EP0531360B1 - Cleaning of aluminium surfaces - Google Patents
Cleaning of aluminium surfaces Download PDFInfo
- Publication number
- EP0531360B1 EP0531360B1 EP91909835A EP91909835A EP0531360B1 EP 0531360 B1 EP0531360 B1 EP 0531360B1 EP 91909835 A EP91909835 A EP 91909835A EP 91909835 A EP91909835 A EP 91909835A EP 0531360 B1 EP0531360 B1 EP 0531360B1
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- EP
- European Patent Office
- Prior art keywords
- cleaning
- acid
- weight
- phosphoric acid
- oxalic acid
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
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- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
Definitions
- the present invention relates to the use of a fluoride-free aqueous solution for cleaning aluminum surfaces of consumer goods and plants for food production and processing, containing phosphoric acid and oxalic acid and optionally other components of detergents for the food industry known per se.
- US-A-1 456 486 describes a powdery aluminum cleaner based on Spanish soap, oxalic acid, with minor constituents of ammonia, zinc oxide and sodium bicarbonate, with an abrasive additive for cleaning corresponding surfaces.
- US-A-1 554 483 describes a process for the purification of aluminum by using organic acids, salts of organic acids or mixtures of organic acids and organic salts in the presence of carbohydrates at temperatures near the boiling point of the detergent solution.
- organic acids salts of organic acids or mixtures of organic acids and organic salts
- acetic acid benzoic acid, citric acid, maleic acid, malonic acid and tartaric acid, oxalic acid is proposed.
- a cleaning temperature close to the boiling point of water cannot be carried out or is undesirable in the food industry when cleaning open systems.
- US-A-1 890 214 also relates to the cleaning of aluminum surfaces near the boiling point of water in the presence of alkali fluorides. It is described that a number of organic fruit acids can be used in conjunction with fluoride. Maleic acid, malonic acid, tartaric acid, citric acid, acetic acid and oxalic acid are included as highly concentrated additives in addition to the alkali fluoride in the corresponding cleaning agents. Regarding oxalic acid, it is disclosed that although this could be used, it causes excessive material removal.
- DE-A-20 54 067 relates to water-dilutable, concentrated compositions for cleaning aluminum surfaces, for deoxidizing, cleaning and leveling or for glossing stainless steel surfaces and for forming an iron phosphate coating on iron-containing surfaces.
- These compositions contain sulfuric acid and phosphoric acid in a certain volume ratio, a surface-active ingredient and a sequestering ingredient consisting of oxalic acid and citric acid in a certain weight ratio.
- the concentration of the acid component, i. H. of the sulfuric acid / phosphoric acid mixture are between about 0.001 and about 0.005% by weight and the concentration of the sequestering component is between about 0.001 and about 0.002% by weight.
- EP-A-0 131 525 describes a process for the preparation of acidic, aqueous solutions which, inter alia, can serve to remove oxide deposits from metallic surfaces, such as steel or aluminum.
- These acidic solutions which have a pH of less than 1, contain 45 to 80% by weight of hydrochloric acid, 20 to 55% by weight of phosphoric acid, 70 to 90% by weight of water and 2 to 20% by weight.
- a hydroxycarboxylic acid preferably citric acid.
- these solutions can also contain dicarboxylic acids, preferably oxalic acid. Sulfuric acid, nitric acid and hydrofluoric acid can also be considered as further acidic components of such solutions.
- DD-A-265 181 describes aqueous solutions which contain 0.01 to 1% by weight of phosphoric acid and 1 to 10% by weight of oxalic acid. These solutions are used for the surface cleaning of etched aluminum foils for electrolytic capacitors after the etching process.
- JP-A-58/48677 relates to a pretreatment agent for steel surfaces before coating them.
- the solutions to be used here contain 1 to 30% by weight of phosphoric acid, 50 to 10,000 mg / l oxalate, a water-soluble solvent and a chelating agent.
- the application of these solutions on the steel surface requires not only a cleaning effect but also the formation of a chemical film.
- the object of the present invention is to provide an aqueous solution for cleaning aluminum surfaces from commodities and equipment for food production and processing, which is fluoride-free on the one hand, because of the toxicological properties of fluorides, and on the other hand, the lowest possible material removal at the Cleaning causes.
- the solutions to be used according to the invention contain no additions of hydrofluoric acid and / or compounds containing fluorine ions, for example alkali metal fluorides such as sodium fluoride.
- the raw materials for the detergent components to be used according to the invention for example phosphoric acid, may contain fluorine ions.
- the solutions to be used according to the invention should not contain more than 500 ppm, preferably not more than 50 ppm and in particular not more than 5 ppm, of fluorine ions, in each case based on the total composition.
- a substitute for the hydrofluoric acid used in technology was thus found, which has the following properties: With a good cleaning effect, a high surface gloss was achieved. The health risk for the cleaning staff is low.
- the main constituent of the solutions to be used according to the invention namely phosphoric acid, is extremely miscible with water and surfactants. A high storage stability can be achieved in commercially available formulations.
- the solutions to be used according to the invention are also completely water-soluble in the customary use concentrations.
- solutions to be used according to the invention can be used, for example, to clean contaminated surfaces, for example barrels, ham molds and aluminum racks, in food production and processing, which are often handled openly.
- a better cleaning result is achieved compared to phosphoric acid alone.
- the cleaning result is also improved compared to combinations of phosphoric acid and hydrofluoric acid.
- both the phosphoric acid and the oxalic acid can be at least partially substituted by corresponding alkali and / or alkaline earth metal salts.
- a particular embodiment of the present invention is therefore that oxalic acid is partially or completely substituted and phosphoric acid partially by its alkali metal and / or alkaline earth metal salts.
- the use of the free acids is preferred for the purposes of the invention.
- the solutions to be used according to the invention may contain further constituents which are selected from surface-active substances, anti-corrosion agents, anti-foaming agents and solubilizers.
- surface-active substances reference should be made in particular to the use of nonionic surfactants and anionic surfactants.
- Cationic surfactants such as quaternary ammonium compounds
- a Ullmann's Encyclopedia of Industrial Chemistry, 1982, pages 455-515 provides an overview of the surfactants that can be used in principle.
- Solubilizers or solvents which can be used according to the invention are also known in principle from Ullmann's Encyclopedia of Industrial Chemistry, volume 16, 4th edition, 1980, pages 279-311.
- fluoride-free aqueous solutions are used, the active substance content of which is based on a concentrate composition consisting of 35% by weight of phosphoric acid and 1.5% by weight of oxalic acid.
- an aqueous solution with an active substance content in the range from 1 to 5% by weight is used, since a customary use concentration of cleaning agents for aluminum surfaces of consumer goods and equipment for food production and processing is about 2% by weight .
- the cleaning is carried out with the aqueous solutions in the temperature range from 35 to 60 ° C.
- the solutions to be used according to the invention can be brought into contact with the aluminum surfaces to be cleaned by various methods. In this sense, it is preferred to bring the aluminum surfaces into contact with the solutions to be used according to the invention by dipping, spraying, foam application or combined processes. Of course, mechanical cleaning can also be carried out here.
- solutions to be used according to the invention can be easily rinsed off with water and give the cleaned surfaces an increased gloss compared to comparable cleaning agents.
- the good rinsing with water is achieved according to the invention in that the solutions to be used according to the invention are packaged in such a way that they can be completely mixed with water in any ratio.
- Phosphoric acid was used in all examples and comparative examples as a 75% strength by weight aqueous solution, so that the actual phosphoric acid levels are 3/4 of the values given in Tables 1 and 2.
- Oxalic acid was used in the form of the dihydrate, which contains 71.4% oxalic acid. Accordingly, the actual content of oxalic acid must be multiplied by a factor of 0.71.
- Table 1 below shows the data obtained for Examples 1 to 7 according to the invention.
- Table 1 example 1 2nd 3rd 4th 5 6 7 water 26 24th 24th 22 44 42 24th Solubilizer / foam stabilizer - 2nd - 2nd 2nd 2nd 2nd Surfactant - - 2nd 2nd 2nd 2nd phosphoric acid 70 70 70 70 50 50 70 Oxalic acid 4th 4th 4th 4th 2nd 4th 2nd Weight loss (g / m2) 0.70 0.72 0.70 0.71 0.69 0.63 0.69 surface glittering
- Example 8 shows the data obtained in Example 8 in comparison to other organic carboxylic acids.
- the cleaning solution of Example 8 has the same composition as that of Example 5, a reduced weight loss is obtained here, which is caused by a possibly slightly changed application temperature.
- the addition of oxalic acid to a cleaning solution containing phosphoric acid without further acidic constituents already brings about a drastic improvement in the weight loss, while the other organic acids have practically no influence on the weight loss.
- a shiny surface of the aluminum sheet was obtained with the aid of example 8 according to the invention, a more or less matt, dull surface was obtained in all comparative examples 1 to 10, which left an impression which was not completely cleaned.
Abstract
Description
Die vorliegende Erfindung betrifft die Verwendung einer fluoridfreien wäßrigen Lösung zur Reinigung von Aluminiumoberflächen von Bedarfgegenständen und Anlagen der Lebensmittelherstellung und -verarbeitung, enthaltend Phosphorsäure und Oxalsäure sowie gegebenenfalls weitere an sich bekannte Bestandteile von Reinigungsmitteln für die Lebensmittelindustrie.The present invention relates to the use of a fluoride-free aqueous solution for cleaning aluminum surfaces of consumer goods and plants for food production and processing, containing phosphoric acid and oxalic acid and optionally other components of detergents for the food industry known per se.
Bisher wurden im Stand der Technik im wesentlichen saure Aluminiumreiniger in der Lebensmittelindustrie verwendet, die auf Phosphorsäurebasis ohne weitere saure Bestandteile hergestellt wurden. Im Handel erhältlich sind vielfach auch phosphorsäurehaltige Reiniger mit einem gewissen Anteil an Flußsäure zur Verbesserung der Reinigung, da bei Phosphorsäurereinigern ohne Flußsäure eine unbefriedigende Reinigung bei schlechter Oberflächenqualität (Glanz) erzielt wird. In Anwesenheit von Flußsäure muß jedoch ein relativ starker Materialabtrag in Kauf genommen werden, der naturgemäß nicht erwünscht ist. Darüberhinaus ist Flußsäure (H₂F₂) toxisch nicht unbedenklich, insbesondere bei der manuellen Reinigung von Bedarfsgegenständen in der Lebensmittelherstellung und -verarbeitung, vor allem bei der Behandlung der Oberflächen in offenen Systemen, bei denen auch ein Kontakt des Reinigungspersonals mit dem Reinigungsmittel nicht auszuschließen ist.So far, acidic aluminum cleaners which have been produced on the basis of phosphoric acid without further acidic constituents have essentially been used in the prior art in the food industry. In many cases, commercially available cleaners containing phosphoric acid with a certain proportion of hydrofluoric acid are also available to improve cleaning, since unsatisfactory cleaning with poor surface quality (gloss) is achieved with phosphoric acid cleaners without hydrofluoric acid. In the presence of hydrofluoric acid, however, a relatively high material removal must be accepted, which is naturally not desirable. In addition, hydrofluoric acid (H₂F₂) is not harmless toxic, especially in the manual cleaning of consumer goods in food production and processing, especially in the treatment of surfaces in open systems, in which contact of the cleaning staff with the cleaning agent can not be excluded.
Bereits in den 20er und 30er Jahren dieses Jahrhunderts wurden Reinigungsmittel für Aluminiumoberflächen entwickelt.Cleaning agents for aluminum surfaces were already developed in the 20s and 30s of this century.
So beschreibt die US-A-1 456 486 einen pulverförmigen Aluminiumreiniger auf der Basis von Spanischer Seife, Oxalsäure, mit geringeren Bestandteilen an Ammoniak, Zinkoxid und Natriumbicarbonat, mit einem Schleifzusatz für die Reinigung von entsprechenden Oberflächen.For example, US-A-1 456 486 describes a powdery aluminum cleaner based on Spanish soap, oxalic acid, with minor constituents of ammonia, zinc oxide and sodium bicarbonate, with an abrasive additive for cleaning corresponding surfaces.
Die US-A-1 554 483 beschreibt ein Verfahren zur Reinigung von Aluminium durch Anwendung organischer Säuren, Salze von organischen Säuren oder Mischungen organischer Säuren und organischer Salze in Anwesenheit von Kohlehydraten bei Temperaturen in der Nähe des Siedepunktes der Reinigungsmittel lösung. Neben Essigsäure, Benzoesäure, Zitronensäure, Maleinsäure, Malonsäure und Weinsäure wird Oxalsäure vorgeschlagen. Eine Reinigungstemperatur in der Nähe des Siedepunktes von Wasser ist jedoch in der Lebensmittelindustrie bei der Reinigung von offenen Systemen nicht durchzuführen oder unerwünscht.US-A-1 554 483 describes a process for the purification of aluminum by using organic acids, salts of organic acids or mixtures of organic acids and organic salts in the presence of carbohydrates at temperatures near the boiling point of the detergent solution. In addition to acetic acid, benzoic acid, citric acid, maleic acid, malonic acid and tartaric acid, oxalic acid is proposed. A cleaning temperature close to the boiling point of water, however, cannot be carried out or is undesirable in the food industry when cleaning open systems.
Auch die US-A-1 890 214 betrifft die Reinigung von Aluminiumoberflächen in der Nähe des Siedepunktes von Wasser in Anwesenheit von Alkalifluoriden. Es wird beschrieben, daß eine Reihe von organischen Fruchtsäuren in Verbindung mit Fluorid Verwendung finden könne. So sind Maleinsäure, Malonsäure, Weinsäure, Zitronensäure, Essigsäure und Oxalsäure als hochkonzentrierte Zusätze neben dem Alkalifluorid in den entsprechenden Reinigungsmitteln enthalten. Bezüglich Oxalsäure wird offenbart, daß diese zwar verwendet werden könnte, jedoch einen zu großen Materialabtrag bewirkt.US-A-1 890 214 also relates to the cleaning of aluminum surfaces near the boiling point of water in the presence of alkali fluorides. It is described that a number of organic fruit acids can be used in conjunction with fluoride. Maleic acid, malonic acid, tartaric acid, citric acid, acetic acid and oxalic acid are included as highly concentrated additives in addition to the alkali fluoride in the corresponding cleaning agents. Regarding oxalic acid, it is disclosed that although this could be used, it causes excessive material removal.
Gegenstand der DE-A-20 54 067 sind mit Wasser verdünnbare, konzentrierte Zusammensetzungen zum Reinigen von Aluminiumoberflächen, zum Desoxidieren, Reinigen und Einebnen beziehungsweise zur Glanzgebung von Oberflächen aus rostfreiem Stahl und zum Bilden eines Eisenphosphatüberzugs auf eisenhaltigen Oberflächen. Diese Zusammensetzungen enthalten Schwefelsäure und Phosphorsäure in einem bestimmten Volumenverhältnis, einen oberflächenaktiven Bestandteil und einen Sequestrierbestandteil, bestehend aus Oxalsäure und Citronensäure in einem bestimmten Gewichtsverhältnis. Beim Verdünnen derartiger Konzentrate mit Wasser für die Reinigung von Aluminium soll die Konzentration des Säurebestandteils, d. h. des Schwefelsäure/Phosphorsäure-Gemisches, zwischen etwa 0,001 und etwa 0,005 Gew.-% und die Konzentration des Sequestrierbestandteils zwischen etwa 0,001 und etwa 0,002 Gew.-% liegen.DE-A-20 54 067 relates to water-dilutable, concentrated compositions for cleaning aluminum surfaces, for deoxidizing, cleaning and leveling or for glossing stainless steel surfaces and for forming an iron phosphate coating on iron-containing surfaces. These compositions contain sulfuric acid and phosphoric acid in a certain volume ratio, a surface-active ingredient and a sequestering ingredient consisting of oxalic acid and citric acid in a certain weight ratio. When diluting such concentrates with water for cleaning aluminum, the concentration of the acid component, i. H. of the sulfuric acid / phosphoric acid mixture are between about 0.001 and about 0.005% by weight and the concentration of the sequestering component is between about 0.001 and about 0.002% by weight.
In der EP-A-0 131 525 wird ein Verfahren zur Herstellung von sauren, wäßrigen Lösungen beschrieben, die unter anderem dazu dienen können, Oxidbeläge von metallischen Oberflächen, wie Stahl oder Aluminium, zu entfernen. Diese sauren Lösungen, die einen pH-Wert von weniger als 1 aufweisen, enthalten 45 bis 80 Gew.-% Salzsäure, 20 bis 55 Gew.-% Phosphorsäure, 70 bis 90 Gew.-% Wasser und 2 bis 20 Gew.-% einer Hydroxycarbonsäure, vorzugsweise Citronensäure. Daneben können diese Lösungen ferner Dicarbonsäuren enthalten, wobei vorzugsweise Oxalsäure genannt wird. Als weitere saure Bestandteile solcher Lösungen kommen auch Schwefelsäure, Salpetersäure und Flußsäure in Betracht.EP-A-0 131 525 describes a process for the preparation of acidic, aqueous solutions which, inter alia, can serve to remove oxide deposits from metallic surfaces, such as steel or aluminum. These acidic solutions, which have a pH of less than 1, contain 45 to 80% by weight of hydrochloric acid, 20 to 55% by weight of phosphoric acid, 70 to 90% by weight of water and 2 to 20% by weight. a hydroxycarboxylic acid, preferably citric acid. In addition, these solutions can also contain dicarboxylic acids, preferably oxalic acid. Sulfuric acid, nitric acid and hydrofluoric acid can also be considered as further acidic components of such solutions.
In der DD-A-265 181 werden wäßrige Lösungen beschrieben, die 0,01 bis 1 Gew.-% Phosphorsäure und 1 bis 10 Gew.-% Oxalsäure enthalten. Diese Lösungen dienen zur Oberflächenreinigung geätzter Aluminiumfolien für Elektrolytkondensatoren im Anschluß an den Ätzprozeß.DD-A-265 181 describes aqueous solutions which contain 0.01 to 1% by weight of phosphoric acid and 1 to 10% by weight of oxalic acid. These solutions are used for the surface cleaning of etched aluminum foils for electrolytic capacitors after the etching process.
Die JP-A-58/48677 betrifft ein Vorbehandlungsmittel für Stahloberflächen vor einer Beschichtung derselben. Die hierbei zu verwendenden Lösungen enthalten 1 bis 30 Gew.-% Phosphorsäure, 50 bis 10 000 mg/l Oxalat, ein wasserlösliches Lösungsmittel sowie einen Chelatbildner. Die Anwendung dieser Lösungen auf dem Stahloberflächen bedingt neben einer Reinigungswirkung ferner die Ausbildung eines chemischen Films.JP-A-58/48677 relates to a pretreatment agent for steel surfaces before coating them. The solutions to be used here contain 1 to 30% by weight of phosphoric acid, 50 to 10,000 mg / l oxalate, a water-soluble solvent and a chelating agent. The application of these solutions on the steel surface requires not only a cleaning effect but also the formation of a chemical film.
Demgegenüber besteht die Aufgabe der vorliegenden Erfindung darin, eine wäßrige Lösung zur Reinigung von Aluminiumoberflächen von Bedarfsgegenständen und Anlagen der Lebensmittelherstellung und -verarbeitung bereitzustellen, die zum einen fluoridfrei ist, wegen der toxikologischen Eigenschaften von Fluoriden, und die zum anderen einen möglichst geringen Materialabtrag bei der Reinigung bewirkt.In contrast, the object of the present invention is to provide an aqueous solution for cleaning aluminum surfaces from commodities and equipment for food production and processing, which is fluoride-free on the one hand, because of the toxicological properties of fluorides, and on the other hand, the lowest possible material removal at the Cleaning causes.
Die vorliegende Erfindung betrifft dementsprechend die Verwendung einer fluoridfreien wäßrigen Lösung zur Reinigung von Aluminiumoberflächen von Bedarfsgegenständen und Anlagen der Lebensmittelherstellung und -verarbeitung, enthaltend Phosphorsäure und Oxalsäure sowie gegebenenfalls weitere an sich bekannte Bestandteile von Reinigungsmitteln für die Lebensmittelindustrie, ausgewählt aus oberflächenaktiven Substanzen, Korrosionsschutzmitteln, Antischaummitteln und Lösevermittlern, dadurch gekennzeichnet, daß man
- a) eine wäßrige Lösung mit einem Aktivsubstanzgehalt im Bereich von 0,5 bis 10 Gew.-% einsetzt,
- b) wobei der Aktivsubstanzgehalt auf eine Konzentratzusammensetzung, bestehend aus
20 bis 60 Gew.-% Phosphorsäure und
0,3 bis 5 Gew.-% Oxalsäure
bezogen ist, - c) und die Reinigung mit dieser wäßrigen Lösung in einem Temperaturbereich von Raumtemperatur bis 60°C durchführt.
- a) an aqueous solution with an active substance content in the range from 0.5 to 10% by weight is used,
- b) wherein the active substance content on a concentrate composition consisting of
20 to 60 wt .-% phosphoric acid and
0.3 to 5 wt% oxalic acid
is related - c) and the cleaning with this aqueous solution in a temperature range from room temperature to 60 ° C.
Wenn im Zusammenhang mit der Erfindung von "fluoridfrei" die Rede ist, so bedeutet dies, daß die erfindungsgemäß zu verwendenden Lösungen keine Zusätze an Flußsäure und/oder fluorionenhaltigen Verbindungen, beispielsweise Alkalimetallfluoride wie Natriumfluorid, enthalten. Darüber hinaus können die Rohstoffe für die erfindungsgemäß zu verwendenden Reinigungsmittel-Komponenten, beispielsweise die Phosphorsäure, je nach Grad der Verunreinigung durchaus Fluorionen enthalten. Dementsprechend sollen die erfindungsgemäß zu verwendenden Lösungen jedoch nicht mehr als 500 ppm, vorzugsweise nicht mehr als 50 ppm und insbesondere nicht mehr als 5 ppm, an Fluorionen, jeweils bezogen auf die Gesamtzusammensetzung, enthalten.If the term "fluoride-free" is used in connection with the invention, this means that the solutions to be used according to the invention contain no additions of hydrofluoric acid and / or compounds containing fluorine ions, for example alkali metal fluorides such as sodium fluoride. In addition, depending on the degree of contamination, the raw materials for the detergent components to be used according to the invention, for example phosphoric acid, may contain fluorine ions. Accordingly, the solutions to be used according to the invention should not contain more than 500 ppm, preferably not more than 50 ppm and in particular not more than 5 ppm, of fluorine ions, in each case based on the total composition.
Es wurde somit ein Ersatzstoff für die in der Technik verwendete Flußsäure gefunden, der die nachfolgenden Eigenschaften aufweist: Bei guter Reinigungswirkung wurde ein hoher Oberflächenglanz erzielt. Die Gesundheitsgefährdung für das Reinigungspersonal ist gering. Der Hauptbestandteil der erfindungsgemäß zu verwendenden Lösungen, nämlich Phosphorsäure, ist mit Wasser und Tensiden außerordentlich gut mischbar. In handelsüblichen Formulierungen läßt sich eine hohe Lagerstabilität erzielen. Auch sind die erfindungsgemäß zu verwendenden Lösungen in den üblichen Einsatzkonzentrationen vollkommen wasserlöslich.A substitute for the hydrofluoric acid used in technology was thus found, which has the following properties: With a good cleaning effect, a high surface gloss was achieved. The health risk for the cleaning staff is low. The main constituent of the solutions to be used according to the invention, namely phosphoric acid, is extremely miscible with water and surfactants. A high storage stability can be achieved in commercially available formulations. The solutions to be used according to the invention are also completely water-soluble in the customary use concentrations.
Mit den erfindungsgemäß zu verwendenden Lösungen lassen sich so beispielsweise in der Lebensmittelherstellung und -verarbeitung verschmutzte Flächen, beispielsweise Fässer, Schinkenformen und Aluminiumgestelle, reinigen, bei denen oftmals offen hantiert wird. Gegenüber Phosphorsäure allein wird ein besseres Reinigungsergebnis erzielt. Ebenso ist das Reinigungsergebnis gegenüber Kombinationen aus Phosphorsäure und Flußsäure verbessert.The solutions to be used according to the invention can be used, for example, to clean contaminated surfaces, for example barrels, ham molds and aluminum racks, in food production and processing, which are often handled openly. A better cleaning result is achieved compared to phosphoric acid alone. The cleaning result is also improved compared to combinations of phosphoric acid and hydrofluoric acid.
Es konnte festgestellt werden, daß mit an sich bekannten Reinigern auf der Basis von Phosphorsäure ohne weitere saure Bestandteile bereits eine gewisse Ätzung von Aluminiumoberflächen beobachtet werden kann. Der Zusatz von Oxalsäure zu phosphorsäurehaltigen Lösungen verminderte jedoch überraschenderweise drastisch den Materialabtrag, wie in den Beispielen der vorliegenden Erfindung dokumentiert wird. Dies ist umso überraschender, da der Zusatz einer organischen Dicarbonsäure, die im Stand der Technik als aggressive Verbindung beschrieben wird (US-A-1 890 214), das Gegenteil hiervon bewirkt.It was found that a certain etching of aluminum surfaces can already be observed with known cleaners based on phosphoric acid without further acidic components. However, the addition of oxalic acid to solutions containing phosphoric acid surprisingly drastically reduced the material removal, as is documented in the examples of the present invention. This is all the more surprising since the addition of an organic dicarboxylic acid, which is described in the prior art as an aggressive compound (US Pat. No. 1,890,214), does the opposite.
Für den Fachmann ist selbstverständlich, daß sowohl die Phosphorsäure als auch die Oxalsäure wenigstens teilweise durch entsprechende Alkali- und/oder Erdalkalimetallsalze substituiert werden kann. Der Ersatz von beispielsweise Oxalsäure durch Natriumoxalat in Anwesenheit einer etwa 50 Gew.-%igen Phosphorsäurelösung bewirkt in der Praxis keine Änderung der Reinigungseigenschaften. Eine besondere Ausführungsform der vorliegenden Erfindung besteht deshalb darin, daß Oxalsäure teilweise oder vollständig und Phosphorsäure teilweise durch deren Alkalimetall- und/oder Erdalkalimetallsalze substituiert wird. Der Einsatz der freien Säuren ist jedoch im Sinne der Erfindung bevorzugt.It is self-evident to the person skilled in the art that both the phosphoric acid and the oxalic acid can be at least partially substituted by corresponding alkali and / or alkaline earth metal salts. The replacement of, for example, oxalic acid with sodium oxalate in the presence of an approximately 50% by weight phosphoric acid solution in practice no change in cleaning properties. A particular embodiment of the present invention is therefore that oxalic acid is partially or completely substituted and phosphoric acid partially by its alkali metal and / or alkaline earth metal salts. However, the use of the free acids is preferred for the purposes of the invention.
Neben Phosphorsäure und Oxalsäure können in den erfindungsgemäß zu verwendenden Lösungen übliche weitere Bestandteile von Reinigungsmitteln für die Lebensmittelindustrie enthalten sein. Eine Übersicht über derartige Bestandteile ist beispielsweise in Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, 1981, Band 20, ab Seite 153 gegeben. Dementsprechend können die erfindungsgemäß zu verwendenden Lösungen weitere Bestandteile enthalten, die ausgewählt sind aus oberflächenaktiven Substanzen, Korrosionsschutzmitteln, Antischaummitteln und Lösevermittlern. Bei den oberflächenaktiven Substanzen ist insbesondere auf die Verwendung von nichtionischen Tensiden und anionischen Tensiden zu verweisen. Auch können selbstverständlich kationische Tenside, wie beispielsweise quartäre Ammoniumverbindungen, in bestimmten Anwendungsbereichen, beispielsweise bei der Desinfektion der Aluminiumoberflächen, eingesetzt werden. Eine Übersicht über die prinzipiell einsetzbaren Tenside gibt Ullmanns Encyklopädie der technischen Chemie, 1982, Seiten 455-515. Erfindungsgemäß einsetzbare Lösevermittler oder Lösungsmittel sind prinzipiell auch aus Ullmanns Encyklopädie der technischen Chemie, Band 16, 4. Auflage, 1980, Seiten 279-311 bekannt.In addition to phosphoric acid and oxalic acid, customary further constituents of cleaning agents for the food industry can be contained in the solutions to be used according to the invention. An overview of such constituents is given, for example, in Ullmanns Encyklopadie der Technische Chemie, 4th edition, 1981, volume 20, from page 153. Accordingly, the solutions to be used according to the invention may contain further constituents which are selected from surface-active substances, anti-corrosion agents, anti-foaming agents and solubilizers. In the case of surface-active substances, reference should be made in particular to the use of nonionic surfactants and anionic surfactants. Cationic surfactants, such as quaternary ammonium compounds, can of course also be used in certain areas of application, for example in the disinfection of aluminum surfaces. A Ullmann's Encyclopedia of Industrial Chemistry, 1982, pages 455-515, provides an overview of the surfactants that can be used in principle. Solubilizers or solvents which can be used according to the invention are also known in principle from Ullmann's Encyclopedia of Industrial Chemistry, volume 16, 4th edition, 1980, pages 279-311.
Gemäß einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung werden fluoridfreie wäßrige Lösungen verwendet, deren Aktivsubstanzgehalt auf eine Konzentratzusammensetzung bestehend aus 35 Gew.-% Phosphorsäure und 1,5 Gew.-% Oxalsäure bezogen ist.According to a further preferred embodiment of the present invention, fluoride-free aqueous solutions are used, the active substance content of which is based on a concentrate composition consisting of 35% by weight of phosphoric acid and 1.5% by weight of oxalic acid.
Ferner ist es erfindungsgemäß bevorzugt, daß man eine wäßrige Lösung mit einem Aktivsubstanzgehalt im Bereich von 1 bis 5 Gew.-% einsetzt, da eine übliche Anwendungskonzentration von Reinigungsmitteln für Aluminiumoberflächen von Bedarfsgegenständen und Anlagen der Lebensmittelherstellung und -verarbeitung etwa 2 Gew.-% beträgt.Furthermore, it is preferred according to the invention that an aqueous solution with an active substance content in the range from 1 to 5% by weight is used, since a customary use concentration of cleaning agents for aluminum surfaces of consumer goods and equipment for food production and processing is about 2% by weight .
Entsprechend einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung wird die Reinigung mit den wäßrigen Lösungen im Temperaturbereich von 35 bis 60 °C durchgeführt.According to a further preferred embodiment of the present invention, the cleaning is carried out with the aqueous solutions in the temperature range from 35 to 60 ° C.
Die erfindungsgemäß zu verwendenden Lösungen können nach verschiedenen Verfahren mit den zu reinigenden Aluminiumoberflächen in Kontakt gebracht werden. Bevorzugt in diesem Sinne ist das in-Kontakt-bringen der Aluminiumoberflächen mit den erfindungsgemäß zu verwendenden Lösungen durch Tauchen, Sprühen, Schaumauftrag oder kombinierte Verfahren. Selbstverständlich kann hier auch eine mechanische Reinigung durchgeführt werden.The solutions to be used according to the invention can be brought into contact with the aluminum surfaces to be cleaned by various methods. In this sense, it is preferred to bring the aluminum surfaces into contact with the solutions to be used according to the invention by dipping, spraying, foam application or combined processes. Of course, mechanical cleaning can also be carried out here.
Die erfindungsgemäß zu verwendenden Lösungen sind gut mit Wasser abspülbar und verleihen den gereinigten Oberflächen einen gegenüber vergleichbaren Reinigungsmitteln erhöhten Glanz. Die gute Abspülbarkeit mit Wasser wird erfindungsgemäß dadurch erreicht, daß man die erfindungsgemäß zu verwendenden Lösungen derart konfektioniert, daß diese in jedem Verhältnis vollständig mit Wasser mischbar sind.The solutions to be used according to the invention can be easily rinsed off with water and give the cleaned surfaces an increased gloss compared to comparable cleaning agents. The good rinsing with water is achieved according to the invention in that the solutions to be used according to the invention are packaged in such a way that they can be completely mixed with water in any ratio.
Die nachfolgenden Beispiele zeigen die besondere Wirkung von Oxalsäure mit vergleichbaren organischen Säuren, die im Stand der Technik für die Anwendung an Aluminiumoberflächen vorgeschlagen wurden. Gegenüber Zitronensäure, Bernsteinsäure, Weinsäure, Äpfelsäure, Glykolsäure, Milchsäure und Malonsäure wird ein deutlich reduzierter Materialabtrag bei der Verwendung von Oxalsäure festgestellt. Darüber hinaus ergibt die visuelle Abmusterung der gereinigten Aluminiumbleche einen verbesserten Glanzeindruck bei der Verwendung von Oxalsäure gegenüber der Verwendung der oben genannten Säuren.The following examples show the special effect of oxalic acid with comparable organic acids, which have been proposed in the prior art for use on aluminum surfaces. Compared to citric acid, succinic acid, tartaric acid, malic acid, glycolic acid, lactic acid and malonic acid, a significantly reduced material removal is found when using oxalic acid. In addition, the visual matching of the cleaned aluminum sheets gives an improved gloss impression when using oxalic acid compared to the use of the acids mentioned above.
In den nachfolgenden Beispielen und Vergleichsbeispielen wurde jeweils wie folgt verfahren:
Reinigungslösungen mit den in den Tabellen 1 und 2 beschriebenen Inhalten wurden hergestellt und diese anschließend mit 98 Gew.-% Wasser verdünnt, und somit Anwendungskonzentrationen der Reinigungslösungen gemäß Tabellen 1 und 2 in 2 Gew.-%iger Lösung erhalten. Die zuvor mit Aceton entfetteten Aluminiumbleche der Legierung Al 99,5 (gemäß Werkstoffnummer 3.0255) einer Größe von 5 x 10 cm wurden im Verlauf von 24 h bei Raumtemperatur in die Lösungen eingetaucht. Die zuvor gewogenen Bleche wurden mit destilliertem Wasser gespült, getrocknet und anschließend erneut gewogen. Der Gewichtsverlust wird in den Tabellen 1 und 2 als Gewichtsabtrag in g/m² bestimmt. Die Einwirkungszeit von 24 h entspricht hierbei einer mehrfachen Reinigung der Aluminiumoberflächen in der technischen Anwendung. Kurzzeitversuche mit einstündiger Einwirkung der Reinigungslösungen ergaben entsprechende Werte.The following examples and comparative examples proceeded as follows:
Cleaning solutions with the contents described in Tables 1 and 2 were prepared and these were subsequently diluted with 98% by weight of water, and use concentrations of the cleaning solutions according to Tables 1 and 2 in 2% by weight solution were thus obtained. The aluminum sheets of the alloy Al 99.5 (according to material number 3.0255) with a size of 5 x 10 cm and degreased with acetone were immersed in the solutions over 24 hours at room temperature. The previously weighed sheets were rinsed with distilled water, dried and then weighed again. The weight loss is determined in Tables 1 and 2 as weight loss in g / m². The exposure time of 24 h corresponds to multiple cleaning of the aluminum surfaces in technical applications. Short-term trials with the cleaning solutions exposed for one hour gave corresponding values.
Die Angaben der Bestandteile sind jeweils als Gewichtsprozent-Angaben zu verstehen. Als Lösevermittler/Schaumstabilisator wurde, soweit vorhanden, in den Beispielen 2, 4 bis 8 und den Vergleichsbeispielen 1 bis 10 jeweils Butyldiglykol eingesetzt. Soweit vorhanden, wurde ein nichtionogenes Tensid (C12/18-Alkyl-dimethylaminoxid (GenaminoxR CS, 30 %ig)) eingesetzt.The details of the components are to be understood in each case as percentages by weight. Where present, butyl diglycol was used as the solubilizer / foam stabilizer in Examples 2, 4 to 8 and Comparative Examples 1 to 10. If available, a nonionic surfactant (C 12/18 alkyl dimethylamine oxide (Genaminox R CS, 30%)) was used.
Phosphorsäure wurde in allen Beispielen und Vergleichsbeispielen als 75 Gew.-%ige wäßrige Lösung eingesetzt, so daß die tatsächlichen Gehalte an Phosphorsäure 3/4 der in den Tabellen 1 und 2 genannten Werte betragen.Phosphoric acid was used in all examples and comparative examples as a 75% strength by weight aqueous solution, so that the actual phosphoric acid levels are 3/4 of the values given in Tables 1 and 2.
Oxalsäure wurde in Form des Dihydrats eingesetzt, das 71,4 % Oxalsäure enthält. Dementsprechend ist der tatsächliche Gehalt an Oxalsäure mit dem Faktor 0,71 zu multiplizieren.Oxalic acid was used in the form of the dihydrate, which contains 71.4% oxalic acid. Accordingly, the actual content of oxalic acid must be multiplied by a factor of 0.71.
Die organischen Carbonsäuren der Vergleichsbeispiele wurden, soweit nicht anders angegeben, in reiner konzentrierter Form eingewogen.Unless stated otherwise, the organic carboxylic acids of the comparative examples were weighed out in pure concentrated form.
Die nachfolgende Tabelle 1 gibt die erhaltenen Daten der erfindungsgemäßen Beispiele 1 bis 7 wieder.
Es zeigt sich, daß eine Veränderung der Konzentration von Phosphorsäure und/oder Oxalsäure innerhalb der erfindungsgemäßen Grenzen praktisch keine wesentliche Änderung des Gewichtsabtrages bewirkt. In allen erfindungsgemäßen Beispielen wurde eine glänzende Oberfläche der Aluminiumbleche erhalten.It turns out that a change in the concentration of phosphoric acid and / or oxalic acid within the limits according to the invention practically does not cause any significant change in the weight loss. In all of the examples according to the invention, a shiny surface of the aluminum sheets was obtained.
Die nachfolgende Tabelle 2 gibt die erhaltenen Daten des Beispiels 8 im Vergleich zu weiteren organischen Carbonsäuren wieder. Obwohl die Reinigungslösung des Beispiels 8 die gleiche Zusammensetzung wie die des Beispiels 5 aufweist, wird hier ein verminderter Gewichtsabtrag erhalten, der seine Ursache in einer gegebenenfalls leicht veränderten Anwendungstemperatur findet. Bemerkenswert ist, daß gegenüber den Vergleichsbeispielen 1 bis 3 der Zusatz von Oxalsäure zu einer Phosphorsäure ohne weitere saure Bestandteile enthaltenden Reinigungslösung bereits eine drastische Verbesserung der Gewichtsabtrages bewirkt, während die weiteren organischen Säuren praktisch keinen Einfluß auf den Gewichtsabtrag zeigen. Während mit Hilfe des erfindungsgemäßen Beispiels 8 eine glänzende Oberfläche des Aluminiumbleches erhalten wurde, wurde in sämtlichen Vergleichsbeispielen 1 bis 10 eine mehr oder weniger matte, stumpfe Oberfläche erhalten, die einen nicht vollständig gereinigten Eindruck hinterläßt.
Claims (6)
- The use of a fluoride-free aqueous solution for cleaning aluminium surfaces of utility articles and equipment used in the manufacture and processing of foods, containing phosphoric acid and oxalic acid and optionally other constituents known per se of cleaning compositions for the food industry selected from surfactants, corrosion inhibitors, antifoam agents and solubilizers, characterized in thata) an aqueous solution with an active substance content of 0.5 to 10% by weight is used,b) the active substance content being based on a concentrate composition consisting of 20 to 60% by weight of phosphoric acid and 0.3 to 5% by weight of oxalic acid,c) and cleaning is carried out with this aqueous solution at a temperature in the range from room temperature to 60°C.
- A process as claimed in claim 1, characterized in that an aqueous solution with an active substance content of 1 to 5% by weight is used.
- The use claimed in claim 1 or 2, characterized in that the active substance content is based on a concentrate composition consisting of
35% by weight of phosphoric acid and
1.5% by weight of oxalic acid. - The use claimed in one or more of claims 1 to 3, characterized in that the oxalic acid is completely or partly substituted and the phosphoric acid partly substituted by its alkali metal or alkaline earth metal salts.
- The use claimed in one or more of claims 1 to 4, characterized in that the aqueous solution is contacted with the aluminium surfaces by immersion, spraying, foam application or combined processes.
- The use claimed in one or more of claims 1 to 5, characterized in that cleaning is carried out at a temperature in the range from 35 to 60°C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4017667A DE4017667A1 (en) | 1990-06-01 | 1990-06-01 | FLUORIDE-FREE CLEANING AGENT FOR ALUMINUM SURFACES |
| DE4017667 | 1990-06-01 | ||
| PCT/EP1991/000961 WO1991019018A1 (en) | 1990-06-01 | 1991-05-23 | Fluoride-free cleaning agents for aluminium surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0531360A1 EP0531360A1 (en) | 1993-03-17 |
| EP0531360B1 true EP0531360B1 (en) | 1995-04-26 |
Family
ID=6407614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91909835A Expired - Lifetime EP0531360B1 (en) | 1990-06-01 | 1991-05-23 | Cleaning of aluminium surfaces |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0531360B1 (en) |
| AT (1) | ATE121806T1 (en) |
| DE (2) | DE4017667A1 (en) |
| DK (1) | DK0531360T3 (en) |
| ES (1) | ES2071313T3 (en) |
| WO (1) | WO1991019018A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498967A (en) * | 2014-12-31 | 2015-04-08 | 苏州禾川化学技术服务有限公司 | Multifunctional aluminum material corrosion-inhibition polishing pickling agent |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008535981A (en) * | 2005-04-13 | 2008-09-04 | ユニリーバー・ナームローゼ・ベンノートシヤープ | Liquid hard surface cleaning composition |
| CN114774933A (en) * | 2022-05-21 | 2022-07-22 | 西安思凯石化科技有限公司 | Environment-friendly cleaning agent for aluminum and aluminum alloy corrosion and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2819193A (en) * | 1952-06-24 | 1958-01-07 | Parker Rust Proof Co | Solution and process for treating metal surfaces |
| US3635826A (en) * | 1969-11-03 | 1972-01-18 | Amchem Prod | Compositions and methods for treating metal surfaces |
| CA1242130A (en) * | 1983-04-12 | 1988-09-20 | Silverio M. Garcia | Acidic compositions having ph values of less than about 1 and method for producing same |
| DD265181A1 (en) * | 1987-09-29 | 1989-02-22 | Mansfeld Kombinat W Pieck Veb | PROCESS FOR SURFACE CLEANING OF ALUMINUM FILM FOR ELECTROLYTE CONDENSERS |
-
1990
- 1990-06-01 DE DE4017667A patent/DE4017667A1/en not_active Withdrawn
-
1991
- 1991-05-23 EP EP91909835A patent/EP0531360B1/en not_active Expired - Lifetime
- 1991-05-23 WO PCT/EP1991/000961 patent/WO1991019018A1/en active IP Right Grant
- 1991-05-23 DE DE59105333T patent/DE59105333D1/en not_active Expired - Fee Related
- 1991-05-23 DK DK91909835.0T patent/DK0531360T3/en active
- 1991-05-23 ES ES91909835T patent/ES2071313T3/en not_active Expired - Lifetime
- 1991-05-23 AT AT91909835T patent/ATE121806T1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498967A (en) * | 2014-12-31 | 2015-04-08 | 苏州禾川化学技术服务有限公司 | Multifunctional aluminum material corrosion-inhibition polishing pickling agent |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0531360T3 (en) | 1995-08-21 |
| ES2071313T3 (en) | 1995-06-16 |
| DE59105333D1 (en) | 1995-06-01 |
| ATE121806T1 (en) | 1995-05-15 |
| DE4017667A1 (en) | 1991-12-05 |
| WO1991019018A1 (en) | 1991-12-12 |
| EP0531360A1 (en) | 1993-03-17 |
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