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EP0200001A1 - Process for coating a metal surface with a lubricating oil - Google Patents
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EP0200001A1 - Process for coating a metal surface with a lubricating oil - Google Patents

Process for coating a metal surface with a lubricating oil Download PDF

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Publication number
EP0200001A1
EP0200001A1 EP86104328A EP86104328A EP0200001A1 EP 0200001 A1 EP0200001 A1 EP 0200001A1 EP 86104328 A EP86104328 A EP 86104328A EP 86104328 A EP86104328 A EP 86104328A EP 0200001 A1 EP0200001 A1 EP 0200001A1
Authority
EP
European Patent Office
Prior art keywords
lubricating oil
metal surface
coating
acid
reaction product
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.)
Granted
Application number
EP86104328A
Other languages
German (de)
French (fr)
Other versions
EP0200001B1 (en
Inventor
Yoshio Nagae
Takashi Nihon Parkerizing Ichikawa Kawakami
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.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
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 Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Priority to AT86104328T priority Critical patent/ATE43650T1/en
Publication of EP0200001A1 publication Critical patent/EP0200001A1/en
Application granted granted Critical
Publication of EP0200001B1 publication Critical patent/EP0200001B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/02—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/40—Esters containing free hydroxy or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
    • C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/286—Esters of polymerised unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/2875—Partial esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl groups
    • C10M2207/2885—Partial esters containing free carboxyl groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C10M2207/2895—Partial esters containing free hydroxy groups used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/023—Amines, e.g. polyalkylene polyamines; Quaternary amines used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/044—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms having cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/08—Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • C10M2215/082—Amides [having hydrocarbon substituents containing less than thirty carbon atoms] containing hydroxyl groups; Alkoxylated derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/26—Amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/26—Amines
    • C10M2215/265—Amines used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • Metal sheets e.g. Steel sheets or sheets of tin-plated steel, treated with an anti-corrosive lubricating oil for the manufacture of cans or similar containers, in order to prevent the formation of corrosion or abrasion points during transport and storage.
  • an anti-corrosive lubricating oil for the manufacture of cans or similar containers, in order to prevent the formation of corrosion or abrasion points during transport and storage.
  • the layers produced must be extremely thin. With increasing shipping or export of sheets, the importance of such lubricating oils has increased significantly.
  • the object of the invention is to provide a method for coating metal surfaces with lubricating oil which does not have the known, in particular the aforementioned disadvantages, and which leads to treated metal surfaces which have superior results with regard to corrosion resistance, lubricating properties, paintability and printability as well as cleaning.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention such that a lubricating oil which, in addition to citric acid ester, contains 5 to 40% by weight of a reaction product of organic carboxylic acid and amine, in an amount of Applying 4 to 250 mg / m 2 by electrostatic coating.
  • the content of the reaction product is given as a proportion of the lubricating oil.
  • a preferred embodiment of the invention consists in applying a lubricating oil whose citric acid ester has the formula has, where R 1 , R 2 and R 3 are hydrocarbon radicals having 1 to 8 carbon atoms.
  • the removability of the lubricating oil decreases with higher carbon chains.
  • citric acid esters are trimethyl citrate, triethyl citrate, tripropyl citrate, tributyl citrate and trioctyl citrate.
  • Another advantageous embodiment of the invention consists in applying a lubricating oil to the metal surface, whose reaction product consists of a carboxylic acid of the formula is formed, wherein R is a hydrocarbon radical having 3 to 18 carbon atoms.
  • the corrosion protection achieved is unsatisfactory and the electrical conductivity of the lubricating oil increases, with the result that the film is more difficult to apply. If the hydrocarbon residue has 19 or more carbon atoms, the removability of the lubricating oil is reduced.
  • the carboxylic acids used can be both aliphatic and aromatic in nature.
  • propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, oleic acid, benzoic acid, toluic acid, p-nitrobenzoic acid and tert-butylbenzoic acid are suitable.
  • corrosion protection removability, odor and electrical conductivity, caprylic acid, capric acid, lauric acid and benzoic acid are particularly preferred.
  • R is hydrogen or hydrocarbon radicals having 1 to 4 carbon atoms
  • R 1 and R 2 are hydrocarbon radicals having 1 to 8 carbon atoms
  • R 3 is a hydrocarbon radical having 1 to 4 carbon atoms
  • the molar ratio of organic carboxylic acid to amine is preferably 1: 1.
  • the lubricating oil to be used in the process according to the invention can contain further additives which are conventional per se, such as animal or vegetable oil or synthetic esters, e.g. Dioctyl sebazate, or acetylated trialkyl citrate, to adjust viscosity and conductivity.
  • Surfactants can be introduced to improve the removability of the lubricating oil.
  • Lubricating oil removability Test sheets were placed in a 2% by weight sodium hydroxide solution at 80 ° C. and rinsed with water. The time until complete wettability with water is determined (the shorter the time, the better the removability).
  • the lubricating oil was applied electrostatically to black plate using a coating device, so that a uniform layer weight of 25 mg / m resulted.
  • the sheet treated in this way was then cut to 70 mm x 150 mm sections and subjected to the tests for lubricity, corrosion resistance, lubricant oil removability and paintability. The results of the test can be found in the final table.
  • the lubricating oil was examined in accordance with the information in Example 1. The results are also in the final table.
  • the lubricating oil was applied and tested under the conditions of Example 1. The results can be found in the final table.
  • Triethyl citrate with an electrical conductivity of 0.08 / uS / cm was again applied and investigated under the conditions of Example 1.
  • the dibutylamine salt of caprylic acid was carried out as in Example 1, applied electrostatically and tested.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

1. Process for coating a metal surface with a lubricating oil containing a citric acid ester characterized in that on the metal surface a lubricating oil containing in addition to citric acid ester 5 to 40% by weight of a reaction product of an organic carboxylic acid and an amine is applied by electrostatic coating in a quantity of 4 to 250 mg/m**2 .

Description

Die Erfindung betrifft ein Verfahren zum Beschichten einer Metalloberfläche mit einem Zitronensäureester enthaltenden Schmieröl sowie dessen Anwendung auf die Beschichtung von Metalloberflächen aus Eisenwerkstoffen.The invention relates to a method for coating a metal surface with a lubricating oil containing citric acid ester and its application to the coating of metal surfaces made of ferrous materials.

Üblicherweise werden Metallbleche, z.B. Stahlbleche oder Bleche aus verzinntem Stahl, für die Herstellung von Dosen oder ähnlichen Behältern mit einem korrosionsschützenden Schmieröl behandelt, um auf diese Weise die Bildung von Korrosion oder Abriebstellen während Transport und Lagerung zu verhindern. Im Hinblick auf die Lackierbarkeit bzw. die Entfernbarkeit des Schmieröls mit irgendwelchen Reinigungsmitteln müssen jedoch die erzeugten Schichten extrem dünn sein. Mit zunehmendem Versand oder Export von Blechen hat sich die Bedeutung derartiger Schmieröle stark erhöht.Metal sheets, e.g. Steel sheets or sheets of tin-plated steel, treated with an anti-corrosive lubricating oil for the manufacture of cans or similar containers, in order to prevent the formation of corrosion or abrasion points during transport and storage. In view of the paintability or the removability of the lubricating oil with any cleaning agents, however, the layers produced must be extremely thin. With increasing shipping or export of sheets, the importance of such lubricating oils has increased significantly.

Im allgemeinen hat man bisher Dioctylsebazat auf die Bleche aufgebracht und anschließend mit einem, einen flüchtigen Korrosionsinhibitor aufweisenden Korrosionsschutzpapier verpackt. Der auf diese Weise erhaltene Korrosionsschutz ist jedoch unbefriedigend. Auch ist die Entfernbarkeit dieser Öle schwierig, so daß es in der Folgebehandlung zu ungenügender Lackhaftung oder ungleichmäßiger Metallabscheidung kommen kann.In general, dioctyl sebazate has hitherto been applied to the metal sheets and then packaged with an anti-corrosive paper containing a volatile corrosion inhibitor. However, the corrosion protection obtained in this way is unsatisfactory. It is also difficult to remove these oils, so that insufficient paint adhesion or uneven metal deposition can occur in the subsequent treatment.

Es ist auch bekannt, Schmieröle auf Basis Zitronensäureester aufzubringen (US-PS 3 923 471, US-PS 4 287 741). Dabei sind zwar die elektrostatische Beschichtbarkeit, das Schmiervermögen und die Lackhaftung befriedigend, jedoch sind vermittelter Korrosionswiderstand und Entfernbarkeit des Schmieröls mangelhaft.It is also known to be based on lubricating oils Apply citric acid esters (U.S. Patent 3,923,471, U.S. Patent 4,287,741). Although the electrostatic coatability, the lubricity and the paint adhesion are satisfactory, the corrosion resistance and the removability of the lubricating oil are poor.

Aufgabe der Erfindung ist es, ein Verfahren zur Beschichtung von Metalloberflächen mit Schmieröl bereitzustellen, das nicht mit den bekannten, insbesondere vorgenannten Nachteilen behaftet ist und zu behandelten Metalloberflächen führt, die bezüglich Korrosionswiderstand, Schmiervermägen, Lackier- und Bedruckbarkeit sowie Reinigung überlegene Ergebnisse aufweisen.The object of the invention is to provide a method for coating metal surfaces with lubricating oil which does not have the known, in particular the aforementioned disadvantages, and which leads to treated metal surfaces which have superior results with regard to corrosion resistance, lubricating properties, paintability and printability as well as cleaning.

Die Aufgabe wird gelöst, indem das Verfahren der eingangs genannten Art entsprechend der Erfindung derart ausgestaltet wird, daß man auf die Metalloberfläche ein Schmieröl, das neben Zitronensäureester 5 bis 40 Gew.-% eines Reaktionsproduktes aus organischer Carbonsäure und Amin enthält, in einer Menge von 4 bis 250 mg/m2 durch elektrostatisches Beschichten aufbringt.The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention such that a lubricating oil which, in addition to citric acid ester, contains 5 to 40% by weight of a reaction product of organic carboxylic acid and amine, in an amount of Applying 4 to 250 mg / m 2 by electrostatic coating.

Der Gehalt an Reaktionsprodukt ist als Anteil am Schmieröl angegeben.The content of the reaction product is given as a proportion of the lubricating oil.

Um zur vorgenannten Lösung zu gelangen, wurden zahlreiche Versuche durchgeführt. Sie dienten hinsichtlich des Schmieröls der Ermittlung des vermittelten Korrosionsschutzes, des Schmiervermögens, der Verträglichkeit mit Lacken und Druckfarben sowie der Entfernbarkeit, hinsichtlich der elektrostatischen Applizierbarkeit der Ermittlung der elektrischen Leitfähigkeit. Bei den zuletzt erwähnten Untersuchungen ist zu berücksichtigen, daß Schmieröle mit hoher elektrischer Leitfähigkeit praktisch nicht mit elektrischen Ladungen zu versehen und daher kaum elektrostatisch zu versprühen sind. Wenn überhaupt, werden nur ungleichmäßige Filme erzeugt. Als unabdingbare Eigenschaft des Schmieröls war mithin auch eine geringe elektrische Leitfähigkeit gefordert.Numerous tests have been carried out to arrive at the aforementioned solution. With regard to the lubricating oil, they were used to determine the corrosion protection imparted, the lubricity, the compatibility with paints and printing inks and the removability with regard to the electrostatic Applicability of the determination of the electrical conductivity. In the last-mentioned investigations, it should be taken into account that lubricating oils with high electrical conductivity are practically not to be provided with electrical charges and therefore can hardly be sprayed electrostatically. If anything, only uneven films are produced. As an indispensable property of the lubricating oil, low electrical conductivity was also required.

E:ne bevorzugte Ausführungsform der Erfindung besteht darin, ein Schmieröl aufzubringen, dessen Zitronensäureester die Formel

Figure imgb0001
besitzt, wobei R1, R2 und R3 Kohlenwasserstoffreste mit 1 bis 8 C-Atomen bedeuten.E: a preferred embodiment of the invention consists in applying a lubricating oil whose citric acid ester has the formula
Figure imgb0001
 has, where R 1 , R 2 and R 3 are hydrocarbon radicals having 1 to 8 carbon atoms.

Bei höheren Kohlenstoffketten geht die Entfernbarkeit des Schmieröles zurück.The removability of the lubricating oil decreases with higher carbon chains.

Besonders geeignete Zitronensäureester sind Trimethylcitrat, Triethylcitrat, Tripropylcitrat, Tributylcitrat und Trioctylcitrat.Particularly suitable citric acid esters are trimethyl citrate, triethyl citrate, tripropyl citrate, tributyl citrate and trioctyl citrate.

Eine weitere vorteilhafte Ausgestaltung der Erfindung besteht darin, auf die Metalloberfläche ein Schmieröl aufzubringen, dessen Reaktionsprodukt aus einer Carbonsäure der Formel

Figure imgb0002
gebildet ist, wobei R ein Kohlenwasserstoffrest mit 3 bis 18 C-Atomen ist.Another advantageous embodiment of the invention consists in applying a lubricating oil to the metal surface, whose reaction product consists of a carboxylic acid of the formula
Figure imgb0002
 is formed, wherein R is a hydrocarbon radical having 3 to 18 carbon atoms.

Wenn die Kohlenwasserstoffkette der Carbonsäure 2 oder nur 1 C-Atom enthält, ist der erzielte Korrosionsschutz unbefriedigend und steigt die elektrische Leitfähigkeit des Schmieröls mit der Folge erschwerter Aufbringung des Filmes. Wenn der Kohlenwasserstoffrest 19 oder mehr C-Atome aufweist, ist die Entfernbarkeit des Schmieröles herabgesetzt.If the hydrocarbon chain of the carboxylic acid contains 2 or only 1 carbon atom, the corrosion protection achieved is unsatisfactory and the electrical conductivity of the lubricating oil increases, with the result that the film is more difficult to apply. If the hydrocarbon residue has 19 or more carbon atoms, the removability of the lubricating oil is reduced.

Die zum Einsatz kommenden Carbonsäuren können sowohl aliphatischer als auch aromatischer Natur sein. Geeignet sind beispielsweise Propionsäure, Buttersäure, Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Oleinsäure, Benzoesäure, Toluylsäure, p-Nitrobenzoesäure und tert-Butylbenzoesäure. Im Hinblick auf Korrosionsschutz, Entfernbarkeit, Geruch und elektrische Leitfähigkeit sind Caprylsäure, Caprinsäure, Laurinsäure und Benzoesäure besonders bevorzugt.The carboxylic acids used can be both aliphatic and aromatic in nature. For example, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, oleic acid, benzoic acid, toluic acid, p-nitrobenzoic acid and tert-butylbenzoic acid are suitable. With regard to corrosion protection, removability, odor and electrical conductivity, caprylic acid, capric acid, lauric acid and benzoic acid are particularly preferred.

Primäre Amine sind wegen eventueller Geruchsbelästigungen weniger geeignet. Daher sieht eine weitere vorteilhafte Ausführungsform der Erfindung vor, ein Schmieröl aufzubringen, dessen Reaktionsprodukt aus einem sekundären oder tertiären Amin gebildet ist. Derartige Amine sind Di- oder Trialkylamin, wie Di- oder Tri-methylamin, -ethylamin, -butylamin, sowie Ethylhexylamin, aber auch Aminoalkohole, wie Dimethylethanolamin, Diethylethanolamin, Dibutylethanolamin, Dihexylethanolamin und dergl. Schließlich können auch Cyclohexylamine, wie Dicyclohexylamin, sowie Morpholin, Die hanolamin und Methylmorpholan eingesetzt werden.Primary amines are less suitable due to possible odor nuisance. A further advantageous embodiment of the invention therefore provides for the application of a lubricating oil whose reaction product consists of a secondary one or tertiary amine is formed. Such amines are di- or trialkylamine, such as di- or tri-methylamine, -ethylamine, -butylamine, and ethylhexylamine, but also aminoalcohols, such as dimethylethanolamine, diethylethanolamine, dibutylethanolamine, dihexylethanolamine and the like. Finally, cyclohexylamines, such as dicyclohexylamine, and also The hanolamine and methylmorpholan are used.

Weiterhin wurde gefunden, daß bei Einsatz eines Reaktionsproduktes, das mit einem 3 OH-Gruppen aufweisenden Amin hergestellt worden ist, cer Korrosionsschutz verringert und die elektrische Leitfähigkeit erhöht wird. Demzufolge ist es vorteilhaft, ein Schmieröl aufzubringen, dessen Reaktionsprodukt aus einem Amin gebildet ist, das maximal 2 OH-Gruppen aufweist.Furthermore, it was found that when using a reaction product which has been prepared with an amine containing 3 OH groups, cer corrosion protection is reduced and the electrical conductivity is increased. Accordingly, it is advantageous to apply a lubricating oil whose reaction product is formed from an amine which has a maximum of 2 OH groups.

Demnach besitzen besonders geeignete Aminverbindungen folgende allgemeine Formel:

Figure imgb0003
wobei R1 und R2 Kohlenwasserstoff-Reste mit 1 bis 4 C-Atomen und R3 Wasserstoff oder Kohlenwasserstoff-Rest mit 1 bis 4 C-Atomen, bzw.
Figure imgb0004
wobei R1, R2 und R3 Kohlenwasserstoff-Reste mit 1Accordingly, particularly suitable amine compounds have the following general formula:
Figure imgb0003
 where R 1 and R 2 are hydrocarbon radicals with 1 to 4 C atoms and R 3 is hydrogen or a hydrocarbon radical with 1 to 4 C atoms, or
Figure imgb0004
 where R 1 , R 2 and R 3 are hydrocarbon radicals with 1

bis 8 C-Atomen, bzw.

Figure imgb0005
wobei P Kohlenwasserstoff-Reste mit 6 C-Atomen, bzw.
Figure imgb0006
wobei R Wasserstoff oder Kohlenwasserstoff-Reste mit 1 bis 4 C-Atomen, bzw.
Figure imgb0007
wobei R1 und R2 Kohlenwasserstoff-Reste mit 1 bis 8 C-Atomen und R3 ein Kohlenwasserstoff-Rest mit 1 bis 4 C-Atomenup to 8 carbon atoms, or
Figure imgb0005
 where P hydrocarbon residues with 6 carbon atoms, or
Figure imgb0006
 where R is hydrogen or hydrocarbon radicals having 1 to 4 carbon atoms, or
Figure imgb0007
 where R 1 and R 2 are hydrocarbon radicals having 1 to 8 carbon atoms and R 3 is a hydrocarbon radical having 1 to 4 carbon atoms

bedeuten.mean.

Das Mol-Verhältnis von organischer Carbonsäure zu Amin ist vorzugsweise 1 : 1.The molar ratio of organic carboxylic acid to amine is preferably 1: 1.

Die Untersuchungsergebnisse haben gezeigt, daß bei einem Anteil am Schmieröl unter 5 Gew.-% der Korrosionsschutz abnimmt. Bei einem Anteil des Reaktionsproduktes über 40 Gew.-% am Schmieröl steigt die elektrische Leitfähigkeit, so daß die Applikation erschwert wird. Schließlich wurde festgestellt, daß bei Schichtgewichten unter 4 mg/m2 die erzeugten Schichten uneinheitlich sind, während Schmiervermögen und Korrosionsschutz geschwächt werden. Bei Schichtgewichten über 250 mg/m2 werden Lackauftrag und Bedruckung sowie die Entfernbarkeit des Schmieröls erschwert.The test results have shown that in one The proportion of lubricating oil below 5% by weight decreases the corrosion protection. If the reaction product contains more than 40% by weight of the lubricating oil, the electrical conductivity increases, so that the application is made more difficult. Finally, it was found that at layer weights below 4 mg / m 2, the layers produced are inconsistent, while lubricity and corrosion protection are weakened. With layer weights over 250 mg / m 2 , coating and printing as well as the removability of the lubricating oil are made more difficult.

Das innerhalb des erfindungsgemäßen Verfahrens einzusetzende Schmieröl kann weitere, an sich übliche Zusätze, wie tierisches oder pflanzliches Öl oder synthetische Ester, z.B. Dioctylsebazat, oder acetyliertes Trialkylcitrat, zur Einstellung von Viskosität und Leitfähigkeit enthalten. Tenside können zur Verbesserung der Entfernbarkeit des Schmieröls eingebracht werden.The lubricating oil to be used in the process according to the invention can contain further additives which are conventional per se, such as animal or vegetable oil or synthetic esters, e.g. Dioctyl sebazate, or acetylated trialkyl citrate, to adjust viscosity and conductivity. Surfactants can be introduced to improve the removability of the lubricating oil.

Das erfindungsgemäße Verfahren ist zum Beschichten einer Vielzahl von Metalloberflächen geeignet. Mit besonderem Vorteil ist es auf die Beschichtung von Blech oder Band aus Stahl bzw. verzinntem Stahl anwendbar. Eine besonders geeignete Stahlqualität ist sogenannter "tin-free-steel", unter dem man Stahl mit Kombinationsschichten aus metallischem Chrom (z.B. 0,02 bis 0,05 g/m2) und darauf aufgelagertem Chromhydroxid (z.B. 0,2 bis 0,5 g/m2, berechnet als Cr(OH)3 . 3 H20), versteht. Diese Schichten werden durch kathodische Schaltung aus Chromsäure und Schwefelsäure oder Fluorwasserstoff enthaltenden Elektrolyten erzeugt.The method according to the invention is suitable for coating a large number of metal surfaces. It is particularly applicable to the coating of sheet metal or strip made of steel or tinned steel. A particularly suitable steel quality is so-called "tin-free steel", under which steel with combination layers of metallic chromium (for example 0.02 to 0.05 g / m 2 ) and chromium hydroxide (for example 0.2 to 0.5) is deposited thereon g / m 2, calculated as Cr (OH) 3. 3 H 2 0), of course. These layers are produced by cathodic switching from electrolytes containing chromic acid and sulfuric acid or hydrogen fluoride.

Die Erfindung wird anhand der folgenden Beispiele beispielsweise und näher erläutert.The invention is illustrated by the following examples for example and explained in more detail.

Zur Ermittlung der Versuchsergebnisse dienten die nachfolgend auf geführten Tests.The tests listed below were used to determine the test results.

Schmiervermögen: Für die Testbleche wurde der Reibungsbeiwert mit Hilfe der Bauden'schen Testvorrichtung ermittelt.Lubricity: For the test sheets, the coefficient of friction was determined using the Bauden test device.

Korrosionswiderstand: 5 Testbleche mit den Abmessungen 75 x 150 mr wurden neschichtet, mit Tarpaulin-Papier zu einem Paket gewickelt und an den Enden mit Klebband verschlossen. Das Paket wurde dann für die Dauer von 20 Tagen in die auf 50°C und 90 % relative Luftfeuchtigkeit gehaltene Testvorrichtung gegeben.Corrosion resistance: 5 test sheets measuring 75 x 150 mr were coated, wrapped in tarpaulin paper to form a package and sealed at the ends with adhesive tape. The package was then placed in the tester maintained at 50 ° C and 90% relative humidity for 20 days.

Schmieröl-Entfernbarkeit: Testbleche wurden in eine 2 Gew.-%ige Natronlauge bei 80°C gegeben und mit Wasser gespült. Die Zeitdauer bis zur vollständigen Benetzbarkeit mit Wasser wird bestimmt (je geringer die Zeitdauer ist, desto besser ist die Entfernbarkeit).Lubricating oil removability: Test sheets were placed in a 2% by weight sodium hydroxide solution at 80 ° C. and rinsed with water. The time until complete wettability with water is determined (the shorter the time, the better the removability).

Lackhaftunq: Die Bleche werden mit einem Epoxiphenol-Lack für Dosen derart überzogen, daß nach dem Härten des Lackes ein Schichtgewicht von 50 + 5 mg/dm2 resultiert. Die Härtung erfolgt bei 200 bis 205°C während einer Zeitdauer von 10 min. Danach werden die Bleche bis auf die Metalloberfläche mit einem Gitterschnitt versehen, so daß Quadrate von 1 mm2 Größe entstehen. Danach wird der Grad des Abplatzens ermittelt und bewertet.Lackhaftunq: The plates are coated with a lacquer for cans Epoxiphenol such that after curing the lacquer layer, a W eight of 50 + 5 mg / dm 2 results. The curing takes place at 200 to 205 ° C for a period of 10 minutes. The sheets are then cross-cut to the metal surface, so that squares of 1 mm 2 in size are produced. The degree of flaking is then determined and evaluated.

Beispiel 1example 1

1 Mol Caprylsäure und 1 Mol Dibutylamin wurden miteinander vermischt und bei einer Temperatur von 50 bis 60°C mit einem Rührer während einer Zeitdauer von 30 min zur Reaktion gebracht. Das erhaltene Dibutylaminsalz der Caprylsäure wurde in einer Menge von 30 Teilen mit 70 Teilen Triethylcitrat vermischt. Auf diese Weise wurde ein korrosionsschützendes Schmieröl erhalten, dessen elektrische Leitfähigkeit 1,3 µS/cm beträgt.1 mole of caprylic acid and 1 mole of dibutylamine were mixed together and reacted at a temperature of 50 to 60 ° C. with a stirrer for a period of 30 minutes. The obtained dibutylamine salt of caprylic acid was mixed in an amount of 30 parts with 70 parts of triethyl citrate. In this way, a corrosion-protecting lubricating oil was obtained, the electrical conductivity of which is 1.3 µS / cm.

Das Schmieröl wurde elektrostatisch auf Schwarzblech mittels einer Beschichtungsvorrichtung aufgebracht, so daß ein einheitliches Schichtgewicht von 25 mg/m resultierte. Das auf diese Weise behandelte Blech wurde dann auf Abschnitte der Größe 70 mm x 150 mm geschnitten und den Tests bezüglich Schmiervermögen, Korrosionswiderstand, Schmieröl-Entfernbarkeit und Lackierbarkeit unterworfen. Die Ergebnisse des Tests finden sich in der abschließenden Tabelle.The lubricating oil was applied electrostatically to black plate using a coating device, so that a uniform layer weight of 25 mg / m resulted. The sheet treated in this way was then cut to 70 mm x 150 mm sections and subjected to the tests for lubricity, corrosion resistance, lubricant oil removability and paintability. The results of the test can be found in the final table.

Beispiel 2Example 2

Zur Herstellung des Reaktionsproduktes diente 1 Mol Laurinsäure und 1 Mol Diethylethanolamin. Beide Verbindungen wurden miteinander vermischt und bei einer Temperatur im Bereich von 50 bis 60°C während einer Zeitdauer von 30 min gerührt. 30 Teile des auf diese Weise erhaltenen Diethylethanolaminsalzes der Laurinsäure und 70 Teile Tributylcitrat wurden unter Bildung eines korrosionsschützenden Schmieröls vermischt. Die Leitfähigkeit des Schmieröls betrug 5,5 /uS/cm.1 mol of lauric acid and 1 mol of diethylethanolamine were used to prepare the reaction product. Both compounds were mixed together and stirred at a temperature in the range from 50 to 60 ° C. for a period of 30 minutes. 30 parts of the diethylethanolamine salt of lauric acid and 70 parts of tributyl citrate thus obtained were mixed to form an anti-corrosion lubricating oil. The conductivity of the lubricating oil was 5.5 / uS / cm.

Die Untersuchung des Schmieröles erfolgte entsprechend den Angaben in Beispiel 1. Die Ergebnisse befinden sich ebenfalls in der abschließenden Tabelle.The lubricating oil was examined in accordance with the information in Example 1. The results are also in the final table.

Beispiel 3Example 3

1 Mol Laurinsäure und 1 Mol Morpholin wurden vermischt und bei einer Temperatur von 50 bis 60°C während 30 min unter Rühren zur Reaktion gebracht. 30 Teile des Morpholinsalzes der Laurinsäure und 70 Teile Triisopropylcitrat wurden unter Bildung eines Schmieröles mit einer elektrischen Leitfähigkeit von 5,5 µS/cm vermischt. Die elektrostatische Beschichtung und die Überprüfung der Qualität des Schmieröles erfolgte wie in Beispiel 1 angegeben. Die Ergebnisse sind in der nachfolgenden Tabelle aufgeführt.1 mol of lauric acid and 1 mol of morpholine were mixed and reacted at a temperature of 50 to 60 ° C for 30 minutes with stirring. 30 parts of the morpholine salt of lauric acid and 70 parts of triisopropyl citrate were mixed to form a lubricating oil with an electrical conductivity of 5.5 µS / cm. The electrostatic coating and the checking of the quality of the lubricating oil were carried out as indicated in Example 1. The results are shown in the table below.

Beispiel 4Example 4

1 Mol tert-Butylbenzoesäure und 1 Mol Dibutylethanolamin wurden vermischt und während einer Zeit von 30 min bei einer Temperatur von 50 bis 60°C unter Rühren zur Reaktion gebracht. Danach wurden 30 Teile des Dibutylethanolaminsalzes der tert-Butylbenzoesäure mit 70 Teilen Triethylcitrat vermischt, wodurch ein Schmieröl mit einer elektrischen Leitfähigkeit von 5,5 /uS/cm entstand.1 mol of tert-butylbenzoic acid and 1 mol of dibutylethanolamine were mixed and reacted with stirring at a temperature of 50 to 60 ° C. for 30 minutes. Then 30 parts of the dibutylethanolamine salt of tert-butylbenzoic acid were mixed with 70 parts of triethyl citrate, whereby a lubricating oil with an electrical conductivity of 5.5 / uS / cm was formed.

Das Schmieröl wurde unter den Bedingungen des Beispiels 1 aufgebracht und geprüft. Die Ergebnisse finden sich in der abschließenden Tabelle.The lubricating oil was applied and tested under the conditions of Example 1. The results can be found in the final table.

Vergleichsbeispiel 1Comparative Example 1

Dioctylsebazat mit einer elektrischen Leitfähigkeit von 0,02 /uS/cm wurde unter den Bedingungen des Beispiels 1 appliziert und geprüft.Dioctyl sebazate with an electrical conductivity of 0.02 / uS / cm was applied and tested under the conditions of Example 1.

Vergleichsbeispiel 2Comparative Example 2

Triethylcitrat mit einer elektrischen Leitfähigkeit von 0,08 /uS/cm wurde wiederum unter den Bedingungen des Beispiels 1 aufgebracht und untersucht.Triethyl citrate with an electrical conductivity of 0.08 / uS / cm was again applied and investigated under the conditions of Example 1.

Vergleichsbeispiel 3Comparative Example 3

Dibutylaminsalz von Caprylsäure wurde wie in Beispiel 1 ausgeführt, elektrostatisch aufgebracht und geprüft.The dibutylamine salt of caprylic acid was carried out as in Example 1, applied electrostatically and tested.

Die Ergebnisse der Vergleichsversuche 1 bis 3 sind ebenfalls in der folgenden Tabelle enthalten.

Figure imgb0008
The results of comparative experiments 1 to 3 are also shown in the table below.
Figure imgb0008

Claims (7)

1. Verfahren zum Beschichten einer Metalloberfläche mit einem Zitronensäureester enthaltenden Schmieröl,
dadurch gekennzeichnet, daß man auf die Metalloberfläche ein Schmieröl, das neben Zitronensäureester 5 bis 40 Gew.-% eines Reaktionsproduktes aus organischer Carbonsäure und Amin enthält, in einer Menge von 4 bis 250 mg/m2 durch elektrostatisches Beschichten aufbringt.1. Method for coating a metal surface with a lubricating oil containing citric acid ester,
characterized in that a lubricating oil containing 5 to 40% by weight of a reaction product of organic carboxylic acid and amine in addition to citric acid ester is applied in an amount of 4 to 250 mg / m 2 by electrostatic coating. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man auf die Metalloberfläche ein Schmieröl aufbringt, dessen Zitronensäureester die Formel
Figure imgb0009
besitzt, wobei R1, R2 und R 3 Kohlenwasserstoffreste mit 1 bis 8 C-Atomen bedeuten.2. The method according to claim 1, characterized in that a lubricating oil is applied to the metal surface, the citric acid ester of which the formula
Figure imgb0009
has, where R1 , R2 and R 3 are hydrocarbon radicals having 1 to 8 carbon atoms. 3. Verfahren nach Anspruch 1 oder 2, dadurch
gekennzeichnet, daß man auf die Metalloberfläche ein Schmieröl aufbringt, dessen Reaktionsprodukt aus einer Carbonsäure der Formel3. The method according to claim 1 or 2, characterized
characterized in that a lubricating oil is applied to the metal surface, the reaction product of which consists of a carboxylic acid of the formula
Figure imgb0010
gebildet ist, wobei R ein Kohlenwasserstoff-Rest mit 3 bis 18 C-Atomen ist.
Figure imgb0010
 is formed, wherein R is a hydrocarbon radical having 3 to 18 carbon atoms. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß man auf die Metalloberfläche ein Schmieröl aufbringt, dessen Reaktionsprodukt aus einem sekundären oder tertiären Amin gebildet ist.4. The method according to claim 1, 2 or 3, characterized in that a lubricating oil is applied to the metal surface, the reaction product of which is formed from a secondary or tertiary amine. 5. Verfahren nach Anspruch 1, 2, 3 oder 4, dadurch gekennzeichnet, daß man auf die Metalloberfläche ein Schmieröl aufbringt, dessen Reaktionsprodukt aus einem Amin gebildet ist, das maximal 2 OH-Gruppen aufweist.5. The method according to claim 1, 2, 3 or 4, characterized in that a lubricating oil is applied to the metal surface, the reaction product of which is formed from an amine which has a maximum of 2 OH groups. 6. Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 5 auf die Beschichtung von Metalloberflächen aus Eisenwerkstoffen (von Stahl).6. Application of the method according to one or more of claims 1 to 5 to the coating of metal surfaces made of ferrous materials (steel).
EP86104328A 1985-04-04 1986-03-28 Process for coating a metal surface with a lubricating oil Expired EP0200001B1 (en)

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Publication number Priority date Publication date Assignee Title
EP0562405A1 (en) * 1992-03-24 1993-09-29 Hoechst Aktiengesellschaft Use of citric acid esters as lubricant for refrigerant compressor
GB2296714A (en) * 1994-12-15 1996-07-10 Abbey Lubricant and anti-corrosion composition
EP0721977A1 (en) * 1994-12-15 1996-07-17 Abbey (Research & Development) Ltd. Coating composition comprising short chain carboxylic acid, citric acid ester and organic ester
US5614268A (en) * 1994-12-15 1997-03-25 Varley; Michael J. Coating composition
GB2296714B (en) * 1994-12-15 1998-03-25 Abbey Coating composition
WO1999023281A1 (en) * 1997-10-30 1999-05-14 Henkel Kommanditgesellschaft Auf Aktien METAL PROCESSING LIQUID FOR THE NEUTRAL pH RANGE
WO2001088068A1 (en) * 2000-05-19 2001-11-22 Usinor Use of an oil composition for temporary treatment of metal surfaces
FR2809116A1 (en) * 2000-05-19 2001-11-23 Usinor Use of a vegetable oil composition for the temporary protection and lubrication of metallic surfaces to impart improved tribological properties and corrosion resistance
US6919302B2 (en) 2000-05-19 2005-07-19 Usinor Use of an oil composition for temporary treatment of metal surfaces
WO2016198202A1 (en) * 2015-06-09 2016-12-15 Henkel Ag & Co. Kgaa Use of citric acid esters as corrosion inhibitor in alcoholic cosmetic compositions that can be sprayed as an aerosol

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ATE43650T1 (en) 1989-06-15
DE3610641A1 (en) 1986-10-09
JPS61230772A (en) 1986-10-15
EP0200001B1 (en) 1989-05-31
DE3663691D1 (en) 1989-07-06

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