EP0494884A1 - Process for manufacturing stable, low-viscosity ow anti-rust emulsions. - Google Patents

Process for manufacturing stable, low-viscosity ow anti-rust emulsions.

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Publication number
EP0494884A1
EP0494884A1 EP90913798A EP90913798A EP0494884A1 EP 0494884 A1 EP0494884 A1 EP 0494884A1 EP 90913798 A EP90913798 A EP 90913798A EP 90913798 A EP90913798 A EP 90913798A EP 0494884 A1 EP0494884 A1 EP 0494884A1
Authority
EP
European Patent Office
Prior art keywords
emulsion
weight
mixture
carbon atoms
emulsions
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
EP90913798A
Other languages
German (de)
French (fr)
Other versions
EP0494884B1 (en
Inventor
Horst-Dieter Speckmann
Gert-Lothar Striepling
Frank Wiechmann
Juergen Geke
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 EP0494884A1 publication Critical patent/EP0494884A1/en
Application granted granted Critical
Publication of EP0494884B1 publication Critical patent/EP0494884B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/06—Hydroxy compounds having hydroxy 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
    • C10M129/32—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms monocarboxylic
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/36—Polyoxyalkylenes etherified
    • 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • C23F11/126—Aliphatic acids
    • C—CHEMISTRY; METALLURGY
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/142—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
    • 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
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/06—Protein or carboxylic compound containing

Definitions

  • the invention relates to a process for the preparation of 0 / W (oil-in-water) rust protection emulsions based on an oil component, water, at least one emulsifier component and a corrosion inhibitor.
  • 0 / W oil-in-water
  • rust protection emulsions based on an oil component, water, at least one emulsifier component and a corrosion inhibitor.
  • the compliance of certain conditions leads to particularly stable and low-viscosity O / W emulsions, ensure ei ⁇ NEN good corrosion protection 'for metal surfaces of iron and steel.
  • Rust protection emulsions are used • for the temporary protection of metallic workpieces from atmospheric influences which cause corrosion. They contain essentially non-polar or polar oils, emulsifiers, corrosion inhibitors and water. Their effect is based on the adsorption of inhibitor molecules on the metal surface and the formation of a protective film from erosion components, which acts as a diffusion barrier for atmospheric oxygen and water. Th. Forster et al. report in "Surface-Surface", 1989, No. 4, pp. 8 to 12, about the mode of action and methods of investigation of rust protection emulsions. Other commercially available systems are based on oil concentrates which contain emulsifiers and corrosion inhibitors, but no water. This means that the emulsifiers and corrosion inhibitors used must be oil-soluble. For the production of O / W emulsions from such oil concentrates, this also means that such systems have to be self-cleaning.
  • phase inversion ie at higher temperatures the outer, aqueous phase can become the inner phase.
  • This process is generally reversible, that is to say that the original type of emulsion re-forms on cooling.
  • position of the phase inversion temperature depends on many factors, such as the type and Phasenvo ⁇ lumen of the 'oil component of the hydrophilic character and structure of the emulsifier or the composition of the EmuIgatorSystems, verglei ⁇ che for example, K. Shinoda and H. Kunieda in "Encyclopedia of Emulsion Technology", Vol. I, ed. P. Becher 1983 (M. Decker, NY), pp. 337 to 367.
  • the object of the invention is to develop a suitable process for the preparation of O / W rust protection emulsions which contain entirely or predominantly polar carboxylic acids as corrosion inhibitors.
  • Such O / W emulsions are said to be capable
  • ER S ATZBLATT be inverted at temperatures below 100 ° C in order to achieve particularly stable, finely divided and low-viscosity emulsions.
  • the emulsions obtained in this way should be able to be diluted with water, the dilutions should also be stable and provide effective corrosion protection.
  • the invention accordingly relates to a process for the preparation of stable, low-viscosity O / W antirust emulsions, wherein a mixture containing an oil component, water and at least one emulsifier component, at a temperature at which all components of the mixture in are in liquid form, emulsify and the emulsion formed is heated to a temperature within or above the phase inversion temperature range of the emulsion or the mixture is emulsified at a temperature within or above the phase inversion temperature range, then the emulsion to a temperature below this temperature range cooled and optionally diluted with water, characterized in that a mixture of the following composition is used to form the emulsion:
  • R is a straight-chain or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms or a radical of the general formula (II)
  • R- saturated, straight-chain or branched alkyl radical having 8 to 18 carbon atoms
  • a co-emulsifier component consisting of at least one fatty alcohol with 12 to 22 carbon atoms
  • carboxylic acids which are able to be effective in their acidic form as corrosion inhibitors and on the other hand the way of producing stable and low-viscosity O / W emulsions which contain such corrosion inhibitors.
  • the carboxylic acids must not impair or even prevent a phase version of the emulsion.
  • suitable emulsifiers which, on the one hand, form such stable emulsions with the corrosion inhibitors mentioned and, on the other hand, do not adversely affect the effectiveness of the corrosion inhibitors on the substrate surface under atmospheric corrosion conditions.
  • the method according to the invention makes it possible to produce such stable and low-viscosity O / W rust protection emulsions.
  • the mixture of all of the emulsion components listed, including the carboxylic acids, is subjected to a phase inversion while the mixture or the emulsion already present is heated to a temperature within or above the phase inversion temperature range.
  • corrosion inhibitors in the desired finely divided form in the emulsion and stably emulsify therein.
  • phase inversion takes place below 100 ° C. This phase inversion takes place both with non-polar oils (paraffin oils) and with slightly polar oils (mineral oils).
  • PIT method i.e. Phase inversion temperature method
  • rust protection emulsions produced show - compared to emulsions of the same composition which have not undergone phase inversion - higher storage stability.
  • more than 40 days pass in the corrosion test, assessed according to DIN 51 359, until 100% corrosion is observed. The effectiveness of the corrosion protection is therefore of the same order of magnitude as the products belonging to the state of the art.
  • Oils of different polarity for example paraffin oils or mineral oils, can be used as the oil component.
  • So-called ester oils ie fatty acid glycerides, can also be used in a mixture with mineral oils and / or paraffin oils.
  • paraffin oils or mineral oils are preferably used as oil component a).
  • emulsifier component b adducts of 2 to 20 moles of ethylene oxide with fatty alcohols with 10 to 22 carbon atoms are suitable.
  • Suitable fatty alcohols for this purpose are native and / or synthetic fatty alcohols, such as decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), nonadecanol, eicosanol, heneico Cosmeticyl and docosanol.
  • adducts of ethylene oxide with such fatty alcohols are usually mixtures of polyglycol ethers of the starting fatty talc alcohols, the average degree of oxyethylation of which corresponds to the molar amount of ethylene oxide added.
  • adducts of 4 to 12 moles of ethylene oxide with fatty alcohols having 12 to 18 carbon atoms are preferably used as emulsifier component b).
  • addition products of 4 moles of ethylene oxide on fatty alcohol mixtures with 12 to 14 C atoms addition products of 4 moles of ethylene oxide on mixtures of fatty alcohols with 12 to 18 C atoms or addition products of 12 moles of ethylene oxide on fatty alcohol mixtures with 16 to 18 carbon atoms.
  • carboxylic acids of the general formula (I) are suitable on the one hand, in which the radical R is a straight-chain or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms.
  • fatty acids for example hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid (palitecic acid), hexadecanoic acid, , Heptadecanoic acid ⁇ octadecanoic acid (stearic acid), nonadecanoic acid, arachic acid, heneicosanoic acid and behenic acid.
  • native or synthetic fatty acids for example hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric
  • carboxylic acids are suitable as corrosion inhibitors in the sense of the invention.
  • Preferred carboxylic acids according to the invention are those of the general formula (I) in which the radical R represents a straight-chain or branched, saturated or unsaturated alkyl radical having 8 to 18 carbon atoms.
  • the corresponding straight-chain and saturated fatty acids can be seen from the above list.
  • Isononanoic acid, oleic acid, linoleic acid or linolenic acid are particularly suitable as branched-chain or unsaturated carboxylic acids of this type.
  • Mixtures of such carboxylic acids are also effective corrosion inhibitors in the sense of the invention; for example a mixture of stearic acid and palmitic acid in a weight ratio of 1: 1.
  • Corrosion inhibitors within the meaning of the invention are furthermore those carboxylic acids of the general formula (I) in which the radical R is a radical of the general formula (II)
  • O VCOCH-CH- (II) represents, wherein the radical R- is a saturated, straight-chain or branched alkyl radical having 8 to 18 carbon atoms.
  • R- is a saturated, straight-chain or branched alkyl radical having 8 to 18 carbon atoms.
  • Suitable alkyl radicals R are therefore unbranched or branched radicals from the group octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, with corresponding straight-chain alkyl radicals having 8 to 12 carbon atoms being preferred according to the invention .
  • 3- (p-dodecylbenzoyl) acrylic acid is used with particular advantage according to the invention.
  • coemulsifier component (d) in addition to the emulsifier component. Because of its hydrophilicity, the co-emulsifier is itself not suitable for the production of O / W emulsions. However, together with the previously defined emulsifier components, particularly stable and finely divided emulsions of polar oil components can be produced according to the invention.
  • saturated fatty alcohols having 12 to 22 carbon atoms in question. The fatty alcohols which are suitable here are mentioned in detail in the above list of fatty alcohols.
  • coemulsifiers of this type are used in amounts of 1 to 6% by weight, based on the mixture.
  • Particularly preferred co-emulsifiers are fatty alcohols with 16 to 18 carbon atoms.
  • REPLACEMENT LEAF Atoms for example a mixture of cetyl alcohol and stearyl alcohol in a weight ratio of 1: 1.
  • the oil component a), the emulsifier component b) and the corrosion inhibitor c) are in a specific weight ratio of a): b): c) ⁇ 1: (0.1 to 0 , 3): (0.1 to 0.3) inserted.
  • the process according to the invention can be carried out in such a way that the phase inversion temperature is first determined by heating a sample of the emulsion prepared in the customary manner using a conductivity measuring device and determining the temperature at which the conductivity decreases sharply.
  • the specific conductivity of the oil-in-water emulsion initially present usually decreases within a temperature range of 2 to 8 ° C. from initially over 1 mS / cm upon transition into an inverted emulsion to values below 0.1 mS / cm. This temperature range is referred to as the phase inversion temperature range.
  • the process according to the invention can either be carried out in such a way that the emulsion, which is initially prepared as usual and contains all the components essential to the invention, is subsequently reduced to a temperature heated temperature, which is within or above the phase inversion temperature range.
  • a further production possibility is to choose a temperature which is within or above the phase inversion temperature range already during the production of a certain emulsion.
  • the emulsion formed is allowed to cool to a temperature below the phase inversion temperature range, or the emulsion is cooled to a corresponding temperature. In this way, concentrates of O / W rust protection emulsions are obtained, which can optionally be diluted with water.
  • the O / W rust protection emulsions produced in the manner according to the invention can be used both in the form of the concentrates and in the form diluted with water. However, they are usually used in the diluted form. Both the concentrates and the emulsions diluted with water ensure very good corrosion protection for metal surfaces made of iron and steel.
  • the corrosion protection activity of the emulsions prepared in accordance with the invention is retained even when the carboxylic acids which act as corrosion inhibitors are present in neutralized form. In view of this, it is possible to subsequently neutralize the O / W rust protection emulsions prepared according to the invention with suitable alkaline agents, for example bases such as NaOH or Ca (0H) 2.
  • the oil-in-water antirust emulsions produced by the temperature inversion according to the invention are particularly finely divided compared to emulsions produced below the phase inversion temperature and are low-viscosity and therefore pourable and pumpable (FIG. 2).
  • these rust protection emulsions have a pronounced storage stability.
  • the sheets which have been treated with corrosion protection emulsions according to the invention show a lower susceptibility to corrosion than sheets which have been treated with conventional corrosion protection emulsions.
  • phase inversion it was possible to obtain rust protection emulsion concentrates which contain more than 50 organic components. Since these concentrates are oil-in-water systems after manufacture and the oil phase is very finely divided, they can be very easily diluted with water without losing the high storage stability (Fig. 3).
  • the emulsifier mixtures and corrosion inhibitors do not necessarily have to be oil-soluble in order to carry out the process according to the invention.
  • Mineral oil Pionier®4556 mineral oil (naphthenic) from the company
  • Eumulgin®Bl add-on product of approx. 12 mol
  • Dehydol® LT4 adduct of approx. 4 moles of ethylene oxide with Ci2-i8-ettalkohole, company Henkel KGaA, Düsseldorf
  • Two emulsions were prepared from mixtures according to formulation D, a production temperature of 45 ° C. below the phase inversion temperature range (PIT) for the first emulsion, and a production temperature of 95 ° C. above PIT for the second emulsion, analogously Example 1.4 - was chosen.
  • the conductivity was determined in the upper and lower area of the measuring vessel (compare the left scale in FIG. 1) and the percentage difference was formed (compare the right scale in FIG. 1).
  • a glass cylinder (height 125 mm, diameter 25 mm), in which two platinum electrodes (type PP 1042 from Radiometer) were attached at a distance of 2 mm from the top and bottom edges, served as the measuring vessel.
  • the vessel was completely filled with the respective emulsion - which contained 50 mg NaCl per liter of emulsion as the conductive salt - so that the electrodes i the upper part of the vessel were completely covered with the emulsion.
  • the measurements were carried out at room temperature.
  • Two emulsions were prepared from mixtures according to formulation A, a production temperature of 60 ° C. - below PIT - for the first emulsion, and a production temperature of 70 ° C. - above PIT, analogous to Example 1.1 - for the second emulsion according to the invention has been. These emulsions were diluted 1: 1 with water and the viscosities of these emulsions were then determined at different shear rates.
  • FIG. 2 shows the results of the measurements which show the viscosity behavior of a diluted emulsion, ie the preferred application form. From this it can be seen that the second emulsion according to the invention (with phase inversion) was significantly lower-viscous than the first emulsion (without phase inversion).
  • Example 1.1 An emulsion according to Example 1.1 was diluted in a ratio of 1: 9 with aqueous NaOH solution and neutralized.
  • the conductivities in the upper and lower area of the measuring vessel were determined (compare the left scale in FIG. 3) and the percentage difference was formed (compare the right column in FIG. 3). The importance of this measuring method with regard to emulsion stability is explained in more detail in Example 2.
  • the corrosion protection properties of emulsions according to the invention and of a comparison emulsion were tested in accordance with D1N 51 359.
  • the test procedure was carried out as follows: steel sheets of quality St 1405 (unalloyed steel, surface-hardened, dimensions 2.5 x 5 cm) were each placed in one of the following Anti-rust emulsions dipped. The steel sheets were held in short contact 'with the rust protection emulsion, then removed and hanged after 24 hours of dripping and drying time in a mecanics ⁇ chamber according to DIN 51 359, in the case of continuous Lucas ⁇ feed of 875 1 / h and a temperature of 50 ° C the relative humidity was 100%. The time period after which 100% corrosion (based on the area of the test sheet) - assessed according to DIN 51 359 - was observed.
  • Example 6.1 Emulsion according to Example 1.1, undiluted and in different dilutions with water (see Table 3).
  • Example 6.2 Emulsion according to Example 1.2 neutralized with
  • Example 6.3 Emulsion according to Example 1.3.
  • Example 6.4 Emulsion according to Example 1.4.
  • Emulsion prepared the emulsification temperature was 45 ° C (non-inverted emulsion). This emulsion was neutralized with diethanolamine.

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Abstract

Dans le procédé décrit, on émulsionne un mélange renfermant un consituant huileux, de l'eau et au moins un constituant émulsifiant, à une température à laquelle tous les constituants du mélange sont présents sous forme liquide, et on porte l'émulsion formée à une température se situant dans/ou au-dessus de la plage thermique d'inversion de phase de l'émulsion, ou bien on émulsionne le mélange à une température se situant dans ou au-dessus de la plage thermique d'inversion de phase, on refroidit ensuite l'émulsion à une température inférieure à cette plage thermique et on la dilue éventuellement avec de l'eau. Ce procédé est caractérisé en ce que l'on utilise pour former l'émulsion un mélange de la composition suivante: a) 10 à 60% en poids d'un constituant huileux, b) 1 à 10% en poids d'un constituant émulsifiant composé d'au moins un produit d'addition de 2 à 20 moles d'oxyde d'éthylène à des alcools gras possédant 10 à 22 atomes de C, c) 1 à 10% en poids d'un inhibiteur de corrosion constitué d'au moins un acide carboxylique de formule générale (I) R-COOH où R est un résidu alkyle à chaîne droite ou ramifié, saturé ou insaturé, avec 6 à 22 atomes de C, ou bien un résidu de formule générale (II), où R1= résidu alkyle saturé à chaîne droite ou ramifié, avec 8 à 18 atomes de C, d) 0 à 10% en poids d'un constituant co-émulsifiant composé d'au moins un alcool gras avec 12 à 22 atomes de C, e) le solde étant de l'eau.In the process described, a mixture containing an oily component, water and at least one emulsifying component is emulsified at a temperature at which all the components of the mixture are present in liquid form, and the emulsion formed is brought to a temperature situated in / or above the thermal phase inversion range of the emulsion, or else the mixture is emulsified at a temperature situated in or above the thermal phase inversion range, then cools the emulsion to a temperature below this thermal range and optionally dilutes it with water. This process is characterized in that a mixture of the following composition is used to form the emulsion: a) 10 to 60% by weight of an oily component, b) 1 to 10% by weight of an emulsifying component composed of at least one adduct of 2 to 20 moles of ethylene oxide with fatty alcohols having 10 to 22 C atoms, c) 1 to 10% by weight of a corrosion inhibitor consisting of at least one carboxylic acid of general formula (I) R-COOH where R is a straight or branched chain, saturated or unsaturated alkyl residue with 6 to 22 C atoms, or else a residue of general formula (II), where R1 = saturated alkyl residue, straight or branched chain, with 8 to 18 C atoms, d) 0 to 10% by weight of a co-emulsifying constituent composed of at least one fatty alcohol with 12 to 22 C atoms, e) the balance being water.

Description

Verfahren zur Herstellung stabiler, niedrig-viskoser O/W-Rost schutze ulsJonen Process for producing stable, low-viscosity O / W rust protect ulsJonen
Die Erfindung betrifft ein Verfahren zur Herstellung von 0/W (Öl- in-Wasser)-Rostschutzemulsionen auf Basis einer Öl-Komponente, Wasser, mindestens einer Emulgator-Komponente und einem Korrosi¬ onsinhibitor. Hierbei führt die Einhaltung bestimmter Bedingungen zu besonders stabilen und niedrig-viskosen O/W-Emulsionen, die ei¬ nen guten Korrosionsschutz 'für Metalloberflächen aus Eisen und Stahl gewährleisten.The invention relates to a process for the preparation of 0 / W (oil-in-water) rust protection emulsions based on an oil component, water, at least one emulsifier component and a corrosion inhibitor. Here, the compliance of certain conditions leads to particularly stable and low-viscosity O / W emulsions, ensure ei¬ NEN good corrosion protection 'for metal surfaces of iron and steel.
Rostschutzemulsionen werden • zum temporären Schutz metallischer Werkstücke vor atmosphärischen, eine Korrosion bewirkenden Ein¬ flüssen eingesetzt. Sie enthalten im wesentlichen unpolare oder polare Öle, Emulgatoren, Korrσsionsinhibitoren und Wasser. Ihre Wirkung beruht auf der Adsorption von Inhibitormolekülen auf der Metalloberfl che und der Bildung eines Schutzfilms aus Eraulsions- bestandteilen, der als Diffusionsbarriere für Luftsauerstoff sowie Wasser wirkt. Th. Förster et al. berichten in "Oberfläche-Surface", 1989, Nr. 4, S. 8 bis 12, über Wirkungsweise und Untersuchungsme¬ thoden von Rostschutzemulsionen. Andere handelsübliche Systeme ba¬ sieren auf Öl onzentraten, die Emulgatoren und Korrosionsinhibi¬ toren - jedoch kein Wasser - enthalten. Dies bedingt, daß die ver¬ wendeten Emulgatoren und Korrosionsinhibitoren öllöslich sein müs¬ sen. Für die Herstellung von O/W-Emulsionen aus solchen Ölkonzen¬ traten bedeutet dies ferner, daß derartige Systeme selbste ulgie¬ rend sein müssen.Rust protection emulsions are used • for the temporary protection of metallic workpieces from atmospheric influences which cause corrosion. They contain essentially non-polar or polar oils, emulsifiers, corrosion inhibitors and water. Their effect is based on the adsorption of inhibitor molecules on the metal surface and the formation of a protective film from erosion components, which acts as a diffusion barrier for atmospheric oxygen and water. Th. Forster et al. report in "Surface-Surface", 1989, No. 4, pp. 8 to 12, about the mode of action and methods of investigation of rust protection emulsions. Other commercially available systems are based on oil concentrates which contain emulsifiers and corrosion inhibitors, but no water. This means that the emulsifiers and corrosion inhibitors used must be oil-soluble. For the production of O / W emulsions from such oil concentrates, this also means that such systems have to be self-cleaning.
Es ist bekannt, daß Öl-in-Wasser-E ulsionen, die mit πicht- ionogenen Emulgatoren hergestellt und stabilisiert sind, beimIt is known that oil-in-water emulsions which are produced and stabilized with non-ionic emulsifiers are used in
ERSATZBLATT Erwärmen eine Phaseninversion erleiden, d.h. daß bei höheren Tem- peraturen die äußere, wäßrige Phase zur inneren Phase werden kann. Dieser Vorgang ist in der Regel reversibel, d.h. daß sich beim Ab¬ kühlen wieder der ursprüngliche Emulsionstyp zurückbildet. Es ist auch bekannt, daß die Lage der Phaseninversionstemperatur von vielen Faktoren abhängig ist, z.B. von der Art und dem Phasenvo¬ lumen der' Ölkomponente, von der Hydrophilie und der Struktur des Emulgators oder der Zusammensetzung des EmuIgatorSystems, verglei¬ che beispielsweise K. Shinoda und H. Kunieda in "Encyclopedia of Emulsion Technology", Vol. I, ed. P. Becher 1983 (M. Decker, N.Y.), S. 337 bis 367. Weiterhin ist' bekannt, daß Emulsionen, die bei oder wenig unterhalb der Phaseninversionstemperatur (PIT) hergestellt werden, sich durch besondere Feinteiligkeit und Stabilität aus¬ zeichnen, während solche, die oberhalb der Phaseπinversionstempe- ratur hergestellt werden, weniger feinteilig sind (vergl. S. Friberg, C. Solans, "J. Colloid Interface Sei.", 66, S. 367 bis 368 (1978)). F. Schambil, F. Jost und M.J. Schwuger berichten in "Progress in Colloid & Polymer Science" 72, (1987), S. 37 bis 47 über die Eigenschaften kosmetischer Emulsionen, die Fettalkohole und Fettalkoholpolyglycolether enthalten und beschreiben dabei auch, daß Emulsionen, die oberhalb der Phaseninversionstemperatur hergestellt wurden, eine niedrige Viskosität und eine hohe Lager¬ stabilität aufweisen. In der bislang unveröffentlichten deutschen Patentanmeldung P 3819 193.8 der Anmelderin wird ein entsprechen¬ des Verfahren zur Herstellung stabiler, niedrig-viskoser O/W-Emulsionen polarer Ölko ponenten beschrieben.REPLACEMENT LEAF Heating undergoes a phase inversion, ie at higher temperatures the outer, aqueous phase can become the inner phase. This process is generally reversible, that is to say that the original type of emulsion re-forms on cooling. It is also known that the position of the phase inversion temperature depends on many factors, such as the type and Phasenvo¬ lumen of the 'oil component of the hydrophilic character and structure of the emulsifier or the composition of the EmuIgatorSystems, verglei¬ che for example, K. Shinoda and H. Kunieda in "Encyclopedia of Emulsion Technology", Vol. I, ed. P. Becher 1983 (M. Decker, NY), pp. 337 to 367. Furthermore, it is known that emulsions which are at or slightly below the Phase inversion temperature (PIT) are produced, are distinguished by a particularly fine particle size and stability, while those which are produced above the phase inversion temperature are less finely divided (see S. Friberg, C. Solans, "J. Colloid Interface Sci. ", 66, pp. 367 to 368 (1978)). F. Schambil, F. Jost and MJ Schwuger report in "Progress in Colloid & Polymer Science" 72, (1987), pp. 37 to 47 about the properties of cosmetic emulsions which contain fatty alcohols and fatty alcohol polyglycol ethers and also describe that emulsions, which were produced above the phase inversion temperature, have a low viscosity and high storage stability. Applicant's previously unpublished German patent application P 3819 193.8 describes a corresponding process for the preparation of stable, low-viscosity O / W emulsions of polar oil components.
Demgegenüber liegt der Erfindung die Aufgabe zugrunde, ein geeig¬ netes Verfahren zur Herstellung von O/W-Rostschutzemulsionen, die ganz oder überwiegend polare Carbonsäuren als Korrosionsinhibitoren enthalten, zu entwickeln. Solche O/W-Emulsionen sollen in der LageIn contrast, the object of the invention is to develop a suitable process for the preparation of O / W rust protection emulsions which contain entirely or predominantly polar carboxylic acids as corrosion inhibitors. Such O / W emulsions are said to be capable
ERSATZBLATT sein, bei Temperaturen unter 100 °C zu invertieren, um auf dies Weise zu besonders stabilen, feinverteilten und niedrig-viskose Emulsionen zu gelangen. Die so erhaltenen Emulsionen sollen ferne mit Wasser verdünnbar sein, die Verdünnungen sollen ebenfalls sta bil sein und einen wirksamen Korrosionsschutz bedingen.ER S ATZBLATT be inverted at temperatures below 100 ° C in order to achieve particularly stable, finely divided and low-viscosity emulsions. The emulsions obtained in this way should be able to be diluted with water, the dilutions should also be stable and provide effective corrosion protection.
Gegenstand der Erfindung ist dementsprechend ein Verfahren zu Herstellung stabiler, niedrig-viskoser O/W-Rostschutzemulsionen, wobei man ein Gemisch, enthaltend eine Öl-Komponente, Wasser un mindestens eine Emulgator-Komponente, bei einer Temperatur, bei de alle Komponenten des Gemisches in flüssiger Form vorliegen, emul giert und die gebildete Emulsion auf eine Temperatur innerhalb ode oberhalb des Phaseninversions-Te peraturbereichs der Emulsion er hitzt oder das Gemisch bei einer Temperatur innerhalb oder oberhal des Phaseninversions-Te peraturbereichs emulgiert, anschließend die Emulsion auf eine Temperatur unterhalb dieses Temperaturbereichs abkühlt und gegebenenfalls mit Wasser verdünnt, dadurch gekennzeichnet, daß man ein Gemisch der folgenden Zusam¬ mensetzung zur Emulsionsbildung einsetzt:The invention accordingly relates to a process for the preparation of stable, low-viscosity O / W antirust emulsions, wherein a mixture containing an oil component, water and at least one emulsifier component, at a temperature at which all components of the mixture in are in liquid form, emulsify and the emulsion formed is heated to a temperature within or above the phase inversion temperature range of the emulsion or the mixture is emulsified at a temperature within or above the phase inversion temperature range, then the emulsion to a temperature below this temperature range cooled and optionally diluted with water, characterized in that a mixture of the following composition is used to form the emulsion:
a) 10 bis 60 Gew.-% einer Öl-Komponente, b) 1 bis 10 Gew.-% einer Emulgator-Komponente, bestehend aus min¬ destens einem Anlagerungsprodukt von 2 bis 20 Mol Ethylenoxid an Fettalkohole mit 10 bis 22 C-Atomen, c) 1 bis 10 Gew.-% eines Korrosionsinhibitors, bestehend aus min¬ destens einer Carbonsäure der allgemeinen Formel (I):a) 10 to 60% by weight of an oil component, b) 1 to 10% by weight of an emulsifier component, consisting of at least one adduct of 2 to 20 moles of ethylene oxide with fatty alcohols having 10 to 22 carbon atoms , c) 1 to 10% by weight of a corrosion inhibitor, consisting of at least one carboxylic acid of the general formula (I):
R-C00H (I)R-C00H (I)
wobei R einen geradkettigen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 6 bis 22 C-Atomen oder einen Rest der allgemeinen Formel (II)where R is a straight-chain or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms or a radical of the general formula (II)
BLATT Rl C0CH=CH-SHEET Rl C0CH = CH-
■<§ (II) ■ <§ (II)
mit R- = gesättigter, geradkettiger oder verzweigter Alkylrest mit 8 bis 18 C-Atomen, darstelltwith R- = saturated, straight-chain or branched alkyl radical having 8 to 18 carbon atoms
d) 0 bis 10 Gew.-% einer Coemulgator-Komponeπte, bestehend aus mindestens einem Fettalkohol mit 12 bis 22 C-Atomen,d) 0 to 10% by weight of a co-emulsifier component consisting of at least one fatty alcohol with 12 to 22 carbon atoms,
e) Rest: Wasser.e) Rest: water.
Im Sinne der Erfindung sind »insbesondere die folgenden Punkte von wesentlicher Bedeutung:For the purposes of the invention, the following points are of particular importance:
Einerseits die Auswahl geeigneter Carboπsäuren, die in der Lage sind, in ihrer sauren Form als Korrosionsinhibitoren wirksam zu sein und andererseits die Art und Weise der Herstellung stabiler und niedrig-viskoser O/W-Emulsionen, die derartige Korrosionsinhi¬ bitoren enthalten. Hierbei dürfen die Carbonsäuren eine Phaseniπ- version der Emulsion nicht beeinträchtigen oder gar verhindern. Weiterhin ist die Auswahl geeigneter Emulgatoren wesentlich, welche einerseits solche stabilen Emulsionen mit den genannten Korrosi- onsiπhibitoren bilden und andererseits die Wirksamkeit der Korro¬ sionsinhibitoren auf der Substratoberf äche unter atmosphärischen Korrosionsbedingungen nicht durch Ree ulgieruπg beeinträchtigen.On the one hand the selection of suitable carboxylic acids which are able to be effective in their acidic form as corrosion inhibitors and on the other hand the way of producing stable and low-viscosity O / W emulsions which contain such corrosion inhibitors. The carboxylic acids must not impair or even prevent a phase version of the emulsion. Furthermore, it is important to select suitable emulsifiers which, on the one hand, form such stable emulsions with the corrosion inhibitors mentioned and, on the other hand, do not adversely affect the effectiveness of the corrosion inhibitors on the substrate surface under atmospheric corrosion conditions.
Überraschenderweise ermöglicht es das erfindungsgemäße Verfahren, solche stabilen und niedrig-viskosen O/W-Rostschutzemulsionen her¬ zustellen. Hierbei wird das Gemisch aller angeführten Emulsions- Komponenten einschließl ch der Carbonsäuren einer Phaseninversioπ unter Erwärmen des Gemisches bzw. der bereits vorliegenden Emulsion auf eine Temperatur innerhalb oder oberhalb des Phaseninversions- Te peraturbereichs unterworfen. Auf diese Weise ist es möglich, die genannten Korrosionsinhibitoren in der gewünschten fein-verteilte Form in die Emulsion einzubringen und stabil darin zu emulgieren.Surprisingly, the method according to the invention makes it possible to produce such stable and low-viscosity O / W rust protection emulsions. The mixture of all of the emulsion components listed, including the carboxylic acids, is subjected to a phase inversion while the mixture or the emulsion already present is heated to a temperature within or above the phase inversion temperature range. In this way it is possible to mentioned corrosion inhibitors in the desired finely divided form in the emulsion and stably emulsify therein.
Innerhalb der oben definierten Zusammensetzung von erfindungs gemäßen O/W-Rostschutzemulsionen, die relativ hohe Anteile vo Carbonsäuren als Korrosionsinhibitoren enthalten, findet eine Pha seninversion unterhalb von 100 °C statt. Diese Phaseninversion er folgt sowohl mit unpolaren Ölen (Paraffinöle), als auch mit leich polaren Ölen (Mineralöle). Diese nach der sogenannten PIT-Methode, d.h. Phaseninversionstemperatur-Methode, hergestellten Rostschutz¬ emulsionen zeigen eine - verglichen mit Emulsionen gleicher Zusam¬ mensetzung, die keine Phaseninversion durchlaufen haben - höhere Lagerstabilität. Außerdem vergehen im Korrosionstest, bewertet nach DIN 51 359, mehr als 40 Tage, bis 100 % Korrosion beobachtet wird. Die Korrosionsschutzwirksamkeit liegt damit in der gleichen Grö¬ ßenordnung wie die dem Stand der Technik angehörigen Produkte.Within the above-defined composition of O / W anti-rust emulsions according to the invention which contain relatively high proportions of carboxylic acids as corrosion inhibitors, a phase inversion takes place below 100 ° C. This phase inversion takes place both with non-polar oils (paraffin oils) and with slightly polar oils (mineral oils). This according to the so-called PIT method, i.e. Phase inversion temperature method, rust protection emulsions produced show - compared to emulsions of the same composition which have not undergone phase inversion - higher storage stability. In addition, more than 40 days pass in the corrosion test, assessed according to DIN 51 359, until 100% corrosion is observed. The effectiveness of the corrosion protection is therefore of the same order of magnitude as the products belonging to the state of the art.
Im Sinne der Erfindung ist es bevorzugt, ein Gemisch der folgenden Zusammensetzung zur Emulsionsbildung einzusetzen:For the purposes of the invention, it is preferred to use a mixture of the following composition for emulsion formation:
a) 20 bis 50 Gew.-% einer Öl-Komponente, b) 2 bis 8 Gew.-% einer Emulgator-Komponente, c) 2 bis 6 Gew.-% eines Korrosionsinhibitors, d) 0 bis 6 Gew.-% einer Coemulgator-Komponente, e) Rest: Wasser.a) 20 to 50% by weight of an oil component, b) 2 to 8% by weight of an emulsifier component, c) 2 to 6% by weight of a corrosion inhibitor, d) 0 to 6% by weight of one Co-emulsifier component, e) balance: water.
Für die einzelnen Komponenten der erfindungsgemäß herzustellenden O/W-Rostschutzemulsionen gilt im einzelnen das Folgende:The following applies in detail to the individual components of the O / W rust protection emulsions to be produced according to the invention:
Als Öl-Komponente können Öle unterschiedlicher Polarität, bei¬ spielsweise Paraffinöle oder Mineralöle, Verwendung finden. Auch sogenannte Esteröle, d.h. Fettsäure-Glyceride, können im Gemisch mit Mineralölen und/oder Paraffinölen eingesetzt werden. Im Sinne der Erfindung werden bevorzugt Paraffinöle oder Mineralöle als Öl-Komponente a) eingesetzt.Oils of different polarity, for example paraffin oils or mineral oils, can be used as the oil component. So-called ester oils, ie fatty acid glycerides, can also be used in a mixture with mineral oils and / or paraffin oils. For the purposes of the invention, paraffin oils or mineral oils are preferably used as oil component a).
Als Emulgator-Komponente b) kommen Anlagerungsprodukte von 2 bis 20 Mol Ethylenoxid an Fettalkohole mit 10 bis 22 C-Atomen in Frage. Hierfür geeignete Fettalkohole sind native und/oder synthetische Fettalkohole, wie Decanol, Undecanol, Dodecanol, Tridecanol, Tetradecanol , Pentadecanol, Hexadecanol (Cetylalkohol), Heptadecanol, Octadecanol (Stearylalkohol), Nonadecanol, Eicosanol, Heneicosanol und Docosanol (Behenylalkohol). Technisch hergestellte Anlagerungsprodukte von Ethylenoxid an derartige Fettalkohole stellen üblicherweise Gemische von Polyglykolethern der Ausgangs- fet-talkohole dar, deren mittlerer Oxethylieruπgsgrad der angela¬ gerten Molmenge an Ethylenoxid entspricht. Im Sinne der Erfindung werden bevorzugt als Emulgator-Komponente b) Anlagerungsprodukte von 4 bis 12 Mol Ethylenoxid an Fettalkohole mit 12 bis 18 C-Atomen eingesetzt. Insbesondere finden hierbei Verwendung: Anlagerungsprodukte von 4 Mol Ethylenoxid an Fettalkohol-Gemische mit 12 bis 14 C-Atomen, Anlagerungsprodukte von 4 Mol Ethylenoxid an Gemische von Fettalkoholen mit 12 bis 18 C-Atomen oder Anlage¬ rungsprodukte von 12 Mol Ethylenoxid an Fettalkohol-Gemische mit 16 bis 18 C-Atomen.As emulsifier component b), adducts of 2 to 20 moles of ethylene oxide with fatty alcohols with 10 to 22 carbon atoms are suitable. Suitable fatty alcohols for this purpose are native and / or synthetic fatty alcohols, such as decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), nonadecanol, eicosanol, heneicosehenyl and docosanol. Technically produced adducts of ethylene oxide with such fatty alcohols are usually mixtures of polyglycol ethers of the starting fatty talc alcohols, the average degree of oxyethylation of which corresponds to the molar amount of ethylene oxide added. For the purposes of the invention, adducts of 4 to 12 moles of ethylene oxide with fatty alcohols having 12 to 18 carbon atoms are preferably used as emulsifier component b). In particular, the following are used here: addition products of 4 moles of ethylene oxide on fatty alcohol mixtures with 12 to 14 C atoms, addition products of 4 moles of ethylene oxide on mixtures of fatty alcohols with 12 to 18 C atoms or addition products of 12 moles of ethylene oxide on fatty alcohol mixtures with 16 to 18 carbon atoms.
Die als Korrosionsinhibitoren c) eingesetzten Carbonsäuren der allgemeinen Formel (I)The carboxylic acids of the general formula (I) used as corrosion inhibitors c)
R-COOH (I)R-COOH (I)
können von unterschiedl icher Struktur sein.can be of a different structure.
ERSATZBLATT Im Sinne der Erfin _-*dung sind einerseits solche Carbonsäuren de allgemeinen Formel (I) geeignet, in denen der Rest R eine geradkettigen oder verzweigten, gesättigten oder ungesättigte Alkylrest mit 6 bis 22 C-Atomen darstellt. Hierzu zählen insbeson dere native oder synthetische Fettsäuren, beispielsweise Hexansäur (Capronsäure), Heptansäure, Octansäure (Caprylsäure), Nonansäure, Decansäure (Caprinsäure), Undecansäure, Dodecansäure (Laurinsäure), Tridecansäure, Tetradecansäure (Myristinsäure), Pentadecansäure, Hexadecansäure (Pal itinsäure), Heptadecansäure< Octadecansäur (Stearinsäure), Nonadecansäure, Arachinsäure, Heneicosansäure un Behensäure. In gleicher Weisis sind entsprechende verzweigtkettig oder ungesättigte Carbonsäuren als Korrosionsinh-ibitoren im Sinn der Erfindung geeignet. Bevorzugt sind hierbei erfindungsgemä solche Carbonsäuren der allgemeinen Formel (I), in denen der Rest R einen geradkettigen oder verzweigten, gesättigten oder ungesät¬ tigten Alkylrest mit 8 bis 18 C-Atomen, darstellt. Aus der vorste¬ henden Aufzählung sind die entsprechenden geradkettigen und gesät¬ tigten Fettsäuren ersichtlich. Als verzweigtkettige oder ungesät¬ tigte Carbonsäuren dieses Typs kommen insbesondere Isononansäure, Ölsäure, Linolsäure oder Linolensäure in Frage. Auch Gemische der¬ artiger Carbonsäuren sind wirksame Korrosionsinhibitoren im Sinne der Erfindung; beispielsweise ein Gemisch aus Stearinsäure und Palmitinsäure im Gewichtsverhältnis 1 : 1.REPLACEMENT LEAF For the purposes of the invention, carboxylic acids of the general formula (I) are suitable on the one hand, in which the radical R is a straight-chain or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms. These include in particular native or synthetic fatty acids, for example hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid (palitecic acid), hexadecanoic acid, , Heptadecanoic acid < octadecanoic acid (stearic acid), nonadecanoic acid, arachic acid, heneicosanoic acid and behenic acid. In the same way, corresponding branched-chain or unsaturated carboxylic acids are suitable as corrosion inhibitors in the sense of the invention. Preferred carboxylic acids according to the invention are those of the general formula (I) in which the radical R represents a straight-chain or branched, saturated or unsaturated alkyl radical having 8 to 18 carbon atoms. The corresponding straight-chain and saturated fatty acids can be seen from the above list. Isononanoic acid, oleic acid, linoleic acid or linolenic acid are particularly suitable as branched-chain or unsaturated carboxylic acids of this type. Mixtures of such carboxylic acids are also effective corrosion inhibitors in the sense of the invention; for example a mixture of stearic acid and palmitic acid in a weight ratio of 1: 1.
Als Korrosionsinhibitoren im Sinne der Erfindung kommen weiterhin solche Carbonsäuren der allgemeinen Formel (I) in Frage, in denen der Rest R einen Rest der allgemeinen Formel (II)Corrosion inhibitors within the meaning of the invention are furthermore those carboxylic acids of the general formula (I) in which the radical R is a radical of the general formula (II)
O VCOCH-CH- (II) darstellt, wobei der Rest R- für einen gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 18 C-Atomen steht. Derartige Alkylbenzoylacrylsäuren sowie deren Verwendung als Korrosionsinhi¬ bitoren in Schmierölen und Schmierfetten sind in der DE-OS 36 00 401 beschrieben. In dieser deutschen Offenlegungsschrift finden sich auch Angaben zur Synthese derartiger Alkylbenzoylacrylsäuren. Als Alkylreste R kommen somit unverzweigte oder verzweigte Reste aus der Gruppe Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl und Octadecyl in Frage, wobei entsprechende geradkettige Alkylreste mit 8 bis 12 C-Atomen erfindungsgemäß bevorzugt sind. Von diesem Typ der Carbonsäuren wird erfindungsgemäß die 3-(p-Dodecylbenzoyl)acryl- säure mit besonderem Vorteil eingesetzt.O VCOCH-CH- (II) represents, wherein the radical R- is a saturated, straight-chain or branched alkyl radical having 8 to 18 carbon atoms. Such alkylbenzoylacrylic acids and their use as corrosion inhibitors in lubricating oils and greases are described in DE-OS 36 00 401. This German published specification also contains information on the synthesis of such alkylbenzoylacrylic acids. Suitable alkyl radicals R are therefore unbranched or branched radicals from the group octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, with corresponding straight-chain alkyl radicals having 8 to 12 carbon atoms being preferred according to the invention . Of this type of carboxylic acid, 3- (p-dodecylbenzoyl) acrylic acid is used with particular advantage according to the invention.
Für das erfindungsgemäße Verfahren hat es sich ferner als vorteil¬ haft erwiesen, zusätzlich zur Emulgator-Komponente eine Coemulgator-Komponente (d) einzusetzen. Der Coemulgator ist auf¬ grund seiner Hydrophilie selbst nicht zur Herstellung von O/W-Emulsionen geeignet, gemeinsam mit den zuvor definierten Emulgator-Komponenten lassen sich jedoch erfindungsgemäß besonders stabile und feinteilige Emulsionen von polaren Öl-Komponenten her¬ stellen. Als Coemulgatoren.kommen 'erfindungsgemäß gesättigte Fett¬ alkohole mit 12 bis 22 C-Atomen in Frage. In der vorstehenden Auf¬ zählung von Fettalkoholen sind die hier geeigneten Fettalkohole im einzelnen genannt. Auch Gemische derartiger Fettalkohole, wie sie bei der technischen Hydrierung von pflanzlichen und tierischen Fettsäuren mit 12 bis 22 C-Atomen oder der entsprechenden Fettsäu¬ remethylester erhalten werden, sind geeignet. Im Sinne der Erfin¬ dung ist es bevorzugt, daß man derartige Coemulgatoren in Mengen von 1 bis 6 Gew.-%, bezogen auf das Gemisch, einsetzt. Besonders bevorzugt als Coemulgatoren sind Fettalkohole mit 16 bis 18 C-For the process according to the invention, it has also proven to be advantageous to use a coemulsifier component (d) in addition to the emulsifier component. Because of its hydrophilicity, the co-emulsifier is itself not suitable for the production of O / W emulsions. However, together with the previously defined emulsifier components, particularly stable and finely divided emulsions of polar oil components can be produced according to the invention. As Coemulgatoren.kommen 'according to the invention, saturated fatty alcohols having 12 to 22 carbon atoms in question. The fatty alcohols which are suitable here are mentioned in detail in the above list of fatty alcohols. Mixtures of such fatty alcohols, as are obtained in the industrial hydrogenation of vegetable and animal fatty acids with 12 to 22 carbon atoms or the corresponding fatty acid methyl esters, are also suitable. For the purposes of the invention, it is preferred that coemulsifiers of this type are used in amounts of 1 to 6% by weight, based on the mixture. Particularly preferred co-emulsifiers are fatty alcohols with 16 to 18 carbon atoms.
ERSATZBLATT Atomen, beispielsweise ein Gemisch aus Cetylalkohol un Stearylalkohol im Gewichtsverhältnis 1 : 1.REPLACEMENT LEAF Atoms, for example a mixture of cetyl alcohol and stearyl alcohol in a weight ratio of 1: 1.
Gemäß einer weiteren bevorzugten Ausführungsform der vorliegende Erfindung werden die Öl-Komponente a), die Emulgator-Komponente b) und der Korrosionsinhibitor c) in einem bestimmten Gewichtsver hältnis von a) : b) : c) ■ 1 : (0,1 bis 0,3) : (0,1 bis 0,3) ein¬ gesetzt. Auf diese Weise gelangt man zu besonders nied ig-viskσsen und lagerbeständigen Rostschutzemulsionen. Besonders bevorzugt ist hier ein Gewichtsverhältnis von a : b : c: = 1 : 0,2 : 0,15.According to a further preferred embodiment of the present invention, the oil component a), the emulsifier component b) and the corrosion inhibitor c) are in a specific weight ratio of a): b): c) ■ 1: (0.1 to 0 , 3): (0.1 to 0.3) inserted. In this way, particularly low-viscosity and storage-stable rust protection emulsions are obtained. A weight ratio of a: b: c: = 1: 0.2: 0.15 is particularly preferred here.
Das erfindungsgemäße Verfahren kann in der Weise durchgeführt wer¬ den, daß zunächst' die Phaseπinversions-Temperatur bestimmt wird, indem man eine Probe der auf übliche Weise hergestellten Emulsion unter Verwendung eines Leitfähigkeitsmeßgerätes erhitzt und die Temperatur bestimmt, bei der die Leitfähigkeit stark abnimmt. Die spezifische Leitfähigkeit der zunächst vorhandenen Öl-in-Wasser- Emulsion nimmt üblicherweise innerhalb eines Temperaturbereichs von 2 bis 8 °C von anfänglich über 1 mS/cm heim Übergang in eine in¬ vertierte Emulsion auf Werte unter 0,1 mS/cm ab. Dieser Tempera¬ turbereich wird als Phaseniπversions-Temperaturbereich bezeichnet.The process according to the invention can be carried out in such a way that the phase inversion temperature is first determined by heating a sample of the emulsion prepared in the customary manner using a conductivity measuring device and determining the temperature at which the conductivity decreases sharply. The specific conductivity of the oil-in-water emulsion initially present usually decreases within a temperature range of 2 to 8 ° C. from initially over 1 mS / cm upon transition into an inverted emulsion to values below 0.1 mS / cm. This temperature range is referred to as the phase inversion temperature range.
Nachdem nun der Phaseninversions-Temperaturbereich für eine be¬ stimmte Zusammensetzung einer Emulsion bekannt ist, kann man das erfindungsgemäße Verfahren entweder in der Weise durchführen, daß man die zunächst wie üblich hergestellte Emulsion, die alle erfin- duπgswesentlichen Komponenten enthält, nachträglich auf eine Tem¬ peratur erhitzt, welche innerhalb oder oberhalb des Phaseninversi- ons-Temperaturbereichs liegt. Eine weitere Herstellungsmöglichkeit besteht darin, daß man bereits bei der Herstellung einer bestimmten Emulsion eine solche Temperatur wählt, welche innerhalb oder ober¬ halb des Phaseninversions-Temperaturbereichs liegt. In der Regel geht man in der zuletzt geschilderten Art und Weise vor; d.h. man vermischt alle für eine bestimmte Emulsion erfindungswesentlichen Komponenten, erhitzt dieses Gemisch auf eine Temperatur oberhalb des Phaseninversions-Temperaturbereich.es und emulgiert das Gemisch durch intensives Rühren. Anschließend läßt man die gebildete Emul¬ sion auf eine Temperatur unterhalb des Phaseninversions-Tempera- turbereichs abkühlen, bzw. man kühlt die Emulsion auf eine ent¬ sprechende Temperatur ab. Auf diese Weise werden Konzentrate "von O/W-Rostschutzemulsionen erhalten, die gegebenenfalls mit Wasser verdünnt werden können.Now that the phase inversion temperature range for a particular composition of an emulsion is known, the process according to the invention can either be carried out in such a way that the emulsion, which is initially prepared as usual and contains all the components essential to the invention, is subsequently reduced to a temperature heated temperature, which is within or above the phase inversion temperature range. A further production possibility is to choose a temperature which is within or above the phase inversion temperature range already during the production of a certain emulsion. Usually one proceeds in the manner described last; ie all components essential to the invention for a specific emulsion are mixed, this mixture is heated to a temperature above the phase inversion temperature range and the mixture is emulsified by intensive stirring. Subsequently, the emulsion formed is allowed to cool to a temperature below the phase inversion temperature range, or the emulsion is cooled to a corresponding temperature. In this way, concentrates of O / W rust protection emulsions are obtained, which can optionally be diluted with water.
Die in der erfindungsgemäßen Weise hergestellten O/W-Rostschutz¬ emulsionen können sowohl in Form der Konzentrate als auch in der mit Wasser verdünnten Form Verwendung finden. Üblicherweise werden sie jedoch in der verdünnten Form angewendet. Sowohl die Konzen¬ trate als auch die mit Wasser verdünnten Emulsionen gewährleisten einen sehr guten Korrosionsschutz für MetallOberflächen aus Eisen und Stahl. Die Korrosionsschutzwirksamkeit der in erfindungsgemäßer Weise hergestellten Emulsionen bleibt auch dann erhalten, wenn die als Korrosionsinhibitoren wirksamen Carbonsäuren in neutralisierter Form vorliegen. Im Hinblick hierauf ist es möglich, die erfindungsgemäß hergestellten O/W-Rostschutzemulsionen nachträglich mit geeigneten alkalischen Mitteln, beispielsweise Laugen wie NaOH oder Ca(0H)2 zu neutralisieren.The O / W rust protection emulsions produced in the manner according to the invention can be used both in the form of the concentrates and in the form diluted with water. However, they are usually used in the diluted form. Both the concentrates and the emulsions diluted with water ensure very good corrosion protection for metal surfaces made of iron and steel. The corrosion protection activity of the emulsions prepared in accordance with the invention is retained even when the carboxylic acids which act as corrosion inhibitors are present in neutralized form. In view of this, it is possible to subsequently neutralize the O / W rust protection emulsions prepared according to the invention with suitable alkaline agents, for example bases such as NaOH or Ca (0H) 2.
Die nach dem erfindungsgemäßen Verfahren durch Temperaturinversion hergestellten Öl-in-Wasser-Rostschutzemulsionen sind im Vergleich zu unterhalb der Phaseninversionstemperatur hergestellten Emulsi¬ onen besonders fein verteilt und niedrig-viskos und daher ausgie߬ bar und pumpbar (Fig. 2). Darüber hinaus weisen diese Rostschutz¬ emulsionen eine ausgeprägte Lagerstabilität auf. Beim Vergleich des Zeitraumes innerhalb dem an Prüfblechen 100 % Korrosion (bewertetThe oil-in-water antirust emulsions produced by the temperature inversion according to the invention are particularly finely divided compared to emulsions produced below the phase inversion temperature and are low-viscosity and therefore pourable and pumpable (FIG. 2). In addition, these rust protection emulsions have a pronounced storage stability. When comparing the period within which 100% corrosion on test plates (evaluated
RSATZBLATT nach DIN 51359) eintritt, zeigen die Bleche, die mit erfindungs gemäßen Korrosionsschutzemulsionen behandelt wurden, eine geringer Korrosionsanfälligkeit als Bleche, die mit herkömmlichen Korrosi onsschutzemulsionen behandelt wurden. Durch Phaseninversion konnte RostschutzemuIsionskonzentrate erhalten werden, die mehr als 50 organische Anteile enthalten. Da diese Konzentrate nach Herstellun Öl-in-Wasser-Systeme darstellen und die Öl-Phase feinstverteil vorliegt, sind sie sehr leicht mit Wasser verdünnbar, ohne dabei die hohe Lagerstabilität zu verlieren (Fig. 3). Gegenüber herkömm¬ lichen, auf Öl-Konzentraten basierenden Systemen müssen zur Durch¬ führung des erfindungsgemäße'n Verfahrens die Emulgatormischungen und Korrosionsinhibitoren nicht notwendigerweise öllös!ich sein.REPLACEMENT LEAF according to DIN 51359) occurs, the sheets which have been treated with corrosion protection emulsions according to the invention show a lower susceptibility to corrosion than sheets which have been treated with conventional corrosion protection emulsions. By phase inversion it was possible to obtain rust protection emulsion concentrates which contain more than 50 organic components. Since these concentrates are oil-in-water systems after manufacture and the oil phase is very finely divided, they can be very easily diluted with water without losing the high storage stability (Fig. 3). Compared to conventional systems based on oil concentrates, the emulsifier mixtures and corrosion inhibitors do not necessarily have to be oil-soluble in order to carry out the process according to the invention.
Das' erfindungsgemäße Verfahren und die Vorteile der auf diese Weise hergestellten O/W-Rostschutzemulsionen werden in den nachfolgenden Beispielen näher erläutert.The 'process of the invention and the advantages of the O / prepared in this manner W rust-inhibiting emulsions are described in greater detail in the following examples.
BeispieleExamples
Die nachstehend angegebenen Formulierungen wurden unter Verwendung von verschiedenen Handelsprodukten hergestellt, deren Zusammenset¬ zung und Herkunft hier näher charakterisiert seien:The formulations given below were prepared using various commercial products, the composition and origin of which are characterized in more detail here:
Mineralöl Pionier®4556: Mineralöl (naphthenbasisch) der FirmaMineral oil Pionier®4556: mineral oil (naphthenic) from the company
Hansen & Rosenthal, HamburgHansen & Rosenthal, Hamburg
Eumulgin®Bl: Anlagerungsprodukt von ca. 12 MolEumulgin®Bl: add-on product of approx. 12 mol
Ethylenoxid an Cetylstearylalkohol (Gemisch aus Cetyl- und Stearylalkohol im Gew.-Verhältnis von ca. 1 : 1), Firma Henkel KGaA, Düsseldorf Lanette® 0: Cetylstearylalkohol (Gemisch aus Cetyl- und Stearylalkohol im Gew.-Verhältnis von ca: 1 : 1), Firma Henkel KGaA, DüsseldorfEthylene oxide on cetylstearyl alcohol (mixture of cetyl and stearyl alcohol in a weight ratio of approx. 1: 1), company Henkel KGaA, Düsseldorf Lanette® 0: cetylstearyl alcohol (mixture of cetyl and stearyl alcohol in a weight ratio of approx. 1: 1), from Henkel KGaA, Düsseldorf
Dehydol @ LS4: Anlagerungsprodukt von ca. 4 Mol Ethylenoxid an Ci2-i4-FettaIkohole, Firma Henkel KGaA, DüsseldorfDehydol @ LS4: adduct of approx. 4 mol ethylene oxide with Ci2-i4-fatty alcohols, company Henkel KGaA, Düsseldorf
Dehydol® LT4: Anlagerungsprodukt von ca. 4 Mol Ethylenoxid an Ci2-i8- ettalkohole, Firma Henkel KGaA, DüsseldorfDehydol® LT4: adduct of approx. 4 moles of ethylene oxide with Ci2-i8-ettalkohole, company Henkel KGaA, Düsseldorf
Rezepturen der Formulierungen A bis DFormulations A to D
Formulierung A:Formulation A:
40 Gew.-% Mineralöl Pionier® 4556,40% by weight of Pionier® 4556 mineral oil,
8 Gew.-% Eumulgin®Bl8% by weight Eumulgin®Bl
6 Gew.-% Stearinsäure/Palmitinsäure (Verhältnis 1 : 1) 46 Gew.-% Wasser6% by weight stearic acid / palmitic acid (ratio 1: 1) 46% by weight water
Formulierung B:Formulation B:
20 Gew.-% Paraffinöl20% by weight paraffin oil
5 Gew.-% Dehydol®LS45% by weight Dehydol®LS4
3 Gew.-% 3-(p-Dodecylbenzoyl)acrylsäure3% by weight of 3- (p-dodecylbenzoyl) acrylic acid
2 Gew.-% Lanette® 0 70 Gew.-% Wasser2% by weight Lanette® 0 70% by weight water
ERSATZBLATT Formulierung C:REPLACEMENT LEAF Formulation C:
20 Gew.-% Mineralöl Pionier® 455620% by weight of Pionier® 4556 mineral oil
3 Gew.-% Eumulgin® Bl3% by weight of Eumulgin® Bl
1 Gew.-% Dehydol®LT41% by weight Dehydol®LT4
3 Gew.-% Stearinsäure/Palmitinsäure (Verhältnis 1 : 1) 73 Gew.-% Wasser3% by weight stearic acid / palmitic acid (ratio 1: 1) 73% by weight water
Formulierung D:Formulation D:
20 Gew.-% Mineralö-l Pionier® 455620% by weight of Pionier® 4556 mineral oil
4 Gew.-% Eumulgin® Bl4% by weight Eumulgin® Bl
3 Gew.-% Laurinsäure 73 Gew.-% Wasser3% by weight lauric acid 73% by weight water
Beispiel 1example 1
Herstellung der erfindungsgemäßen O/W-Rostschutzemulsionen auf Ba¬ sis der Formulierungen A bis D:Preparation of the O / W rust protection emulsions according to the invention based on the formulations A to D:
Die für die Formulierungen A bis D angegebenen Einzelkomponeπten wurden miteinander vermischt und jeweils bei einer Temperatur, die oberhalb des Phaseninversions-Temperaturbereiches des jeweiligen Gemisches lag, durch intensives Rühren emulgiert. Die einzelnen Daten sind aus der nachstehenden Tabelle 1 ersichtlich. Tabelle 1The individual components specified for formulations A to D were mixed with one another and in each case emulsified by intensive stirring at a temperature which was above the phase inversion temperature range of the respective mixture. The individual data are shown in Table 1 below. Table 1
Beispiel Formulierung Phaseninversions- Emulgier-Example formulation phase inversion emulsifying
Te peraturbereich TemperaturTemperature range temperature
Beispiel 2Example 2
Vergleich der Stabilität von Emulsionen gleicher Zusammensetzung aber unterschiedlicher Herstellungstemperatur (Fig. 1).Comparison of the stability of emulsions of the same composition but different manufacturing temperatures (Fig. 1).
Es wurden zwei Emulsionen aus Mischungen gemäß Formulierung D her¬ gestellt, wobei für die erste Emulsion eine Herstellungstemperatur von 45 °C - unterhalb des Phaseninversioπs-Temperaturbereichs (PIT) -, für die zweite Emulsion eine Herstellungstemperatur von 95 °C - oberhalb PIT, analog Beispiel 1.4 - gewählt wurde. Zur Beurteilung der Stab lität der jeweil gen Emulsion wurde jewe ls die Leitfä¬ higkeit im oberen bzw. unteren Bereich des Meßgefäßes ermittelt (vergleiche die linke Skala von Fig. 1) und die prozentuale Diffe¬ renz gebildet (vergleiche die rechte Skala von Fig. 1). Als Me߬ gefäß diente hierbei ein Glaszylinder (Höhe 125 mm, Durchmesser 25 mm), in dem - im Abstand von 2 mm vom oberen bzw. vom unteren Rand - jeweils zwei Platin-Elektroden (Typ PP 1042 der Firma Radiometer) angebracht waren. Zur Messung wurde das Gefäß mit der jeweiligen Emulsion - die als Leitsalz jeweils 50 mg NaCl pro Liter Emulsion enthielt - vollständig gefüllt, so daß auch die Elektroden i oberen Teil des Gefäßes mit der Emulsion vollständig bedeckt waren. Die Messungen wurden jeweils bei Raumtemperatur durchgeführt.Two emulsions were prepared from mixtures according to formulation D, a production temperature of 45 ° C. below the phase inversion temperature range (PIT) for the first emulsion, and a production temperature of 95 ° C. above PIT for the second emulsion, analogously Example 1.4 - was chosen. To assess the stability of the respective emulsion, the conductivity was determined in the upper and lower area of the measuring vessel (compare the left scale in FIG. 1) and the percentage difference was formed (compare the right scale in FIG. 1). A glass cylinder (height 125 mm, diameter 25 mm), in which two platinum electrodes (type PP 1042 from Radiometer) were attached at a distance of 2 mm from the top and bottom edges, served as the measuring vessel. For the measurement, the vessel was completely filled with the respective emulsion - which contained 50 mg NaCl per liter of emulsion as the conductive salt - so that the electrodes i the upper part of the vessel were completely covered with the emulsion. The measurements were carried out at room temperature.
Im Falle einer instabilen Emulsion zeigt sich eine Tendenz zum Au¬ frahmen - im Sinne eines Trennprozesses der Emulsion über den Me߬ zeitraum - durch unterschiedliche Leitfähigkeiten im oberen bzw. im unteren Bereich des Meßgefäßes; der prozentuale Differenzwert ist von Null verschieden. Im Falle einer stabilen Emulsion hingegen ergeben sich hierbei nahezu keine Unterschiede in der Leitfähigkeit in den unterschiedlichen Meßbereichen; die prozentuale Differenz ist dementsprechend Null bzw.* nur gering.In the case of an unstable emulsion, there is a tendency to frame - in the sense of a separation process of the emulsion over the measurement period - through different conductivities in the upper and in the lower area of the measuring vessel; the percentage difference is different from zero. In the case of a stable emulsion, however, there are almost no differences in the conductivity in the different measuring ranges; the percentage difference is accordingly zero or * only slight.
Fig. 1 zeigt die Ergebnisse der Messungen. Hieraus ist ersichtlich, daß- die erste Emulsion - Herstellungstemperatur 45 °C (unterhalb PIT) - schon über einen Meßzeitraum von nur 20 Stunden instabil, die zweite, erfindungsgemäße Emulsion - Herstellungstemperatur 95 °C (oberhalb PIT) - jedoch über einen wesentlich längeren Zeitraum stabil war.1 shows the results of the measurements. From this it can be seen that the first emulsion - production temperature 45 ° C (below PIT) - already unstable over a measurement period of only 20 hours, the second emulsion according to the invention - production temperature 95 ° C (above PIT) - but over a considerably longer period was stable.
Beispiel 3Example 3
Vergleich der Viskosität von Emulsionen gleicher Zusammensetzung aber unterschiedlicher Herstellungstemperatur (Fig. 2).Comparison of the viscosity of emulsions of the same composition but different manufacturing temperatures (Fig. 2).
Es wurden zwei Emulsionen aus Mischungen gemäß Formulierung A her¬ gestellt, wobei für die erste Emulsion eine Herstellungstemperatur von 60 °C - unterhalb PIT -, für die zweite, erfindungsgemäße Emulsion eine Herstellungstemperatur von 70 °C - oberhalb PIT, analog Beispiel 1.1 - gewählt wurde. Diese Emulsionen wurden im Verhältnis 1 : 1 mit Wasser verdünnt und anschließend die Viskositäten dieser Emulsionen bei unterschiedlichen Scherge¬ schwindigkeiten bestimmt. Fig. 2 zeigt die Ergebnisse der Messungen, die das Viskositätsver¬ halten einer verdünnten Emulsion, d.h. der bevorzugten Anwendungs¬ form, wiedergeben. Hieraus ist ersichtlich, daß die zweite, erfin¬ dungsgemäße Emulsion (mit Phaseninversion) wesentlich niedrig-vis¬ koser war als die erste Emulsion (ohne Phaseninversion).Two emulsions were prepared from mixtures according to formulation A, a production temperature of 60 ° C. - below PIT - for the first emulsion, and a production temperature of 70 ° C. - above PIT, analogous to Example 1.1 - for the second emulsion according to the invention has been. These emulsions were diluted 1: 1 with water and the viscosities of these emulsions were then determined at different shear rates. FIG. 2 shows the results of the measurements which show the viscosity behavior of a diluted emulsion, ie the preferred application form. From this it can be seen that the second emulsion according to the invention (with phase inversion) was significantly lower-viscous than the first emulsion (without phase inversion).
Beispiel 4Example 4
Lagerstabilität erfindungsgemäßer EmulsionenStorage stability of emulsions according to the invention
Die Lagerstabilität bei Raumtemperatur der erfindungsgemäßen Emul¬ sionen gemäß Beispiel 1.1 bis 1.3 wurde visuell beurteilt. Hierbei wurden die Emulsionen in Form der Konzentrate eingesetzt; die Emulsionen gemäß Beispiel 1.1 und 1.3 in unveränderter Form, die Emulsion gemäß Beispiel 1.2 wurde zuvor mit Ca(0H)2 neutralisiert. Die Ergebnisse sind aus Tabelle 2 ersichtlich.The storage stability at room temperature of the emulsions according to the invention according to Examples 1.1 to 1.3 was assessed visually. The emulsions were used in the form of concentrates; the emulsions according to Examples 1.1 and 1.3 in unchanged form, the emulsion according to Example 1.2 was previously neutralized with Ca (0H) 2. The results are shown in Table 2.
Tabelle 2Table 2
Emulsion gemäß Beispiel Lagerstabilität bei RaumtemperaturEmulsion according to example storage stability at room temperature
1.1 > 6 Monate1.1> 6 months
1.2 > 1 Monat1.2> 1 month
1.3 > 6 Monate1.3> 6 months
Diese Ergebnisse zeigen, daß die erfindungsgemäßen Konzentrate eine sehr gute Lagerstabilität aufweisen. 17These results show that the concentrates according to the invention have very good storage stability. 17
Beispiel 5Example 5
Stabilität einer verdünnten erfindungsgemäßen Emulsion (Fig, 3)Stability of a diluted emulsion according to the invention (Fig. 3)
Eine Emulsion gemäß Beispiel 1.1 wurde im Verhältnis 1 : 9 mit wäßriger NaOH-Lösung verdünnt und neutralisiert. Zur Beurteilung der Stabilität dieser Emulsion wurden die Leitfähigkeiten im oberen und unteren Bereich des Meßgefäßes ermittelt (vergleiche die linke Skala von Fig. 3) und die prozentuale Differenz gebildet (verglei¬ che die rechte Spalte von Fig. 3). Die Bedeutung dieses Meßverfah¬ rens hinsichtlich der Emulsionsstabilität wird im Beispiel 2 näher erläutert.An emulsion according to Example 1.1 was diluted in a ratio of 1: 9 with aqueous NaOH solution and neutralized. In order to assess the stability of this emulsion, the conductivities in the upper and lower area of the measuring vessel were determined (compare the left scale in FIG. 3) and the percentage difference was formed (compare the right column in FIG. 3). The importance of this measuring method with regard to emulsion stability is explained in more detail in Example 2.
Fig. 3 zeigt die Ergebnisse der Messungen. Hieraus ist ersichtlich, daß auch die verdünnte Emulsion, d.h. in ihrer bevorzugten Anwen¬ dungsform, über einen Zeitraum von nahezu 100 Stunden stabil war. Im Vergleich zur Konzentrat-Form, d.h. derjenigen Form, in der die Emulsionen üblicherweise gelagert werden, ist dieser Zeitraum für die Stabilität einer mit Wasser verdünnten Emulsion, d.h. derjeni¬ gen Form, in der derartige Emulsionen üblicherweise zur Anwendung gelangen, völlig hinreichend.3 shows the results of the measurements. It can be seen from this that the diluted emulsion, i.e. in its preferred application form was stable over a period of almost 100 hours. Compared to the concentrate form, i.e. In the form in which the emulsions are usually stored, this period is for the stability of an emulsion diluted with water, i.e. the form in which such emulsions are usually used is completely sufficient.
Beispiel 6Example 6
Prüfung des KorrosioπsschutzvermögensExamination of the protection against corrosion
Das Korrosionsschutzvermögen von erfindungsgemäßen Emulsionen sowie einer Vergleichsemulsion wurde nach D1N 51 359 geprüft. Das Prüf¬ verfahren wurde wie folgt durchgeführt: Stahlbleche der Qualität St 1405 (unlegierter Stahl, oberflächenvergütet, Abmessungen 2,5 x 5 cm) wurden jeweils in eine der nachstehend angegebenen Rostschutzemulsionen getaucht. Die Stahlbleche wurden in kurzem Kontakt' mit der Rostschutzemulsion gehalten, danach entnommen und nach 24 Stunden Abtropf- bzw. Trockendauer in eine Feuchtigkeits¬ kammer nach DIN 51 359 gehängt, in der bei kontinuierlicher Luft¬ zufuhr von 875 1/h und einer Temperatur von 50 °C die relative Luftfeuchte 100 % betrug. Es wurde jeweils die Zeitdauer ermittelt, nach der 100 % Korrosion (bezogen auf die Fläche des Prüfblechs) - bewertet nach DIN 51 359 - zu beobachten war.The corrosion protection properties of emulsions according to the invention and of a comparison emulsion were tested in accordance with D1N 51 359. The test procedure was carried out as follows: steel sheets of quality St 1405 (unalloyed steel, surface-hardened, dimensions 2.5 x 5 cm) were each placed in one of the following Anti-rust emulsions dipped. The steel sheets were held in short contact 'with the rust protection emulsion, then removed and hanged after 24 hours of dripping and drying time in a Feuchtigkeits¬ chamber according to DIN 51 359, in the case of continuous Luft¬ feed of 875 1 / h and a temperature of 50 ° C the relative humidity was 100%. The time period after which 100% corrosion (based on the area of the test sheet) - assessed according to DIN 51 359 - was observed.
Zum Test wurden jeweils eingesetzt:The following were used for the test:
Beispiel 6.1: Emulsion gemäß Beispiel 1.1, unverdünnt und in unterschiedlichen Verdünnungen mit Wasser (siehe Tabelle 3).Example 6.1: Emulsion according to Example 1.1, undiluted and in different dilutions with water (see Table 3).
Beispiel 6.2: Emulsion gemäß Beispiel 1.2 neutralisiert mitExample 6.2: Emulsion according to Example 1.2 neutralized with
Ca(0H)2, unverdünnt, und in unterschiedlichen Verdünnung mit Wasser (siehe Tabelle 3).Ca (0H) 2, undiluted, and in different dilutions with water (see Table 3).
Beispiel 6.3: Emulsion gemäß Beispiel 1.3.Example 6.3: Emulsion according to Example 1.3.
Beispiel 6.4: Emulsion gemäß Beispiel 1.4.Example 6.4: Emulsion according to Example 1.4.
Vergleichsbeispiel: Auf Basis der Formulierung D wurde eineComparative example: On the basis of formulation D, a
Emulsion hergestellt, wobei die Emulgiertemperatu 45 °C betrug (nicht-invertierte Emulsion). Diese Emulsion wurde mit Diethaπolamin neutralisiert.Emulsion prepared, the emulsification temperature was 45 ° C (non-inverted emulsion). This emulsion was neutralized with diethanolamine.
Die Ergebnisse der Tests sind aus Tabelle 3 ersichtlich: Tabel le 3The results of the tests are shown in Table 3: Table 3
Beispiel Verdünnungen mit Wasser 100 % Korrosion nachExample dilution with water 100% corrosion after
7; 1 : 9 40 Tagen 40 Tagen 40 Tagen 26 Tagen 13 Tagen7; 1: 9 40 days 40 days 40 days 26 days 13 days
Bei -den Beispielen 6.1 und 6.2 wurde die vorstehend angegebene Zeitdauer jeweils bei der unverdünnten Emulsion sowie bei allen Verdünnungen erreicht. In Examples 6.1 and 6.2, the time period specified above was achieved for the undiluted emulsion and for all dilutions.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Verfahren zur Herstellung stabiler, niedrig-viskoser O/W-Rostschutzemulsionen, wobei man ein Gemisch, enthaltend eine Öl-Komponente, Wasser und mindestens eine Emulgator-Komponente, bei einer Temperatur, bei der alle Komponenten des Gemisches in flüs¬ siger Form vorliegen, emulgiert und die gebildete Emulsion auf eine Temperatur innerhalb oder oberhalb des Phaseninversions-Tempera- turbereichs der Emulsion erhitzt oder das Gemisch bei einer Tempe¬ ratur innerhalb oder oberhalb des Phaseπinversions-Temperaturbe- reichs emulgiert, anschließend die Emulsion auf eine Temperatur unterhalb dieses Temperaturbereichs abkühlt und gegebenenfalls mit Wasser verdünnt, dadurch gekennzeichnet, daß man ein Gemisch der folgenden Zusam¬ mensetzung zur Emulsionsbildung einsetzt:1. Process for the preparation of stable, low-viscosity O / W anti-rust emulsions, wherein a mixture containing an oil component, water and at least one emulsifier component, at a temperature at which all components of the mixture in liquid form are present, emulsified and the emulsion formed is heated to a temperature within or above the phase inversion temperature range of the emulsion or the mixture is emulsified at a temperature within or above the phase inversion temperature range, then the emulsion to a temperature below this temperature range cooled and optionally diluted with water, characterized in that a mixture of the following composition is used to form the emulsion:
a) 10 bis 60 Gew.-% einer Öl-Komponente, b) 1 bis 10 Gew.-% einer Emulgator-Komponente, bestehend aus min¬ destens einem Anlagerungsprodukt von 2 bis 20 Mol Ethylenoxid an Fettalkohole mit 10 bis 22 C-Atomen, c) 1 bis 10 Gew.-% eines Korrosionsinhibitors, bestehend aus min¬ destens einer Carbonsäure der allgemeinen Formel (I):a) 10 to 60% by weight of an oil component, b) 1 to 10% by weight of an emulsifier component, consisting of at least one adduct of 2 to 20 moles of ethylene oxide with fatty alcohols having 10 to 22 carbon atoms , c) 1 to 10% by weight of a corrosion inhibitor, consisting of at least one carboxylic acid of the general formula (I):
R-C00H (I)R-C00H (I)
wobei R einen geradkettigen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 6 bis 22 C-Atomen oder einen Rest der allgemeinen Formel (II)where R is a straight-chain or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms or a radical of the general formula (II)
mit Rl = gesättigter, geradkettiger oder verzweigter Alkylres mit 8 bis 18 C-Atomen, darstellt with Rl = saturated, straight-chain or branched alkyl radicals having 8 to 18 carbon atoms
d) 0 bis 10 Gew.-% einer Coemulgator-Komponente, bestehend au mindestens einem Fettalkohol mit 12 bis 22 C-Atomen,d) 0 to 10% by weight of a co-emulsifier component consisting of at least one fatty alcohol with 12 to 22 carbon atoms,
e) Rest: Wasser.e) Rest: water.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man ein Gemisch der folgenden Zusammensetzung zur Emulsionsbildung ein¬ setzt: a) 20 bis 50 Gew.-% einer Öl-Komponente, b) 2 bis 8 Gew.-% einer Emulgator-Komponente, c)- 2 bis 6 Gew.- eines Korrosionsinhibitors, d) 0 bis 6 Gew.-% einer Coemulgator-Komponente e) Rest: Wasser.2. The method according to claim 1, characterized in that one uses a mixture of the following composition for emulsion formation: a) 20 to 50 wt .-% of an oil component, b) 2 to 8 wt .-% of an emulsifier component , c) - 2 to 6% by weight of a corrosion inhibitor, d) 0 to 6% by weight of a co-emulsifier component e) balance: water.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekenn¬ zeichnet, daß das Gemisch 1 bis 6 Gew.-% der Coemulgator-Komponente d) enthält.3. The method according to any one of claims 1 or 2, characterized gekenn¬ characterized in that the mixture contains 1 to 6 wt .-% of the co-emulsifier component d).
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß man als Öl-Komponente a) ein Paraffinöl und/oder ein Mineralöl einsetzt.4. The method according to any one of claims 1 to 3, characterized gekenn¬ characterized in that a paraffin oil and / or a mineral oil is used as the oil component a).
5. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß man als Emulgator-Komponente b) mindestens ein Anlagerungsprodukt von 4 bis 12 Mol Ethylenoxid an Fettalkohole mit 12 bis 18 C-Atomen einsetzt.5. The method according to any one of claims 1 to 3, characterized gekenn¬ characterized in that at least one adduct of 4 to 12 moles of ethylene oxide with fatty alcohols having 12 to 18 carbon atoms is used as the emulsifier component b).
6. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß man als Korrosionsinhibitor c) mindestens eine6. The method according to any one of claims 1 to 3, characterized gekenn¬ characterized in that the corrosion inhibitor c) at least one
T Carbonsäure der allgemeinen Formel (I), in der R einen geradkettigen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 8 bis 18 C-Atomen oder einen Rest der allgemeinen Formel (II) mit R* = gesättigter, geradkettiger Alkylrest mit 8 bis 12 C-Atomen darstellt, einsetzt.T Carboxylic acid of the general formula (I) in which R is a straight-chain or branched, saturated or unsaturated alkyl radical having 8 to 18 carbon atoms or a radical of the general formula (II) with R * = saturated, straight-chain alkyl radical having 8 to 12 carbon atoms Represents atoms.
7. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß man als Coemulgator-Komponente d) mindestens einen Fettalkohol mit 16 bis 18 C-Atomen einsetzt.7. The method according to any one of claims 1 to 3, characterized gekenn¬ characterized in that at least one fatty alcohol having 16 to 18 carbon atoms is used as coemulsifier component d).
8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekenn¬ zeichnet, daß man die Komponenten a, b und c im Gewichtsverhältnis a : b : c = 1 : (0,1 bis 0,3) : (0,1 bis 0,3), vorzugsweise im Gewirhtsverhältnis a : b : c = 1 : 0,2 : 0,15, einsetzt.8. The method according to any one of claims 1 to 7, characterized gekenn¬ characterized in that components a, b and c in the weight ratio a: b: c = 1: (0.1 to 0.3): (0.1 to 0.3), preferably in the weight ratio a: b: c = 1: 0.2: 0.15.
TT TT
EP90913798A 1989-10-04 1990-09-25 Process for manufacturing stable, low-viscosity ow anti-rust emulsions Expired - Lifetime EP0494884B1 (en)

Applications Claiming Priority (3)

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DE3933137A DE3933137A1 (en) 1989-10-04 1989-10-04 METHOD FOR PRODUCING STABILIZED, LOW VISCOUS O / W ANTI-VIRUSULUS EMULSIONS
DE3933137 1989-10-04
PCT/EP1990/001626 WO1991005033A1 (en) 1989-10-04 1990-09-25 Process for manufacturing stable, low-viscosity ow anti-rust emulsions

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ZA907907B (en) 1991-07-31
US5230730A (en) 1993-07-27
JPH05500988A (en) 1993-02-25
DE59007778D1 (en) 1995-01-05
KR920703770A (en) 1992-12-18
WO1991005033A1 (en) 1991-04-18
BR9007717A (en) 1992-07-07

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