EP2059628A1 - Zusammensetzungen auf basis von carbonsäuren zum vorübergehenden schutz von metalloberflächen und aus den zusammensetzungen erhaltene trockene filme - Google Patents

Zusammensetzungen auf basis von carbonsäuren zum vorübergehenden schutz von metalloberflächen und aus den zusammensetzungen erhaltene trockene filme

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Publication number
EP2059628A1
EP2059628A1 EP07803766A EP07803766A EP2059628A1 EP 2059628 A1 EP2059628 A1 EP 2059628A1 EP 07803766 A EP07803766 A EP 07803766A EP 07803766 A EP07803766 A EP 07803766A EP 2059628 A1 EP2059628 A1 EP 2059628A1
Authority
EP
European Patent Office
Prior art keywords
composition according
acid
composition
acids
mixture
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.)
Withdrawn
Application number
EP07803766A
Other languages
English (en)
French (fr)
Inventor
Nicole Genet
Olivier Lerasle
Thierry Kouvtanovitch
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.)
TotalEnergies Marketing Services SA
Original Assignee
Total Raffinage Marketing SA
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 Total Raffinage Marketing SA filed Critical Total Raffinage Marketing SA
Publication of EP2059628A1 publication Critical patent/EP2059628A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/008—Temporary coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086—Organic or non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
    • 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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers 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
    • C10M2207/125—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
    • C10M2207/1253—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 used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
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    • 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
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
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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
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
    • C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/041—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms used as base material
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/0425—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof used as base material
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    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
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    • C10M2215/224—Imidazoles
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    • C10M2217/044—Polyamides
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • 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
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31714—Next to natural gum, natural oil, rosin, lac or wax

Definitions

  • the present invention relates to a protective composition for metal surfaces sensitive to atmospheric oxidation based on carboxylic acids and at least one neutralizing agent. It also relates to the method of depositing said composition on these surfaces as well as its use for the protection of various specific metal surfaces. After forming plates and / or metal tubes, it is common to store long months under shelter before using them. This storage has great disadvantages for manufacturers because of the gradual deterioration of the surface condition of these metal parts. Indeed, in the absence of protection against the oxidation of air and moisture, it forms on the surface of these materials an oxidation layer, or pitting phenomena ...
  • any alteration of the surface of these materials may hinder their implementation, increasing, for example, the risk of breakage or cracks during the forming step or stamping.
  • this deterioration can significantly affect the effectiveness of subsequent treatments on metal surfaces. Indeed, one observes phenomena of flaking or cracking of the coatings which one covers them.
  • a first type of coating usually used consists of oily or semi-oily compositions obtained by mixing water and mineral oil in emulsion in the presence of a corrosion inhibitor as in US Pat. No. 4,342,596.
  • Another type of oily coating comprises a mixture emulsified in water paraffins and partially esterified paraffins, a small proportion of amides resulting from the reaction of an amine on a long chain carboxylic acid, a mixture of alcohol, hydrocarbons and a surfactant described in US Patent 4,479,981.
  • Such coatings are shown to have good stability and a good barrier to atmospheric oxidation. In addition, they play a lubricating role in subsequent treatments of the materials thus protected. However, for simple storage, the oily nature of these coatings is a nuisance and a significant source of pollution.
  • the Applicant proposes to provide a technical solution for obtaining an improved coating to protect metal surfaces from atmospheric corrosion in the form of a non-oily dry film.
  • an improved coating to protect metal surfaces from atmospheric corrosion in the form of a non-oily dry film.
  • the invention provides a protective composition for metal surfaces sensitive to atmospheric oxidation, based on carboxylic acids and at least one neutralizing agent, characterized in that the composition comprises an eutectic mixture of at least two carboxylic acids comprising n carbon atoms, with 6 ⁇ n ⁇ 22.
  • the invention also relates to a process for applying this composition to metal objects having metal surfaces, as well as to the dry film thus obtained and the metal objects coated with this dry film.
  • the dry film is obtained by evaporation of the solvent, generally water, contained in the composition according to the invention.
  • the invention therefore relates to the dry yarn obtained by evaporation of the composition according to the invention.
  • the invention has several advantages, including significant improvement in anticorrosive properties.
  • it is possible to achieve the same effectiveness of anti-corrosion protection by applying a quantity of the composition according to the invention, less important than that of a composition of the prior art, based on carboxylic acids and a neutralizing agent.
  • the protection against corrosion is higher in the case of the composition according to the invention.
  • the invention therefore also relates to a composition characterized in that it contains water as sole solvent.
  • the pH is in general between 6 and 9, and preferably between 7 and 9, advantageously between 7 and 8.
  • Such a pH in particular basic pH, makes it possible to obtain thin and ultrathin films, of the order of a few molecular layers.
  • the thickness of the thin film is typically less than one micron, and for example between 1 and 500 nm.
  • the dry film obtained can then be easily removed by washing with water and drying. This can also remain on the metal surface under a subsequent coating, because for some paints and varnishes, the presence of the dry film improves the adhesion of subsequent layers.
  • these coatings according to the invention are excellent. They make it possible, among other things, to dispense with an oiling with polluting mineral oils, of the product coated during its shaping.
  • the composition according to the invention comprises a eutectic mixture of at least two carboxylic acids comprising n carbon atoms, n being preferably even.
  • the fatty acids that may be used in the context of the invention may be derived from products from the green sector, that is to say from agricultural production, particularly for non-food use (sunflower, flax, rapeseed oil). ). They advantageously replace the polluting mineral oils used for the lubrication of metal surfaces.
  • n is greater than or equal to 10. According to another modality, n is less than or equal to 18.
  • the eutectic mixture is a mixture of two carboxylic acids, the first comprising from 10 to 16 carbon atoms, and the second from 14 to 22 carbon atoms.
  • the respective mass proportions of said acids are advantageously x ⁇ 5% - y ⁇ 5%, x and y being the respective mass proportions of the two acids in said binary mixture to the exact composition of the eutectic.
  • the difference between each value of n for each of the two acids ranges from 2 to 10.
  • the eutectic mixture is a mixture of three carboxylic acids comprising from 10 to 16 carbon atoms for the first, from 14 to 18 for the second, and from 16 to 22 for the third acid carboxylic acid.
  • the respective mass proportions of said acids are x ⁇ 3% - y ⁇ 3% - z ⁇ 3% for a tertiary mixture, x, y and z, being the respective mass proportions of the three acids in a mixture with the exact composition of the eutectic.
  • the protective composition according to the invention may advantageously contain from 0.5 to 5% by weight of at least one anti-corrosion agent.
  • Said anti-corrosion agent may be chosen from triazole derivatives such as benzotriazole and tolyltriazole, imidazole derivatives such as benzimidazole, citric acid or sorbic acid derivatives, and mixtures thereof.
  • the carboxylic acids that are suitable for the invention may be mono-, di-, or tri-acids, in linear or branched form, saturated or containing one or more unsaturations. Among them, those containing an even number of carbon atoms are preferred. Which may be mentioned saturated fatty acids peer capric acid HClO, lauric acid HC12, myristic acid HCl 4, HC16 palmitic acid, stearic HCIS acid, arachidic acid and behenic HC20 HC22 acid .
  • the fatty acids containing an odd number of carbon atoms are perfectly suitable for producing the composition according to the invention. Among them, mention may be made of heptanoic acid HC7, nonanoic acid HC9 and undecylenic acid HCn: 1.
  • At least one of the acids is of plant origin.
  • the neutralizing agent whose function is especially to buffer the protective composition, by varying the pH thereof between 6 and 9, and preferably between 7 and 9, advantageously between 7 and 8, may be chosen from those classically used by those skilled in the art.
  • these include alkali or alkaline-earth metal hydroxides, including sodium, potassium, calcium or magnesium hydroxides, aminoalkyls, cyclic, aromatic or non-aromatic amines, acyclic, alicyclic, heterocycle amines, primary, secondary or tertiary amines, especially alkylamines, imides and imines, and mixtures thereof.
  • Sodium hydroxide NaOH, potassium hydroxide KOH, primary, secondary or ternary amines are preferred.
  • the protective composition according to the invention may comprise at least one surfactant and / or at least one dispersant, said surfactant possibly being chosen from alkylpolyglycosides, ethoxylated fatty alcohols, ethoxylated fatty acids and ethoxylated oils. ethoxylated sorbitan esters, and said dispersant being selected from high molecular weight polyols, carboxylic acid salts such as (meth) acrylic copolymers, polyamide derivatives such as polyamide waxes.
  • the metal surface protection composition according to the invention may also contain one or more additives, which the person skilled in the art will easily be able to choose from among the numerous additives conventionally used. These include, but are not limited to, anti-foam additives, bactericides, dyes, odor masks, and mixtures thereof.
  • the invention also relates to the process for treating metal objects having a metal surface comprising at least one step of applying the composition according to the invention to a metal surface advantageously chosen from zinc, iron, aluminum, aluminum, copper, lead, and their alloys as well as steels, galvanized steels, aluminas, copper, the application step being by watering, spraying or immersion.
  • concentration and the amount of the protective composition to be applied according to the treatment method of the invention will depend on the degree of protection desired, the nature of the treated metal surface and its environment. Generally, it is prepared by dilution of a concentrated composition (between 100 to 500 g / L of active material) to a concentration which may be, before its application, between 1 to 50 g / l.
  • concentration of acids is between 1 and 500 g / l of active material, expressed as the total of carboxylic acids, of preferably between 100 and 500 g / L of active material (concentrated solution) or between 1 and 50 g / L of active material (dilute solution).
  • Another subject of the invention is the metal surface treated with a composition according to the invention, and more advantageously the metal surface covered with a dry film based on one of these compositions.
  • the invention also relates to a method of manufacturing a composition according to any one of the preceding claims, by mixing its constituents, optionally with heating.
  • the mixing step allows the solution of the acids in the solvent, most often composed exclusively of water.
  • the invention also relates to a method of washing coated objects according to the invention, for obtaining objects with a clean surface and non-oxidized.
  • the invention further relates to a method of forming the coated objects according to the invention.
  • the invention also relates to a process for painting or varnishing coated objects according to the invention.
  • FIG. 2 represents the evolution of the response current as a function of the corrosion potential for protection solutions based on
  • HC7 / HC11 1 of the prior art, I ⁇ ) of a C12 / C16 binary eutectic mixture (-) and a ternary eutectic mixture HC12 / HC16 / HC18 ⁇ "**"! / According to the invention .
  • FIG. 3 represents the evolution of the response current as a function of the corrosion potential on carbon steel at 25 ° C. for protection solutions based on HC7 / HC11: 1 of the prior art ( ⁇ ⁇ ⁇ ), a binary eutectic mixture Ci2 / ⁇ IC6 .rrrJ / and a ternary eutectic mixture HC12 / HC16 / HC22: 1 ⁇ z V y according to the invention.
  • FIG. 4 represents the evolution of the response current as a function of the corrosion potential on carbon steel at 25 ° C.
  • FIG. 5 represents the evolution of the response current as a function of the corrosion potential on galvanized steel at 25 ° C. for HC7 / HC11: 1 protection solutions of the prior art ( ⁇ O-) and of a ternary eutectic mixture HCi2 / HCi6 / HC22: 1 neutralized with a TEA / DGA (°) mixture according to the invention.
  • the term “eutectic” refers to a mixture having a eutectic behavior, containing at least two carboxylic acids, the eutectic behavior resulting in the mixture having a single melting point, lower than melting point of each of the carboxylic acids taken separately.
  • the term “exact composition of the eutectic” refers to the composition that corresponds, in the phase diagram, when the liquidus has a minimum that touches the solidus.
  • the inhibitory power of the various protective compositions is determined by standardized electrochemical measurements, based on ISO 17475, on samples of common carbon steel, electrogalvanised steel and galvanized steel.
  • the experimental cell consists of a thermostatically controlled glass chamber and three electrodes:
  • an electrode consisting of the steel sample, which is the working electrode undergoing corrosion, a saturated calomel reference electrode for measuring the potential, and a platinum auxiliary electrode for measuring the current.
  • the steel sample has a circular surface of 43 cm 2 in contact with an aqueous solution obtained by dilution of the concentrated mixture of neutralized carboxylic acids according to the prior art or according to the invention in corrosive water of the ASTM type. D 1384.
  • the potential sweep of the sample (representing the aggressiveness of the medium) is carried out and the current in response is measured.
  • aqueous solutions containing the neutralizing agent TriEthanolAmine (TEA) in an amount sufficient to buffer the final solution (pH between 7 and 8).
  • the mixing temperature is maintained at at least 30 ° C.
  • the mixtures made are diluted in corrosive water ASTM D 1384, so as to obtain a concentration of active ingredient of 10 g / L.
  • Comparative Example 1 Case of Binary Canectic HC12 / HC16.
  • the present example aims to show the anti-corrosion effect of dry films obtained by combining two carboxylic acids according to the invention, for the protection of metal surfaces sensitive to atmospheric oxidation.
  • two protective compositions A and B based on carboxylic acids and at least one neutralizing agent are prepared, composition A being that of the prior art, and composition B being prepared according to the present invention.
  • the total concentration of carboxylic acids in the final concentrated solution is 300 g / L for composition A and 150 g / L for composition B.
  • composition B contains the binary eutectic mixture HC12 / HC16 in the respective proportions 72/28% by weight, whose melting temperature is approximately 37 ° C., buffered by an excess of TEA.
  • the electrochemical tests, whose procedure is described above, are carried out on corrosive water ASTM D 1384 alone ( ⁇ ⁇ r ⁇ ) and on the solution containing the protective composition A of the prior art ( ⁇ - ⁇ ⁇ ), and the solution containing the protective composition B according to the invention ( ⁇ -1).
  • FIG. 1 The electrochemical results at 25 ° C. on carbon steel are shown in FIG. 1.
  • the introduction of carboxylic acids in solution makes it possible to reveal a protective bearing in the field of natural corrosion of the material.
  • the intensity of the current flowing through the steel sample in the protection range is slightly lower in the case of the steel plate covered with the composition B prepared according to FIG. the invention. This means that corrosion is significantly less active and the protection is better. Moreover, it is found that the recovery of the corrosive activity, schematized in this way in FIG. 1, is softer in the case of the eutectic mixture of the invention B. This results in generalized corrosion that is less harmful to the part. metallic.
  • the inhibitory power of the compositions A and B tested was furthermore determined by measuring the polarization resistances (Rp) and the corrosion currents (Icorr). The results are grouped in the following Table II.
  • the present example aims to show the anti-corrosive effect of dry films obtained by combining three carboxylic acids in eutectic proportions according to the invention, for the protection of metal surfaces sensitive to atmospheric oxidation.
  • a composition C is prepared according to the invention.
  • the total concentration of carboxylic acids in the final concentrated solution is 150 g / L, and its contents appear in Table III below.
  • Composition C contain ternary eutectic mixture HC12 / HC16 / HC18 in respective proportions of 57/23/20 weight%, whose melting temperature is about 0 C. 33.5
  • This figure also shows the appearance of a protective bearing in the field of natural corrosion of the material, by the use of carboxylic acids.
  • the total concentration of carboxylic acids in the final concentrated solution is 150 g / L, and its contents appear in Table V below.
  • Composition D contains the ternary eutectic mixture HC12 / HC16 / HC22.0 in the respective proportions 57.5 / 22.5 / 20% by weight, the melting point of which is approximately 34.5 ° C.
  • the mixture is neutralized by the TEA so as to reach a pH in the diluted solution of the order of 7-8.
  • This composition is compared with composition B according to the invention and composition A according to the prior art.
  • compositions and HC12 / HC16 / HC22.0 provide better protection than in the case of protection provided with the composition according to the prior art.
  • the ternary eutectic composition D seems to provide a slightly lower protection than that of the binary eutectic composition C on this support. The two curves are still quite close, this difference seems rather insignificant.
  • compositions E and F contain the ternary eutectic mixture HC12 / HC16 / HC22 1 in the respective proportions 28.5 / 11.5 / 60% by weight, whose melting point is approximately 13.5 ° C.
  • the mixture E is neutralized by the TEA so as to reach a pH in the diluted solution of the order of 7-8.
  • the mixture F is neutralized with a TEA / DGA mixture (in the proportions 2/3, 1/3) so as to reach a pH in the diluted solution of the order of 8-9.
  • the protective films formed by the two ternary eutectic compositions according to the invention have a very high polarization resistance. Electronic exchanges related to corrosion are therefore very difficult through the film. The corrosion current remains low, even if it is slightly higher than the case of the binary eutectic composition.

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EP07803766A 2006-08-08 2007-06-21 Zusammensetzungen auf basis von carbonsäuren zum vorübergehenden schutz von metalloberflächen und aus den zusammensetzungen erhaltene trockene filme Withdrawn EP2059628A1 (de)

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FR0607225A FR2904829B1 (fr) 2006-08-08 2006-08-08 Compositions a base d'acides carboxyliques pour protection temporaire de surfaces metalliques et films secs obtenus a partir desdites compositions
PCT/FR2007/001028 WO2008017739A1 (fr) 2006-08-08 2007-06-21 Compositions a base d'acides carboxyliques pour protection temporaire de surfaces metalliques et films secs obtenus a partir desdites compositions

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WO2012070256A1 (ja) * 2010-11-22 2012-05-31 株式会社キッツ バルブ・管継手等の銅合金製配管器材の銅及び亜鉛溶出防止方法とこれを用いた銅合金製配管器材並びに皮膜形成剤
FR2974112B1 (fr) * 2011-04-13 2013-05-03 Labema Lab Procede de traitement de protection des metaux a base de composition hydrosoluble d'huile(s) vegetale(s) saponifiee(s), et produits et compositions obtenus.
WO2016176795A1 (zh) * 2015-05-03 2016-11-10 南通长航船舶配件有限公司 船舶防锈涂料
US20250101330A1 (en) * 2023-09-25 2025-03-27 University Of North Texas Liquid and semisolid lubricant compositions, methods of making, and uses thereof

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