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EP0531360B1 - Nettoyage de surfaces en aluminium - Google Patents

Nettoyage de surfaces en aluminium Download PDF

Info

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
Authority
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.)
Expired - Lifetime
Application number
EP91909835A
Other languages
German (de)
English (en)
Other versions
EP0531360A1 (fr
Inventor
Alfred Laufenberg
Werner Lüdecke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0531360A1 publication Critical patent/EP0531360A1/fr
Application granted granted Critical
Publication of EP0531360B1 publication Critical patent/EP0531360B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Laminated Bodies (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Cookers (AREA)

Claims (6)

  1. Utilisation d'une solution aqueuse exempte de fluorure, pour le nettoyage des surfaces en aluminium des objets de première nécessité et des installations de fabrication et de transformation des aliments, renfermant de l'acide phosphorique et de l'acide oxalique, ainsi que, le cas échéant, d'autres constituants connus en soi d'agents nettoyants pour l'industrie alimentaire, sélectionnés parmi les substances tensioactives, les agents anticorrosion, les agents antimousse et les agents de solubilisation, caractérisée en ce que l'on
    a) utilise une solution aqueuse avec une concentration en substances actives située dans l'intervalle de 0,5 à 10 % en poids,
    b) dans laquelle la concentration en substances actives se rapporte à une composition de concentré constituée de:
    20 à 60 % d'acide phosphorique et
    0,3 à 5 % en poids d'acide oxalique,
    c) et que l'on procède au nettoyage avec cette solution aqueuse dans une plage de température s'étendant de la température ambiante à 60 °C.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise une solution aqueuse avec une concentration en substances actives dans la plage s'étendant de 1 à 5 % en poids.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que la concentration en substances actives se rapporte à une composition de concentré constituée de
    35 % en poids d'acide phosphorique et
    1,5 % en poids d'acide oxalique.
  4. Utilisation selon une ou plusieurs des revendications 1 à 3, caractérisée en que l'acide oxalique est remplacé partiellement ou totalement et l'acide phosphorique, partiellement, par leurs sels de métaux alcalins ou alcalinoterreux.
  5. Utilisation selon une ou plusieurs des revendications 1 à 4, caractérisée en que l'on met la solution aqueuse en contact avec les surfaces en aluminium par immersion, pulvérisation, application de mousse ou procédés combinés.
  6. Utilisation selon une ou plusieurs des revendications 1 à 5, caractérisée en que l'on effectue le nettoyage dans la plage de température de 35 à 60 °C.
EP91909835A 1990-06-01 1991-05-23 Nettoyage de surfaces en aluminium Expired - Lifetime EP0531360B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4017667 1990-06-01
DE4017667A DE4017667A1 (de) 1990-06-01 1990-06-01 Fluoridfreie reinigungsmittel fuer aluminiumoberflaechen
PCT/EP1991/000961 WO1991019018A1 (fr) 1990-06-01 1991-05-23 Produit sans fluorures de nettoyage de surfaces en aluminium

Publications (2)

Publication Number Publication Date
EP0531360A1 EP0531360A1 (fr) 1993-03-17
EP0531360B1 true EP0531360B1 (fr) 1995-04-26

Family

ID=6407614

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91909835A Expired - Lifetime EP0531360B1 (fr) 1990-06-01 1991-05-23 Nettoyage de surfaces en aluminium

Country Status (6)

Country Link
EP (1) EP0531360B1 (fr)
AT (1) ATE121806T1 (fr)
DE (2) DE4017667A1 (fr)
DK (1) DK0531360T3 (fr)
ES (1) ES2071313T3 (fr)
WO (1) WO1991019018A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104498967A (zh) * 2014-12-31 2015-04-08 苏州禾川化学技术服务有限公司 一种多功能铝材缓蚀抛光酸洗剂
US12134114B2 (en) 2018-11-15 2024-11-05 Ecolab Usa Inc. Acidic cleaner

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101160384B (zh) * 2005-04-13 2011-04-13 荷兰联合利华有限公司 液体硬质表面清洁组合物
CN114774933A (zh) * 2022-05-21 2022-07-22 西安思凯石化科技有限公司 一种环保型铝及铝合金腐蚀用清洗剂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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 (fr) * 1983-04-12 1988-09-20 Silverio M. Garcia Compositions acides a ph inferieur a 1, et leur production
DD265181A1 (de) * 1987-09-29 1989-02-22 Mansfeld Kombinat W Pieck Veb Verfahren zur oberflaechenreinigung geaetzter aluminiumfolie fuer elektrolytkondensatoren

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104498967A (zh) * 2014-12-31 2015-04-08 苏州禾川化学技术服务有限公司 一种多功能铝材缓蚀抛光酸洗剂
US12134114B2 (en) 2018-11-15 2024-11-05 Ecolab Usa Inc. Acidic cleaner

Also Published As

Publication number Publication date
DE59105333D1 (de) 1995-06-01
DE4017667A1 (de) 1991-12-05
ATE121806T1 (de) 1995-05-15
EP0531360A1 (fr) 1993-03-17
ES2071313T3 (es) 1995-06-16
DK0531360T3 (da) 1995-08-21
WO1991019018A1 (fr) 1991-12-12

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