EP0784663A1 - Composition aqueuse de revetement de metal et procede presentant une capacite amelioree de mouillage de surfaces souillees par des contaminants huileux - Google Patents

Composition aqueuse de revetement de metal et procede presentant une capacite amelioree de mouillage de surfaces souillees par des contaminants huileux

Info

Publication number
EP0784663A1
EP0784663A1 EP95933805A EP95933805A EP0784663A1 EP 0784663 A1 EP0784663 A1 EP 0784663A1 EP 95933805 A EP95933805 A EP 95933805A EP 95933805 A EP95933805 A EP 95933805A EP 0784663 A1 EP0784663 A1 EP 0784663A1
Authority
EP
European Patent Office
Prior art keywords
component
aqueous liquid
metal object
metal
cold working
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Withdrawn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
EP95933805A
Other languages
German (de)
English (en)
Other versions
EP0784663A4 (fr
Inventor
Richard J. Church
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 Corp
Original Assignee
Henkel Corp
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 Corp filed Critical Henkel Corp
Publication of EP0784663A1 publication Critical patent/EP0784663A1/fr
Publication of EP0784663A4 publication Critical patent/EP0784663A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C9/00—Cooling, heating or lubricating drawing material
    • B21C9/02—Selection of compositions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J3/00—Lubricating during forging or pressing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/06—Copolymers with vinyl aromatic monomers
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0239—Lubricating
    • B21B45/0245—Lubricating devices
    • B21B45/0263—Lubricating devices using solid lubricants
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2209/02—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
    • C10M2209/086—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 polycarboxylic, e.g. maleic acid
    • 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
    • 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
    • C10M2209/108—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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/06—Perfluorinated 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • 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

Definitions

  • This invention relates to aqueous liquid compositions suitable for forming a pro ⁇ tective coating containing an organic binder material on metal surfaces that are contacted with the compositions, either by direct deposition of a protective film on the metal while the liquid composition is in contact with the metal, or, more commonly, by depositing a liquid film of the liquid composition on the metal and converting this liquid film to a protective solid film by removing water from the initially deposited liquid film and, op ⁇ tionally, heating or otherwise causing the solid constituents of the liquid film to coalesce and/or react, so as to produce an adherent solid film on the metal surface.
  • the solid film thus deposited may be protective against corrosion, damage during cold working of the underlying metal, or the like.
  • the metal surfaces processed as described above may or may not have other surface layers, such as phosphate or chromate conversion coatings, coatings formed by anodization, complex oxide layers such as those that can be formed with a commercially available product named BONDERTTE® 770X from the Parker
  • aqueous liquid compositions that deposit protective coatings on metal sur ⁇ faces are known. Many of them contain organic polymers in solution or stable disper ⁇ sion, and it has been observed that most such polymer containing aqueous liquids do not readily wet any part of a metal surface that is soiled with oil, grease, or similar organic materials. It is therefore customary to perform thorough and often elaborate, multistep cleaning processes to prepare metal surfaces for the formation of good protective coat ⁇ ings.
  • a major object of this invention is to provide aqueous liquids containing dis ⁇ persed or dissolved organic polymer molecules that are able to wet surfaces bearing or ⁇ ganic soils more readily than otherwise similar solutions known from the prior art.
  • a re ⁇ lated object is to reduce the need for at least some of the cleaning measures now custom- ary, particularly to reduce the number of separate cleaning process steps that are required, while still obtaining protective coatings at least as satisfactory as those now achieved from otherwise similar solutions.
  • Another object is to provide compositions that avoid or at least reduce the generation of foam which often is characteristic of aqueous compo ⁇ sitions with good wetting power.
  • a more particular object is to obtain some or all of the benefits noted above for particular types of aqueous compositions that provide metal, especially aluminum, copper, and most especially steel, surfaces with surface layers pro ⁇ tective against damage during cold working, drawing, or like mechanical processing
  • percent, “pans of, and ratio values are by weight;
  • the term “polymer” includes “oligomer”, “copoly- mer”, “terpolymer”, and the like and also includes any molecules containing a polymeric moiety that constitutes at least 20 % of the mass of the molecule, even if another part of the molecule, particularly one or more end groups, is not polymeric;
  • the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred;
  • description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the de- scription, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed;
  • specification of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole (any counterions thus implicitly specified should preferably be selected from among other constituents explicitly specified in ionic form, to
  • surfactants selected from the group consisting of fluormated carboxylate salt anionic surfactants and perfluoroalkyl poly(oxyethylene) nonionic surfactants enables aqueous liquid compositions comprising dissolved and/or dispersed organic film forming polymer(s) satisfactorily to wet both clean and organical ⁇ ly soiled metal surfaces, while most other surfactants, including some other types of fluorinated surfactants and other chemical types of surfactants that are recommended for wetting improvement in general terms by their suppliers are far less effective.
  • a poly ⁇ mer is defined as "film forming" for the purposes of this description if, when a solution or suspension of the polymer in water, containing at least 10 % nonvolatile solids, is dried at a temperature of at least 25 ⁇ C from a liquid film thickness of 1 millimeter, a continuous and coherent film that is solid at 25° C is produced.
  • Aqueous liquid compo ⁇ sitions containing wetting effective amounts of the effective surfactants according to this invention are prone to foaming, but this tendency can be adequately controlled with addi ⁇ tion of proper antifoam agents.
  • one embodiment of this invention is an aqueous liquid compo- sition suitable for protectively coating a metal substrate, said aqueous liquid composition comprising, preferably consisting essentially of, or more preferably consisting of, water and: (A) dissolved or dispersed constituents, including at least some dissolved, dispersed, or both dissolved and dispersed organic film forming polymer molecules, that are capable of reacting with one another, with a metal surface being treated, or both, or of spontaneously coalescing, or of both reacting and spontaneously coalescing, during or after at least one of (i) contact of the aqueous liquid composition with a metal surface, (ii) separation of a metal surface from such contact, and (iii) re ⁇ moval of water from any liquid film remaining on the metal after such contact and subsequent removal from contact of the metal with the aqueous liquid com ⁇ position, said contact of the aqueous liquid composition with the metal surface and said removal of water from any liquid film remaining on the metal after such contact and subsequent
  • Embodiments of the invention include working aqueous liquid compositions suit ⁇ able for contacting directly with metal surfaces to provide protective coatings thereon as described above, liquid or solid concentrates that will form such working aqueous liquid compositions upon dilution with water only, processes of using working aqueous liquid compositions according to the invention as defined above to form protective coatings on metal surfaces, protective solid coatings on metal surfaces formed in such a process, and metal articles bearing such a protective coating Description of Preferred Embodiments
  • the total concentration in an aqueous coating composition of the surfactants char ⁇ acteristic of this invention, i e , component (B) as defined above, preferably is, with in ⁇ creasing preference in the order given, at least 0 0001, 00002, 00004, 0 0006, 0 0008, 0 0010, 0 0012, 00014, 0 0016, 00018, 0 0020, 0 0040, 0 0080, 0 015, 0 030, 0 045, 0 060, 0 070, 0 080, 0 090, or 0 10 %
  • the concentration of surfactants characteristic of the inven ⁇ tion in an aqueous liquid composition independently preferably is, with increasing prefer ⁇ ence in the order given, not more than 0.8, 06, 04, 0.3, 0.25, 0.20, 0 18, 0 16, 0 14, 0.12, or 0.1 1 %.
  • the chemical nature and amount of component (A) in a working aqueous liquid composition according to the invention depend on the purpose of the treatment and in general preferably are the same as or similar to the chemical nature and amount of mater ⁇ ials used for similar protective purposes in the prior art.
  • ethoxylated alcohol(s) ethoxylated alcohol(s)
  • ethoxylated alcohol(s) more preferably those selected from the group consisting of alcohols having a chemical structure that can be produced by condensing ethylene oxide with primary, preferably straight chain, aliphatic alcohols having only one hydroxyl group and, with increasing preference in the order given, an average of at least 18, 25, 30, 35, 40, 43, 46 or 48 carbon atoms per molecule and independently, with in ⁇ creasing preference in the order given, an average of not more than 75, 65, 60, 57, 55, 52, or 51 carbon atoms per molecule.
  • the molecules of eth- oxylated alcohols used in a composition according to this invention contain, with increas ⁇ ing preference in the order given, at least 20, 30, 35, 40, 43, 47, or 49 %, and independ ⁇ ently preferably contain, with increasing preference in the order given, not more than 80, 70, 62, 57, 54, or 51 % of their total mass in the oxyethylene units.
  • the total concentration of ethoxylated alcohols in a working composition i.e., a liquid composition ready to be applied directly to a me ⁇ tallic surface to be protected by the solid coating formed after drying onto the metallic surface the liquid coating initially applied, preferably is, with increasing preference in the order given, not less than 1.0, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, or 6.3 % and independently preferably is not more than 50, 40, 35, 31, 28, 25, 22, 18, 17, 16, 15, 14,
  • a particularly preferred compon ⁇ ent (C) comprises, more preferably consists essentially of, or still more preferably con ⁇ sists of: (C. 1 ) a primary inhibitor component selected from the group consisting of non-sulfur- containing organic azole compounds, preferably organic triazoles, more preferab ⁇ ly benzotriazole or tolyltriazole; and (C.2) a secondary inhibitor component selected from the group consisting of organic azoles that also contain mercapto moieties, preferably mercaptobenzothiazole or mercaptobenzimidazole .
  • the concentration of component (C.1 ) in a working aque ⁇ ous liquid composition according to this invention preferably is, with increasing prefer ⁇ ence in the order given, not less than 10, 40, 100, 200, 400, 800, 1200, 1400, 1500, 1600, 1700, 1750, 1800, 1850, 1900, 1925, 1950, or 1975 pans per million (hereinafter often abbreviated "ppm") of the total composition and independently preferably is, with in- creasing preference in the order given, not more than 20,000, 10,000, 5000, 3500, 3300,
  • component (C. 1) is preferred for component (C. 1) to be selected from benzotriazole and tolyltriazole, and in fact a mixture of these two is more preferred than either of them alone.
  • the amount of each of benzotriazole and tolyltriaz- ole, expressed as a percentage of the total of component (C.1 ) preferably is, with increas ⁇ ing preference in the order given, independently for each of these two triazoles, not less than 5, 10, 15, 20, 25, 30, 35, 38, 41, 43, 45, 47, 48, or 49 % and independently preferab ⁇ ly is, with increasing preference in the order given, not more than 95, 90, 85, 80, 75, 70, 65, 62, 59, 57, 55, 53, 52, or 51 %.
  • the concentration of component (C.2) in a working aqueous liquid composition according to this invention preferably is, with increasing preference in the order given, not less than 1, 4, 10, 15, 20, 25, 30, 35, 38, 41, 43, 45, 47, or 49 ppm of the total composition and independently preferably is, with increasing preference in the order given, not more than 2000, 1000, 500, 350, 300, 250, 200, 175, 165, 155, 145, 135, 125, 120, 115, 110, 107, 110, 108, 106, 105, 104, 103, 102, or 101 ppm.
  • l) preferably is, with increasing preference in the order given, not less than 0.001: 1, 0.002: 1, 0.004: 1, 0 007 1 , 0 01 1 1 0, 0 015.1 0, 0 019 1 0, 0 020 1 0, 0 021 1 0, 0 022 1 0, 0 023 1 0, or 0 024 1.0 and independently preferably is, with increasing preference in the order given, not more than 2.1, 1.1, 0.5.1, 0.3.1, 0.2.1, 0 1 : 1, 0.09.1.0, 0 08 1.0, 0 07 1 0, 0 06 1.0, 0 05 1 0, 0 04 1 0, 0 035:1 00, 0.033 1 00, 0 031 1 00, 0 029 1 00, 0 028 1.00, 0 027 1.00, or 0 026 1 00
  • These ratios unlike the concentration preferences stated above, apply to concentrates as well as to working compositions.
  • compositions according to the in ⁇ vention be free from various materials often used in prior art coating compositions.
  • compositions according to this invention in most instances preferably contain, with increasing preference in the order given, and with independent preference for each component named, not more than 5, 2, 1, 0.5, 025, 0.12, 0 06, 0 03, 0.015, 0.007, 0.003, 0.001 , 0 0005, 0.0002, or 0.0001 % of any of (i) hydrocarbons, (ii) fatty oils of natural origin, (iii) other ester oils and greases that are liquid at 25° C, (iv) metal salts of fatty acids, (v) hexavalent chromium, (vi) nickel cations, (vii) cobalt cations, (viii) copper cat- ions, (ix) manganese in any ionic form, (x) graphite, and (xi) molybdenum sulfide
  • a prefe ⁇ ed component (A) according to a first prefened specific em ⁇ bodiment of this invention comprises, more preferably consists essentially of, or still more preferably consists of, the following subcomponents
  • copolymers of styrene with i) maleic anhydride, (ii) maleic acid, (iii) salts of maleic acid with ammonia, alkali metal hydroxides, and amines, or (iv) mixtures of any two or more of these, said copolymers containing a sufficient number of salt groups to be soluble and/or dispersible in wat- er; and
  • each of components (A. l .A) and (A.1 B) must be present in a chemical form other than esters formed by reaction with each other.
  • the term "maleic moiety" is defined as a portion of a polymer chain that conforms to one of the following general chemical formulas:
  • each of Q 1 and Q 2 which may be the same or different, is selected from the group consisting of hydrogen, alkali metal, ammonium, and substituted ammonium cat ⁇ ions.
  • the copolymers of styrene and maleic moieties to be used in the first preferred spe ⁇ cific embodiment of the invention preferably have a molar ratio of styrene to the maleic moieties in the range from 1 : 1 to 3.1, more preferably in the range from 1.5: 1 to 2.6: 1, still more preferably in the range from 1.8: 1 to 2.3 : 1.
  • the copolymers of styrene and maleic moieties to be used in the first preferred specific embodiment of the invention preferably are selected from polymers that have an average molecular weight in the range from 1 100 to 2700, more preferably in the range from 1600 to 1950, still more preferably in the range from 1650 to 1750.
  • these copolymers of styrene and maleic moieties to be used in this first prefened specific embodiment of the inven ⁇ tion contain no more than 25, or with increasing preference no more than 12, 5, 3, or 0 5 % of units derived from other monomers.
  • compositions according to this first preferred specific embodiment of this in- vention provide a very pliable and ductile lubricating film, thereby leading to superior cold forming processes.
  • Inorganic boron containing materials optional component (A. l .C), and extreme pressure additives, optional component (A.1 D) above, are generally preferred compon ⁇ ents in compositions according to this first preferred specific embodiment of the inven- tion, while other solid lubricants and hydrocarbons, optional items (A.1.E) and (A_ 1.F) above, generally are preferably omitted, although they may be useful in some applicat- ions.
  • Concentrates according to the first preferred specific embodiment of the invention preferably contain from 10 - 40 %, or more preferably from 20 - 40 %, of dispersed or dissolved solids.
  • Lubricant compositions according to this first preferred specific em- s bodiment of the invention suitable for direct application to metal surfaces to be lubricat ⁇ ed, preferably contain from 3 - 20, more preferably from 6 - 17, still more preferably from 10 - 14, % of total dissolved solids.
  • the pH of the liquid compositions for direct application to metal surfaces fall within the range o from 6 to 1 1, more preferably in the range from 7.5 to 9.0, or still more preferably from
  • alkaline materials preferably ammonium, sodium, potassium, or lithium hydroxide, in addition to the amines noted above, may be added to the composi ⁇ tions in order to achieve a pH within these ranges.
  • compositions according to this first preferred specific embodiment s of the invention are often used at fairly high temperatures such as 70° C or more. At such temperatures, if the compositions contain unsubstituted ammonium cations, or other ammonium cations derived from high volatility amines, there is a substantial concentra ⁇ tion of ammonia or free amine in the vapor space over the liquid working composition at equilibrium. Such concentrations can be objectionable to workers using the process.
  • ammonia and/or amine concentrations are conven ⁇ tionally measured by a Drager test apparatus, which gives readings in NH 3 equivalents, with amines as well as with ammonia itself
  • the cations other than hy ⁇ drogen used in a composition according to this first preferred specific embodiment of the invention be chosen from ammonium ions of amines having sufficiently low volatility 5 that the equilibrium overpressure of NH 3 equivalents as measured by a Drager test appa ⁇ ratus in the atmosphere over compositions according to this first preferred specific em ⁇ bodiment of the invention at a temperature of 70° C is, with increasing preference in the order given, not more than 50, 35, 25, 14, 9, 6, or 4 parts per million (hereinafter "ppm") of ammonia equivalent.
  • ppm parts per million
  • At least 50, 78, or 91 mole percent of the cations other than hydrogen present in compon ⁇ ent (A. l.A) as described above be selected from the group consisting of substituted am- momum cations derived by adding a proton to amines that will dissolve to form at least
  • the amines contain at least one hydroxyl group per molecule
  • the substituted ammonium cations are selected from the cations formed by adding a proton to diethyleth- anol amine, dimethylethanol amine, diethanol amine, monoethanol amine, or ⁇ s ⁇ -prop- anol amine
  • component (A.1 B) of compositions according to this first preferred specific embodiment of the invention Preferred characteristics for component (A.1 B) of compositions according to this first preferred specific embodiment of the invention have already been given above, under the general description of "ethoxylated alcohols"
  • the ratio by weight of component (A.1.A) to component (A 1 B) in compositions according to this first preferred specific embodiment of the invention is preferably be ⁇ tween 6 1 and 1 6, or, in order of increasing preference, between 4 1 to 1 4, 2 5 1 to
  • Component (A_l C) of compositions according to this first prefe ⁇ ed specific em- bodiment of the invention is preferably selected from the group consisting of bone acid and condensed boric acids, alkali metal and ammonium salts of boric acid and condensed bone acids; more preferably, component (A 1 C) is selected from boric acid, borax, and mixtures thereof, most preferably a mixture of boric acid and borax in a ratio of 2 0 1 0 is used
  • the ratio of the total of the stoichiometric equivalent as HjBOj of the boron in component (A 1 C) to the total of the solids content in components (A.1 A) and (A 1 B) preferably is, with increasing preference in the order given, not less than 0 02 1 0, 0 04 1 0, 006 1 0, 0 08 1 0, 0 10 1 0, 0 12 1 0, 0 14 1 0, 0 16 1 0, 0 18.1 0, 0 19.1.0, 0 2
  • Component (A.1 D) of the compositions according to this first preferred specific embodiment of the invention is preferably selected from partial esters, or salts of partial esters, of phosphoric acid with alcohols having a molecular structure that contains both (i) a part having the structure -(CH j ),.,-, where m is an integer between 12 and 22 contributing ⁇ ive, more preferably between 16 and 22 inclusive, and (ii) a part having the structure (CH 2 -CH 2 -O) p , where p is an integer having a sufficiently large value that the total alco- hol is soluble in water to the extent of, with increasing preference in the order given, at least 0. 1 , 0.4, 0.9, 1.3, 1.8, and 3 %.
  • component (A. I D) When component (A. I D) is used, it is preferably present in a ratio by weight to the total of components (A. l .A) and (A. I B) within the range from 1 : 10 to 1 :200, or more preferably from 1 :25 to 1 :70, still more preferably s from 1 :40 to 1 :55.
  • component (A. I E) is used, it preferably is selected from the group consisting of graphite, molybdenum disulfide, mica, and talc.
  • component (A.1 F) is used, it preferably is selected from substantially unsatur- ated aliphatic hydrocarbon compounds, including oligomers of ethene, propene, or mix- o tures of ethene and propene, with a molecular weight in the range from 750 - 3000, more preferably in the range from 1000 - 2000.
  • the specific area! density (also often called "add-on weight [or mass]”) of a com ⁇ position according to this first prefened specific embodiment of this invention, or any other embodiment containing ethoxylated alcohols and intended to protect the metal sub- s strate to which it is applied during mechanical cold working, after application from a li ⁇ quid composition to the metal surface and air drying of liquid thus applied, preferably is, with increasing preference in the order given, at least O. l, 0.3, 0.5, 0.7, 0.9, 1. 1 , 1.3, 1.5, 1.7, or 1.9 and independently preferably is, with increasing preference in the order given, not more than 20, 15, 12, 10, 9, 8, 7, or 6 grams per square meter of surface ("g m 2 ").
  • a lubricant composition according to this first prefened specific embodiment of this invention preferably is used on clean bare steel without any intermediate coating.
  • a lubricant composition according to this first prefened specific embodiment of this invention can also be used over an underlying phosphate conversion coating layer formed on the steel.
  • the phosphate conversion coating may be 5 formed by methods known per se in the art, and iron and manganese phosphate conver ⁇ sion coatings, as well as the zinc based phosphate type conversion coating which is usual as the pretreatment before lubricating with stearate soaps, may be used with this inven ⁇ tion.
  • any phosphate conversion coating used before application of a lubricant composi ⁇ tion preferably has 0 a specific areal density that is, with increasing preference in the order given, at least 0.2, 0.3, 0.5, 0.7, 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0 g m 2 and independently is, with increasing pref ⁇ erence in the order given, not more than 50, 30, 20, 15, 12, or 10 g/m 2 .
  • component (A) as described above comprises, more preferably consists essentially of, or still more prefer ⁇ ably consists of, the following subcomponents: (A.2.
  • A.2.D an extreme pressure and conosion resistant additive component as known per se in the art
  • A.2.E a component of dispersed or dissolved solid lubricant, exclusive of inor- i5 ganic boron containing materials, as known per se in the art
  • (A.2.F) a component selected from solid and liquid hydrocarbons.
  • compositions according to this second prefened embodiment of the invention also provide a very pliable and ductile lubricating film, as does the first specific embodi ⁇ ment described above.
  • the pH value of working compositions according to this second prefened embod ⁇ iment of the invention preferably is, with increasing preference in the order given, not less than 3, 4, 5, 6, 7, 7.3, 7.6, 7.9, 8.1, 8.3, 8.5, 8 7, 8 8, 8 9, or 9 0 and independently preferably is, with increasing preference in the order given, not more than 12, 1 1 , 10 7, 10.4, 10.2, 10.0, 9.9, 9.8, 9.7, 9.6, or 9.5.
  • the total solids content of a working composition according to this second pre ⁇ ferred specific embodiment of the invention preferably is, with increasing preference in the order given, not less than 1, 2, 3, 4, 5, 5.5, 6.0, 6.5, 7.0, 7.4, 7.7, 8.0, 8.3, 8.5, 8.7, 8.8, or 8.9 % and independently preferably is, with increasing preference in the order given, pot more than 50, 35, 25, 20, 18, 17, 16, 15.5, or 15.1 %.
  • the alkene polymerized to make component (A.2.A) preferably is selected from the group consisting of ethene (more commonly called “ethylene”), propene, 2-methyl propene, and 1- and 2-butenes; more preferably it is ethene or propene, most preferably ethene.
  • ethene more commonly called "ethylene”
  • propene propene
  • 2-methyl propene 2-methyl propene
  • 2-butenes more preferably it is ethene or propene, most preferably ethene.
  • acrylic acid is most prefened, and methacryiic acid and other homologs of acrylic acid, i e , mol ⁇ ecules differing from acrylic acid by the addition of one or more -CH 2 - groups, with not more than six, preferably not more than four, carbon atoms per molecule are next most prefened.
  • the fraction of the mass of the polymer made up of alkene residues preferably is, with increasing preference in the order given, not less than 1, 2, 4, 15, 30, 40, 50, 55, 60, 65, 70, 75, 80, or 84 %; independently, the fraction of the mass of the polymer made up of alkene residues preferably is, with increasing preference in the order given, not more than 99, 97, 95, 92, 90, 89, 87, or 86 %.
  • the fraction of the mass of the polymer made up of acrylic acid and/or acrylate residues preferably is, with increas ⁇ ing preference in the order given, not less than 1, 2, 4, 6, 8, 10, 11, 12, 13, or 14 %; inde ⁇ pendently, the fraction of the mass of the polymer made up of acrylic acid and/or acrylate residues preferably is, with increasing preference in the order given, not more than 50, 40, 35, 30, 25, 20, 18, or 16 %.
  • commercially available polymers in latex form are prefened for com ⁇ ponent (A.2.A); a variety of such commercial products are available.
  • the counterions for the neutralized acrylic acid units in the polymers are prefer ⁇ ably selected from the group consisting of magnesium, calcium, zinc, and alkali metal ions, with the divalent ions in this group more prefened. If alkali metal ions are used, the compositions preferably contain optional component (A.2.C) as described above. Even if other counterions are used, the compositions may contain component (A.2.C), but the favorable effect of this component is normally less than when the counterions are alkali metal ions.
  • the oxyalkylene units in component (A.2.B) of a composition according to this second prefened embodiment of this invention preferably have not more than 4, more preferably not more than 3, most preferably 2, carbon atoms per unit.
  • Component (A.2.B) of the compositions according to this second prefened specific embodiment of the invention is preferably selected from molecules having a chemical structure that can be produced by condensing an alkylene oxide with primary, preferably straight chain, ali- phatic alcohols having only one hydroxyl group and, with increasing preference in the order given, an average of at least 18, 25, 30, 35, 40, 43, 46 or 48 carbon atoms per mole ⁇ cule and independently, with increasing preference in the order given, an average of not more than 75, 65, 60, 57, 55, 52, or 51 carbon atoms per molecule.
  • the molecules of component (A.2.B) contain, with increasing preference in the order given, at least 20, 30, 35, 40, 43, 47, or 49 %, and independently preferably contain, with increasing preference in the order given, not more than 80, 70, 62, 57, 54, or 51 % of their total mass in the oxyalkylene units.
  • the ratio by weight of component (A.2.A) to component (A.2.B) in compositions according to this second prefened embodiment of the invention preferably is, with in ⁇ creasing preference in the order given, at least 1:10, 1 :8, 1.0:6.5, 1.0:5.0, 1.0:3.5, 1.0:2.5, 1.0:2.0, 1.0:1.7, 1.0:1.5, 1.0:1.3, 1.0:1.20, 1.0:1.17, 1.0:1.12, 1.0: 1.10, 1.0: 1.07, 1 0 1 04, 1.0: 1.03, 1.0:1.02, or 1.0:1.01, and independently preferably is, with increasing prefer ⁇ ence in the order given, not more than 10: 1, 5:1.0, 3:1.0, 2.5:1.0, 2.0.1.0, 1.8 1 0, 1 6 1.0, 1.50: 1.0, 1.40:1.0, 1.35:1.0, 1.30: 1.0, 1.25:1.0, 1.20: 1.0, 1.15: 1.0, 1.12: 1.0, 1.09: 1.0,
  • Component (A.2.C) of compositions according to this second prefened specific embodiment of the invention is preferably selected from the group consisting of boric acid and condensed boric acids, alkali metal and ammonium salts of boric acid and con- densed boric acids; more preferably, component (A.2.C) is selected from boric acid, bor ⁇ ax, and mixtures thereof; most preferably a mixture of boric acid and borax in a ratio of 2.0.1 0 is used.
  • the ratio of the total of the stoichio- metric equivalent as H 3 BO 3 of the boron in component (A.2.C) to the total of the solids content in components (A.2.A) and (A.2.B) preferably is, with increasing preference in the order given, not less than 0.01 : 1.0, 0.02:1.0, 0.04: 1.0, 0.06:1.0, 0.08: 1.0, 0.10: 1.0,
  • the add-on mass of a composition according to this second prefened specific em ⁇ bodiment of this invention present in place on the surface of metal to be cold worked preferably is, with increasing preference in the order given, not less than 0.1, 0.2, 0.4, 0 7, 1.0, 2.0, 2.5, 2.9, 3.2, 3.5, 3.7, 3.8, 3.9, 4.0, 4. 1, or 4.2 grams of solids per square meter of surface (hereinafter often abbreviated "g/m 2 ”) and independently preferably is, with increasing preference in the order given, not more than 60, 40, 30, 20, 17, 15, 13, 12, 1 1, 10, 9.0, 8.5, 8.0, 7.7, 7.4, 7.1, 6.9, 6.7, or 6.6 g/m 2 .
  • the practice of this invention may be further appreciated by consideration of the following, non-limiting, working examples, and the benefits of the invention may be fur ⁇ ther appreciated by reference to the comparison examples.
  • Test panels containing both clean and soiled areas of metal were prepared by placing one drop of REACTOBOND® 909 Makeup (hereinafter often abbreviated as
  • Test panels prepared in this manner were then coated with one of two exemplary drawing lubricant forming solution having the compositions shown in Table 1 , to pro ⁇ quiz dry add-on masses of 3.0 - 4.0 grams per square meter After coating, the panels were dried in an oven and then examined for visual evidence of dewetting on any part of the surface.
  • the surfactants tested are shown in Table 2.
  • PLURONICTM and TETRONICTM surfactants are available commercially from BASF Corp., Performance Chemicals Div.
  • FLUORADTM surfactants are available commercially from Minnesota Mining and Manu ⁇ facturing Co.
  • TRITONTM surfactants are available commercially from Union Carbide Corp.
  • ZONYLTM surfactants are available from E. I. du Pont de Nemours & Co.
  • FLUO- WETTM surfactants are available from Hoechst Chemical Co.
  • RADTM FC-129 surfactant contains 32 % of water, 14 % of 2-butoxyethanol, and 4 % of ethanol, with the balance consisting of potassium fluoroalkyl carboxylates, including at least 40 % of the one having Chemical Abstracts Service Registry Number ("CASR#") 2991-51-7 but possibly also including one or more of those having CASR#'s 67584-62-7, 67584-53-6, 67584-52-5, and 67584-51-4
  • FLUORADTM FC-430 surfactant contains 98.5 % of fluoroaliphatic polymeric esters and ⁇ 1.5 % of toluene.
  • FLUORADTM FC- 120 surfactant contains 25 % of ammonium perfluoroalkyl sulfonates and 37.5 % of each Table 2: SURFACTANTS
  • FLUORADTM FC-135 surfactant contains 50 % of fluoro ⁇ chemical alkyl quaternary ammonium iodides, 34 % 2-propanol, and 16 % of water.
  • DK-100 defoamer commercially available from Genessee Polymers of Flint, Michigan, at a concentration of 0.01 %, was effective in satisfactorily suppressing foam in compositions containing the prefened fluorochemical surfactants, without adversely affecting their other properties.

Abstract

Tensioactif anionique de sel carboxylate fluoré et/ou tensioactif non ionique de polyoxyéthylène de perfluoroalkyle permettant à des agents de traitement liquides aqueux contenant un polymère de mouiller des surfaces à la fois propres et contaminées par des matériaux huileux, tandis que la plupart des autres tensioactifs, y compris d'autres tensioactifs fluorés, ne répondent pas à cette exigence. Ces excellents tensioactifs de mouillage s'utilisent avec une combinaison d'azoles exempts de soufre, de préférence benzotriazole et tolyltriazole, ainsi que d'azoles contenant du soufre, de préférence 2-mercaptobenzothiazole ou mercaptobenzimidazole, afin d'empêcher la décoloration, la souillure ou la corrosion de surfaces en métal en cours de revêtement avec un agent protecteur organique à partir d'une dispersion ou d'une solution aqueuse.
EP95933805A 1994-10-07 1995-09-21 Composition aqueuse de revetement de metal et procede presentant une capacite amelioree de mouillage de surfaces souillees par des contaminants huileux Withdrawn EP0784663A4 (fr)

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Publication number Priority date Publication date Assignee Title
US5547595A (en) * 1995-02-07 1996-08-20 Henkel Corporation Aqueous lubricant and process for cold forming metal, particularly pointing thick-walled metal tubes
US6010539A (en) * 1996-04-01 2000-01-04 E. I. Du Pont De Nemours And Company Cleaning formulations for textile fabrics
US6251847B1 (en) * 1996-12-06 2001-06-26 Henkel Corporation Composition and method for cleaning/degreasing metal surfaces, especially composites of copper and aluminum
US6211132B1 (en) * 1996-12-13 2001-04-03 Henkel Corporation Composition and method for deburring/degreasing/cleaning metal surfaces
AU6962998A (en) * 1997-11-13 1999-06-07 Minnesota Mining And Manufacturing Company Methods of working metal and compositions useful as working fluids therefor
US5874390A (en) * 1997-12-22 1999-02-23 Cincinnati Milacron Inc. Aqueous machining fluid and method
US6399548B1 (en) * 2000-09-22 2002-06-04 Chevron Oronite Company Llc Functional fluids
US8012374B2 (en) 2004-11-04 2011-09-06 The University Of Cincinnati Slow-release inhibitor for corrosion control of metals
US7972659B2 (en) 2008-03-14 2011-07-05 Ecosil Technologies Llc Method of applying silanes to metal in an oil bath containing a controlled amount of water

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873458A (en) * 1973-05-18 1975-03-25 United States Steel Corp Resin-containing lubricant coatings
US4675158A (en) * 1985-07-30 1987-06-23 Calgon Corporation Mercaptobenzothiazole and tolyltriazole corrosion inhibiting compositions
US4750933A (en) * 1984-05-30 1988-06-14 Basf Aktiengesellschaft Floor polish emulsions based on ethylene copolymer
WO1992016603A1 (fr) * 1991-03-22 1992-10-01 Henkel Corporation Lubrification pour le formage a froid de metaux
US5281436A (en) * 1992-06-09 1994-01-25 Cal-West Automotive Products Protective coating composition and method of using such composition
US5330788A (en) * 1992-08-10 1994-07-19 Henkel Corporation Temporary coating system

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS615935A (ja) * 1984-06-21 1986-01-11 三菱油化株式会社 複合断熱材
US5218031A (en) * 1991-06-10 1993-06-08 Man-Gill Chemical Company Aqueous coating compositions, process and coated substrates
US5428095A (en) * 1992-06-09 1995-06-27 Cal-West Automotive Protective coating composition and method of using such composition
US5300142A (en) * 1992-08-11 1994-04-05 Henkel Corporation Compositions and process for highlighting surface defects in, and prevention of adhesion of hot metal to, metal surfaces

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873458A (en) * 1973-05-18 1975-03-25 United States Steel Corp Resin-containing lubricant coatings
US4750933A (en) * 1984-05-30 1988-06-14 Basf Aktiengesellschaft Floor polish emulsions based on ethylene copolymer
US4675158A (en) * 1985-07-30 1987-06-23 Calgon Corporation Mercaptobenzothiazole and tolyltriazole corrosion inhibiting compositions
WO1992016603A1 (fr) * 1991-03-22 1992-10-01 Henkel Corporation Lubrification pour le formage a froid de metaux
US5281436A (en) * 1992-06-09 1994-01-25 Cal-West Automotive Products Protective coating composition and method of using such composition
US5330788A (en) * 1992-08-10 1994-07-19 Henkel Corporation Temporary coating system

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 8612 Derwent Publications Ltd., London, GB; Class A84, AN 86-077789 XP002104178 & JP 61 005935 A (MITSUBISHI PETROCHEMICAL CO LTD), 11 January 1986 *
See also references of WO9611247A1 *

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