagen im Bereich von 0,476 bis 0,514.The surface friction of the unpainted beverage cans was determined on a tilting table. For this, 3 doses are treated equally used. Two cans are placed side by side on the tilting table arranged so that its longitudinal axis is perpendicular to the tilt axis. A third can with its longitudinal axis is perpendicular to this pair of cans to the tilt axis so that it is about 0.5 cm is shifted in the direction of the tilt axis, whereby it is opposed to the lower cans are placed with the open side in the direction of the tilt axis. The tilting table is then automatically tilted at a constant speed and the angle of inclination α was found at which the upper box slipped while touching a switch. The tangent of the angle of inclination α, in which the slipping takes place, is called the coefficient of friction. In order to obtain statistically reliable statements, 6 used the same treated doses, of which 3 each for an experiment to be chosen. 6 independent measurements with different ones are carried out Combinations of cans. The 6 measurements become the Average determined. The treatment solutions according to the invention and the comparison solutions determined according to the prior art coefficient of friction showed no significant differences and were in the range from 0.476 to 0.514.

    Dagegen zeigt sich Effekt der erfindungsgemäßen Behandlung gegenüber einer Behandlung ohne Zusatz von Hydroxycarbonsäuren der Gruppe b) in einer deutlich verringerten Porosität einer Lackierung, die als "Metal Exposure Value" (MEV) bestimmt wurde. Die Bestimmung erfolgte an innen lackierten Dosen gemäß der Bedienungsanleitung des Enamel Rater MK der Firma Manfred Kunke, Taunusstr. 29, Berlin (Deutschland) bei einer Prüfspannung von 6,3 Volt. Dabei wurden die als Elektrode geschalteten Dosen mit einer Elektrolytlösung gefüllt (50,6 g Kochsalz und 1,19 g Dioctyl-Natrium-Sulfosuccinat in 5 l vollentsalztem Wasser), in die als Gegenelektrode ein Metallbügel eingetaucht wurde. Nach Anlegen der Spannung wurde nach 4 sec. der Strom in mA gemessen und als MEV-Wert gesetzt. Als Prüfkriterium für Getränkedosen für Erfrischungsgetränke wird ein oberer MEV-Wert von 5 mA angegeben. Die erhaltenen Ergebnisse sind in der Tabelle eingetragen. Die Tabelle enthält ebenfalls die Anzahl der Dosen, die pro Behandlungslösung jeweils vermessen wurden, den mittleren MEV-Wert, den maximal beobachteten MEV-Wert und die Anzahl der Dosen, bei denen die Spezifikation von einem maximalen MEV-Wert von 5 mA überschritten wurde. Die Zusammensetzung der Probelösungen geht aus der Tabelle hervor. Vorbehandlungslösungen und "Metal Exposure Value" (MEV) Grundrezeptur: 400 mg/l Tris(2-hydroxyethyl)talgammonium-Acetat 145 mg/l Hexafluorozirkonsäure 66 mg/l Phosphorsäure 266 mg/l Salpetersäure 32 mg/l Flußsäure 200 mg/l Entschäumer (Alkylpolyalkoxyester, FoamasterR C14, Henkel KGaA, Düsseldorf) Zusätze von Natriumgluconat und Tannin Versuch Nr. Natriumgluconat (mg/l) Tannin (mg/l) Dosenzahl mittlerer MEV (mA) maximaler MEV (mA) Dosen mit MEV > 5 mA Vergleich - - 8 5,5 42,1 1 Beisp.1 67 - 8 3,9 17,7 2 Beisp.2 133 - 7 1,3 6,0 1 Beisp.3 200 - 8 2,1 6,0 1 Beisp.4 125 - 9 1,25 6,4 1 Beisp.5 125 83 8 4,0 11,4 1 Beisp.6 125 167 7 0,6 2,3 0 Beisp.7 125 250 9 0,2 0,8 0 In contrast, the effect of the treatment according to the invention compared to a treatment without addition of hydroxycarboxylic acids of group b) is shown in a significantly reduced porosity of a coating, which was determined as the "Metal Exposure Value" (MEV). The determination was made on internally lacquered cans according to the operating instructions of the Enamel Rater MK from Manfred Kunke, Taunusstr. 29, Berlin (Germany) at a test voltage of 6.3 volts. The cans connected as electrodes were filled with an electrolyte solution (50.6 g of sodium chloride and 1.19 g of dioctyl sodium sulfosuccinate in 5 l of completely deionized water), into which a metal bracket was immersed as a counter electrode. After applying the voltage, the current was measured in mA after 4 seconds and set as the MEV value. An upper MEV value of 5 mA is specified as the test criterion for beverage cans for soft drinks. The results obtained are entered in the table. The table also contains the number of doses that were measured per treatment solution, the mean MEV value, the maximum observed MEV value and the number of doses at which the specification was exceeded by a maximum MEV value of 5 mA. The composition of the sample solutions is shown in the table. Pretreatment Solutions and Metal Exposure Value (MEV) Basic recipe: 400 mg / l tris (2-hydroxyethyl) tallow ammonium acetate 145 mg / l hexafluorozirconic acid 66 mg / l phosphoric acid 266 mg / l nitric acid 32 mg / l hydrofluoric acid 200 mg / l defoamer (alkyl polyalkoxy ester, Foamaster R C14, Henkel KGaA, Düsseldorf) Additions of sodium gluconate and tannin Trial No. Sodium gluconate (mg / l) Tannin (mg / l) Number of cans mean MEV (mA) maximum MEV (mA) Cans with MEV> 5 mA comparison - - 8th 5.5 42.1 1 Ex. 1 67 - 8th 3.9 17.7 2nd Ex. 2 133 - 7 1.3 6.0 1 Ex. 3 200 - 8th 2.1 6.0 1 Ex.4 125 - 9 1.25 6.4 1 Ex. 5 125 83 8th 4.0 11.4 1 Ex. 6 125 167 7 0.6 2.3 0 Ex. 7 125 250 9 0.2 0.8 0

    Claims (11)

    1. An aqueous solution for the treatment of surfaces of aluminium or tin and alloys thereof which has a pH value in the range from 2.3 to 3.3 and which contains at least the following components:
      a) 0.14 to 2.25 mmoles/l of a component selected from surface-active quaternary ammonium salts or amine oxides corresponding to general formula (I):
      Figure 00180001
      in which R1 is a saturated or mono- or polyunsaturated alkyl radical containing 8 to 22 carbon atoms, R2 and R3 independently of one another represent an alkyl or hydroxyalkyl radical containing 1 to 8 carbon atoms or an aryl or alkylaryl radical containing 6 to 10 carbon atoms, R4 has the same meaning as R2 or R3 or is an -O- group and X- is a monovalent anion or a monovalent equivalent of a polyvalent anion and a = 0 where R4 = -O-, but otherwise has a value of 1,
      b) 0.25 to 1.5 mmoles/l of one or more mono-, di- or tribasic hydroxycarboxylic acids containing 4 to 7 carbon atoms in the molecule, the sum total of hydroxyl and carboxyl groups being at least 3, or anions thereof,
      c) 0.4 to 2 mmoles/l of one or more complex fluorides and
      d) 20 to 500 mg/l of mineral acids selected from phosphoric acid, nitric acid and sulfuric acid or anions thereof.
    2. An aqueous solution as claimed in claim 1, characterized in that it additionally contains one or more of the following components:
      e) 50 to 500 mg/l tannin
      f) 10 to 100 mg/l hydrofluoric acid or fluoride ions
      g) 50 to 500 mg/l defoamer.
    3. An aqueous solution as claimed in one or both of claims 1 and 2, characterized in that component
      a) is an amine oxide or a quaternary ammonium salt in which R1 is a mixture of alkyl groups as in fatty acid mixtures obtainable by hydrolysis of coconut oil, palm kernel oil or animal tallow
      and/or component
      b) is selected from monobasic or dibasic hydroxycarboxylic acids containing 6 carbon atoms and at least 4 hydroxyl groups
      and/or component
      c) is hexafluorozirconic acid
      and/or 10 to 100% by weight of component
      d) consists of phosphoric acid or anions thereof.
    4. An aqueous solution as claimed in one or more of claims 1 to 3, characterized in that component
      a) is a quaternary ammonium salt, in which R2, R3 and R4 are hydroxyalkyl groups containing 1 to 4 carbon atoms
      and/or component
      b) is gluconic acid or anions thereof.
    5. An aqueous solution as claimed in one or more of claims 1 to 4, characterized in that it contains component a) in concentrations of 0.5 to 1.1 mmole/l and/or component b) in concentrations of 0.3 to 1.15 mmole/l.
    6. An aqueous solution as claimed in one or more of claims 1 to 5, characterized in that it contains tannin in concentrations of 100 to 400 mg/l.
    7. An aqueous solution as claimed in one or more of claims 1 to 6, characterized in that it additionally contains water-soluble or water-dispersible polymers in concentrations of 100 to 1000 mg/l.
    8. An aqueous solution as claimed in claim 7, characterized in that the polymers are selected from h) homopolymers or heteropolymers of ethylene oxide, propylene oxide and/or butylene oxide, i) homopolymers or heteropolymers of acrylic acid, maleic acid and/or derivatives thereof, k) homopolymers or heteropolymers of vinylphenol and/or vinylphenol derivatives, l) homopolymers or heteropolymers of vinyl alcohol and/or vinyl alcohol derivatives.
    9. An aqueous concentrate which forms a treatment solution according to one or more of claims 1 to 8 on dilution with water in a ratio by volume of 1:50 to 1:200.
    10. A process for the production of a protective layer on surfaces of aluminium or tin and alloys thereof which prevents corrosion, reduces friction and improves enamelling, characterized in that the surfaces are contacted for 10 to 120 seconds with an aqueous solution according to one or more of claims 1 to 8 having a temperature of 30 to 60°C.
    11. A process as claimed in claim 10, characterized in that the metal surfaces are surfaces of cans of aluminium or aluminium alloys.
    EP95940171A 1994-11-23 1995-11-14 Anticorrosive and friction-reducing treatment of metallic surfaces Expired - Lifetime EP0793738B1 (en)

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    JPH10509766A (en) 1998-09-22
    DE4441710A1 (en) 1996-05-30
    TW283740B (en) 1996-08-21
    EP0793738A1 (en) 1997-09-10
    AR000259A1 (en) 1997-06-18
    CA2205996A1 (en) 1996-05-30
    MX9703762A (en) 1998-07-31
    ZA959938B (en) 1996-05-23
    BR9509759A (en) 1997-09-16
    WO1996016205A1 (en) 1996-05-30
    ATE178951T1 (en) 1999-04-15
    TR199501469A2 (en) 1996-07-21
    DE59505673D1 (en) 1999-05-20
    AU698370B2 (en) 1998-10-29
    AU4171996A (en) 1996-06-17

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