EP4174155A1 - Borfreies wasserbasiertes schmiermittel für die plastische verarbeitung - Google Patents

Borfreies wasserbasiertes schmiermittel für die plastische verarbeitung Download PDF

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Publication number
EP4174155A1
EP4174155A1 EP21204637.9A EP21204637A EP4174155A1 EP 4174155 A1 EP4174155 A1 EP 4174155A1 EP 21204637 A EP21204637 A EP 21204637A EP 4174155 A1 EP4174155 A1 EP 4174155A1
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EP
European Patent Office
Prior art keywords
lubricating composition
aqueous lubricating
surfactants
composition
composition according
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Withdrawn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
EP21204637.9A
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English (en)
French (fr)
Inventor
Marco Meoli
Ulrike Schmidt-Freytag
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP21204637.9A priority Critical patent/EP4174155A1/de
Priority to PCT/EP2022/077762 priority patent/WO2023072549A1/en
Publication of EP4174155A1 publication Critical patent/EP4174155A1/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/103—Clays; Mica; Zeolites
    • 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
    • C10M2205/16—Paraffin waxes; Petrolatum, e.g. slack wax
    • 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
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/12—Polysaccharides, e.g. cellulose, biopolymers
    • C10M2209/126—Polysaccharides, e.g. cellulose, biopolymers used as thickening agents
    • 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
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/055—Particles related characteristics
    • C10N2020/06—Particles of special shape or size
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • C10N2030/40—Low content or no content compositions
    • C10N2030/44—Boron free or low content boron compositions
    • 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
    • C10N2040/242—Hot 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold 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

  • the present disclosure is directed to an aqueous lubricating composition which is to be used in the cold working of metallic substrates. More particularly, the present disclosure is directed to an aqueous lubricating composition in which is dispersed a particulate solid lubricant which is to be deposited on a surface of the metallic substrate, which aqueous lubricating composition is free from boron compounds.
  • the practice of cold working refers to the plastic deformation of metals which is performed below the recrystallization temperature. In most manufacturing environments, this cold working is performed at room temperature but the employment of slightly higher temperatures - but still below the recrystallization temperature - can provide increased ductility and reduced strength in the metal to be worked.
  • the major cold-working operations can be classified under four heading: squeezing; bending; shearing; and, drawing, which drawing encompasses tube, bar, wire and shell drawing and also spinning and ironing. Focusing on squeezing processes, as these account for the greatest tonnage of worked products, these are commonly processes which have hot-working counterparts and include: cold rolling; swaging; cold forging; and extrusion.
  • these cold working processes do present a number of advantages. Most obviously the energetic expenditure of heating is not required but additional benefits include: the obtainment of better surface finishes to the worked metal; superior dimensional control of the worked metal; minimization of directional properties of the worked metal; improved strength of the worked metal; and the superior reproducibility of cold working processes.
  • GB2003923A (Foseco Int .) discloses a metal working lubricant composition comprising: (i) a water-soluble metallic soap; and, (ii) an alkali metal chloride, an alkali metal sulphate and an alkali metal borate.
  • WO00/63324 A1 (Chevron Chemical Co .) discloses a lubricant composition having a base oil of lubricating viscosity, a dispersed hydrated alkali metal borate, and a polyalkylene succinic anhydride or non-nitrogen derivative thereof.
  • EP 917559 A (Henkel Corporation) describes a waterborne lubricant for the cold plastic working of metals, said waterborne lubricant comprising, in addition to water: (a) a component of water-soluble inorganic salt; (b) a homogeneously dispersed component of solid lubricant; (c) a homogeneously emulsified component of at least one substance selected from the group consisting of mineral oils, animal and plant oils and fats, and synthetic oils; and, (d) surfactant, in which the solid lubricant to water-soluble inorganic salt weight ratio ((b)/(a)) is from 0.05:1 to 2:1 and the weight ratio of the oily component to the sum of the water-soluble inorganic salt and the solid lubricant ((c):(a+b)) is from 0.05:1 to 1:1.
  • EP 2450423 A (Henkel AG & Co. KGaA ) discloses a water-based lubricant for plastic working, comprising a resin component containing a copolymer or homopolymer of monomers having an ethylenically unsaturated bond, including at least maleic anhydride (a), an inorganic component (b), and a solid lubricating component (c), wherein maleic anhydride moieties of the resin component (a) are blocked with a nitrogen-containing compound at a blocking ratio of 10 to 80%, and unblocked of maleic anhydride moieties are neutralized with an alkaline component at a degree of neutralization of 40 to 100%.
  • a resin component containing a copolymer or homopolymer of monomers having an ethylenically unsaturated bond including at least maleic anhydride (a), an inorganic component (b), and a solid lubricating component (c), wherein maleic anhydride moieties of the resin component
  • JP2011246684A (Nihon Parkerizing ) discloses an aqueous lubricant for plastic working of a metallic material, said lubricant comprising: alkaline metal borate salts (a), wherein the alkaline metal borate salts (a) contain lithium borate and wherein the molar ratio of lithium to all the alkaline metals in the alkaline metal borate salts (a) is 0.1 to 1.0; and, wherein the molar ratio (B/M) of boron (b) to alkaline metals M in the alkaline metal borate salts (a) is 1.5 to 4.0.
  • CN107805541A (Maanshan Tuori Metal Surface Tech Co. Ltd ) provides a lubricant for plastic working, said lubricant comprising by weight: 10-50% of stearic acid; 1-10% of borate; 1-10% of a rust inhibitor; 1-10% of an inorganic alkali; 0.1-0.5% of an antifoaming agent; and, the balance of water.
  • an aqueous lubricating composition comprising, based on the weight of the composition:
  • the aqueous lubricating composition comprises, based on the weight of the composition
  • the aqueous lubricating composition may, optionally, have a pH of from 7 to 10, preferably from 7 to 9.
  • the aqueous lubricating composition will conventionally comprise from 60 to 90 wt.%, preferably from 65 to 85 wt.%, more preferably from 65 to 80 wt.% of water, based on the weight of the composition.
  • the aqueous lubricating composition may, alternatively or additionally to the water content characterization, be characterized by a viscosity of from 0.005 to 1 Pa ⁇ s, as measured using a Brookfield viscometer at 25°C.
  • the total amount of rheological control agent(s) c) included in the composition should be from 1 to 10 wt.%, preferably from 2 to 8 wt.% of the total amount by weight of components a) and b). It is preferred that the or each rheological control agent included in the composition is a thixotrope.
  • An exemplary aqueous lubricating composition in accordance with the present invention comprises, based on the weight of the composition:
  • the invention further provides a process for the plastic cold working of a solid metallic substrate by mechanically forcing said solid metallic substrate through an aperture bounded by at least one solid surface of at least one metal working tool, said process comprising the steps of:
  • room temperature is 23°C plus or minus 2°C.
  • Mn and Mw are determined by gel permeation chromatography (GPC) with tetrahydrofuran (THF) as the eluent in accordance with DIN 55672-1:2007-08.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • PD polydispersity
  • d 50 particle size is meant that the particle size distribution is such that at least 50% of the particles by weight have a particle size diameter of less than the specified value. Unless otherwise stated, that particle size is determined by laser diffraction.
  • aqueous lubricating composition refers to that composition which actually contacts the metallic substrate. As is known in the art, such contacting can occur in a socalled “bath” which is shaped, sized and disposed to enable at least part of the substrate to be immersed therein.
  • the bath should moreover be sized to allow for movement of the aqueous lubricating composition around and throughout the loaded substrate, which movement can be further enhanced with recirculation and / or ultrasonics.
  • the pH of the composition within the bath, the temperature of the bath, and contact time of the substrate are result effective variables which should be monitored either manually or automatically, whenever possible.
  • alloy refers to a substance composed of two or more metals or of a metal and a non-metal which have been intimately united, usually by being fused together and dissolved in each other when molten.
  • X alloy therefore denotes an alloy of which the metal X is the majority constituent component and wherein X will generally comprise at least 40 wt.% - more typically at least 50 wt.% or at least 60 wt.% - of the alloy, on a metals basis.
  • C 1 -C n alky l refers to a monovalent group that contains 1 to n carbons atoms, that is a radical of an alkane and includes straight-chain and branched organic groups.
  • a " C 1 -C 18 alkyl” group refers to a monovalent group that contains from 1 to 18 carbons atoms, that is a radical of an alkane and includes straight-chain and branched organic groups.
  • alkyl groups include, but are not limited to: methyl; ethyl; propyl; isopropyl; n-butyl; isobutyl; secbutyl; tert-butyl; n-pentyl; n-hexyl; n-heptyl; and, 2-ethylhexyl.
  • such alkyl groups may be unsubstituted or may be substituted with one or more halogen.
  • R a tolerance for one or more non-halogen substituents within an alkyl group will be noted in the specification.
  • C 1 - C n hydroxyalkyl refers to a HO-(alkyl) group having from 1 to n carbon atoms, where the point of attachment of the substituent is through the oxygen-atom and the alkyl group is as defined above.
  • alkoxy group refers to a monovalent group represented by -OA where A is an alkyl group: non-limiting examples thereof are a methoxy group, an ethoxy group and an iso-propyloxy group.
  • C 1 -C 12 alkoxyalkyl refers to an alkyl group having an alkoxy substituent as defined above and wherein the moiety (alkyl-O-alkyl) comprises in total from 1 to 12 carbon atoms: such groups include methoxymethyl (—CH 2 OCH 3 ), 2-methoxyethyl (—CH 2 CH 2 OCH 3 ) and 2-ethoxyethyl.
  • alkylene as used herein, is defined as a saturated, divalent hydrocarbon radical. In general in the present disclosure, such alkylene groups may be unsubstituted or may be substituted with one or more halogen.
  • C 3 ⁇ C 30 cycloalkyl is understood to mean a saturated, mono- or polycyclic hydrocarbon group having from 3 to 30 carbon atoms.
  • such cycloalkyl groups may be unsubstituted or may be substituted with one or more halogen.
  • R a tolerance for one or more non-halogen substituents within a cycloalkyl group will be noted in the specification.
  • Examples of cycloalkyl groups include: cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; adamantane; and, norbornane.
  • cycloalkylene means a divalent radical formed by the removal of two hydrogen atoms from one or more rings of a cycloalkyl group.
  • an " C 6 -C 18 aryf' group used alone or as part of a larger moiety - as in "aralkyl group” - refers to monocyclic, bicyclic and tricyclic ring systems in which the monocyclic ring system is aromatic or at least one of the rings in a bicyclic or tricyclic ring system is aromatic.
  • the bicyclic and tricyclic ring systems include benzofused 2-3 membered carbocyclic rings.
  • such aryl groups may be unsubstituted or may be substituted with one or more halogen. Where applicable for a given moiety (R), a tolerance for one or more non-halogen substituents within an aryl group will be noted in the specification.
  • Exemplary aryl groups include: phenyl; (C 1 -C 4 )alkylphenyl, such as tolyl and ethylphenyl; indenyl; naphthalenyl, tetrahydronaphthyl, tetrahydroindenyl; tetrahydroanthracenyl; and, anthracenyl. And a preference for phenyl groups may be noted.
  • C 2 -C 20 alkenyl refers to hydrocarbyl groups having from 2 to 20 carbon atoms and at least one unit of ethylenic unsaturation.
  • the alkenyl group can be straight chained, branched or cyclic and may optionally be substituted with one or more halogen. Where applicable for a given moiety (R), a tolerance for one or more non-halogen substituents within an alkenyl group will be noted in the specification.
  • alkenyl also encompasses radicals having "cis” and “trans” configurations, or alternatively, “ E “ and “Z' configurations, as appreciated by those of ordinary skill in the art.
  • alkenylene means a divalent group formed by the removal of two hydrogen atoms from al alkenyl group as defined above.
  • alkylary l refers to alkyl-substituted aryl groups, both groups being defined as above.
  • aralkyl means an alkyl group substituted with an aryl radical as defined above.
  • hetero refers to groups or moieties containing one or more heteroatoms, such as N, O, Si and S.
  • heterocyclic refers to cyclic groups having, for example, N, O, Si or S as part of the ring structure.
  • heteroalkyl alkyl, cycloalkyl and aryl groups as defined hereinabove, respectively, containing N, O, Si or S as part of their structure.
  • base refers to a species: which is capable of abstracting a proton in either a polar or non-polar solvent; or, which is capable of donating a hydroxide anion (OH - ).
  • amine is used in accordance with its ordinary meaning in the art and broadly refers to a compound containing a nitrogen atom with a lone pair.
  • C 1 -C 9 heteroaryl amine refers to a compound wherein at least one carbon atom of an aromatic ring - which may be present in a monocyclic or polycyclic ring system - is substituted with a nitrogen atom.
  • a C 1 -C 9 heteroaryl amine has from 1 to 3 carbon atoms of the aromatic ring substituted with nitrogen atoms.
  • the heteroaryl amine may be unsubstituted or substituted with one or more C 1 -C 4 alkyl groups at any position of the heteroaryl ring.
  • a heteroaryl amine in addition to having at least one carbon atom of the hydrocarbon ring substituted with a nitrogen atom, can also have one or more carbon atoms substituted with other heteroatoms.
  • heteroaryl amines include, but are not limited to pyridine, pyrrole, pyrimidine, imidazole, quinazoline, purine, pyrazole, and triazole.
  • C 1 -C 9 heterocyclic amine refers to an aliphatic compound which may be monocyclic or polycyclic, wherein at least one carbon atom - and preferably 1 or 2 carbon atoms - of a given hydrocarbon ring is substituted with a nitrogen atom.
  • the number of ring carbon atoms is in toto from 1 to 9.
  • a heterocyclic amine can be unsubstituted or substituted with one or more C 1 -C 4 alkyl groups, as defined above, at any position of the heterocycle, including the one or more nitrogen atoms.
  • a heterocyclic amine in addition to having at least one carbon atom of a hydrocarbon ring substituted with a nitrogen atom, can also have one or more carbon atoms substituted with other heteroatoms.
  • heterocyclic amines include, but are not limited to, piperazine, pyrrolidine, and morpholine.
  • amino acid is an organic acid having one or more than one alkaline radical such as amino, guanidino, imino or hydrazine radicals attached at any carbon atom other than that of the carboxyl group.
  • basic amino acid refers to an amino acid having an additional alkaline radical that can accept a proton. Examples of basic amino acids include, but are not limited to arginine and lysine, including both the L- and D- forms of each.
  • amino sugar refers to a monosaccharide unit having one or more hydroxyl groups substituted with an —NR 2 group, wherein each R is independently selected from H or C 1 -C 4 alkyl.
  • amino sugars include, but are not limited to glucosamine and N-methylglucamine.
  • Viscosities of the composition compositions may be determined using the Brookfield Viscometer, Model RVT at standard conditions of 20°C and 50% Relative Humidity (RH).
  • the viscometer is calibrated using silicone oils of known viscosities, which vary from 5,000 cps to 50,000 cps.
  • a set of RV spindles that attach to the viscometer are used for the calibration.
  • Measurements of the aqueous lubricating compositions are done using the No. 6 spindle at a speed of 20 revolutions per minute for 1 minute until the viscometer equilibrates. The viscosity corresponding to the equilibrium reading is then calculated using the calibration.
  • compositions are defined herein as being “substantially free” of certain compounds, elements, ions or other like components.
  • the term “substantially free” is intended to mean that the compound, element, ion or other like component is not deliberately added to the composition and is present, at most, in only trace amounts which will have no (adverse) affect on the desired properties of the coating.
  • An exemplary trace amount is less than 1000 ppm by weight of the composition.
  • the term “substantially free” encompasses the term “free”, the latter term indicating those embodiments where the specified compound, element, ion, or other like component is completely absent from the composition or is not present in any amount measurable by techniques generally used in the art.
  • the aqueous lubricating composition of the present disclosure comprises from 1 to 20 wt.%, based on the weight of the composition of a) at least one water-soluble inorganic salt.
  • the aqueous lubricating composition should preferably comprise from 2 to 20 wt.%, for example from 5 to 20 wt.% of a) said at least one water-soluble inorganic salt.
  • the or each included water-soluble inorganic salt is in the dissolved state in the aqueous lubricating composition.
  • the chemical nature of the salt(s) is not critical save for the fact that inorganic salts containing boron - such as borate salts - are precluded.
  • the water-soluble inorganic salt should form a coating upon the metallic substrate which is to be cold worked.
  • Non-limiting examples of suitable water-soluble inorganic salts include: phosphate salts, such as calcium phosphate; polyphosphate salts including alkali metal polyphosphates; alkali metal silicates, in particular sodium and potassium silicate; alkali metal tungstates, in particular sodium tungstate; molybdate salts including ammonium molybdate and alkali metal molybdates, in particular sodium molybdate; sulphate salts including alkali metal sulphates, in particular sodium sulphate and potassium sulphate; and, carbonate salts including alkali metal carbonates, in particular sodium or potassium carbonate.
  • phosphate salts such as calcium phosphate
  • polyphosphate salts including alkali metal polyphosphates
  • alkali metal silicates in particular sodium and potassium silicate
  • alkali metal tungstates in particular sodium tungstate
  • molybdate salts including ammonium molybdate and alkali metal molybdates, in particular sodium moly
  • polyphosphate refers to a group comprising at least 2, for example from 2 to 6, tetrahedral phosphate (PO 4 ) units linked together via shared oxygen atoms: the polyphosphate may be linear or cyclic.
  • exemplary alkali metal polyphosphates having utility in the present disclosure include but are not limited to: tetrasodium pyrophosphate; tetrapotassium pyrophosphate; sodium tripolyphosphate; potassium tripolyphosphate; sodium metaphosphate; potassium metaphosphate; sodium hexametaphosphate; potassium hexametaphosphate; lithium hexametaphosphate; and, mixtures thereof.
  • component a) comprise a mixture of sodium sulphate, potassium tripolyphosphate and sodium tripolyphosphate.
  • the aqueous lubricating composition comprises b) at least one particulate solid lubricant.
  • the particles of the lubricant are conventionally dispersed within the composition: when that composition is applied to the surface of the substate to be worked and is subsequently dried thereon, the particles become deposited on that surface. Depending on the nature of the solid lubricant, some coalescence of the deposited particles may occur upon drying, leading to the development of a lubricating film on the substrate surface.
  • the ratio by weight of b) said at least one particulate solid lubricant to a) said at least one water-soluble inorganic salt [(b):(a)] in the waterborne lubricant should be in the range from 0.1:1 to 1:1.
  • said weight ratio [(b):(a)] is in the range from 0.2:1 to 1:1, in particular from 0.4:1 to 1:1 or from 0.4:1 to 0.8:1.
  • the particular value of this ratio should be selected based on inter alia the specific shape of the metal stock to be subjected to plastic working, the working conditions and the working device.
  • the resulting coating When the weight ratio has a value below 0.1:1, the resulting coating will have diminished lubricating properties and, as such, scuffing and seizure of the metal workpiece can occur.
  • a weight ratio in excess of 1:1 can result in a reduced coating hardness and in a reduced adhesion between the substrate and the coating: when the metal is introduced to the mouth of the tool under these circumstances, the dried coating formed on the surface is very prone to debonding, which results in impaired lubricating properties.
  • the particulate solid lubricant will conventionally be selected from: i) lamellar solids, including talc, micas, graphite, zinc sulphide (ZnS), cadmium sulphide (CdS), molybdenum disulfide (MoS 2 ), molybdenum selenide (MoSe 2 ); tungsten disulfide (WS 2 ), selenium disulfide (SeS 2 ), calcium fluoride (CaF 2 ) and sodium-aluminum fluorides, such as cryolite and modified cryolite as disclosed in US Patent No.
  • lamellar solids including talc, micas, graphite, zinc sulphide (ZnS), cadmium sulphide (CdS), molybdenum disulfide (MoS 2 ), molybdenum selenide (MoSe 2 ); tungsten disulfide (WS 2 ), selenium disulfide (S
  • metal soaps including the metal salts of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid and behenic acid; iii) lubricious oxides, including titanium oxide, cadmium oxide, cobalt oxide, zinc oxide and silica (SiO 2 ); iv) non-lamellar, lubricious metallic compounds such as cerium fluoride (CeF 3 ), calcium hydroxide, calcium carbonate, zinc phosphate, zinc calcium phosphate and manganese phosphate; v) soft elemental metals including gold, silver, lead, tin, indium and barium; vi) solid polymeric lubricants including polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), polyacetals, polyimides, polyether ether ketone (PEEK) and ultra-high molecular weight polyethylene (UHWPE);
  • PTFE polytetrafluoro
  • the term "mica” above encompasses both synthetic mica and natural micas such as sericite and muscovite.
  • the metal soaps will conventionally include calcium, aluminum, magnesium, barium, zinc, lead, lithium or potassium as the constituent metals; a preference for the use of calcium stearate as the metal soap may be mentioned.
  • exemplary waxes having utility in the aqueous lubricating compositions include: paraffin wax [ CAS No. 8002-74-2 ]; polyethylene wax [ CAS No. 9002-88-4 ]; polyethylene-polypropylene waxes; co-polymeric polyethylene waxes, for example copolymers of ethylene with at least one monomer selected from (meth)acrylic acid, maleic anhydride, vinyl acetate and vinyl alcohol, which copolymers are available under, for instance CAS Nos.
  • any waxes included in the present composition meet at least one of the following conditions: i) an acid number of less than 200 mg KOH/g, preferably less than 100 mg KOH/g; ii) a melting point of from 40 to 200°C, preferably from 60 to 180°C; and, iii) a number average molecular weight (Mn) of at least 200 g/mol, preferably at least 400 g/mol.
  • these conditions are not intended to be mutually exclusive: waxes may meet one, two or desirably three of these conditions.
  • the solid lubricant comprises or consists of: at least one phosphate salt selected from the group consisting of zinc phosphate, zinc calcium phosphate and manganese phosphate; and, at least one wax selected from polyethylene waxes, oxidized polyethylene waxes, polypropylene waxes, oxidized polypropylene waxes and co-polymeric waxes based on ethylene or propylene as the majority monomers.
  • the or each wax included in the composition should be further characterized by a number average molecular weight (Mn) of from 400 to 30,000 g/mol, preferably from 1000 to 25,000 g/mol.
  • the or each solid particulate lubricant may be initially provided: i) in finely divided powder form, in particular in a micronized form characterized by a dso particle size of less than 5 microns, as measured by laser diffraction; and / or, ii) as an aqueous dispersion, the particles of which dispersion may desirably be characterized by a dso particle size of less than 5 microns, as measured by dynamic light scattering.
  • the or each solid particulate lubricant included in the aqueous composition may have a dso particle of less than 2 microns, preferably less than 1 micron, as measured by laser diffraction.
  • the aqueous lubricating composition of the present disclosure comprises from 0.1 to 5 wt.%, based on the weight of the composition of c) at least one rheological control agent.
  • the aqueous composition may preferably comprise from 0.1 to 2.5 wt.%, for example from 0.1 to 2 wt.% of c) said least one rheological control agent.
  • the total amount of rheological control agent(s) c) included in the composition should be from 1 to 10 wt.%, for example from 2 to 8 wt.% of the total amount by weight of components a) and b).
  • rheological control agent references a compound which is capable of absorbing liquid, such as but not limited to water, physically swell and thereby alter the liquid viscometric and flow properties.
  • a rheological control agent may also function as a thickening agent and serve to keep the components of the composition - in particular the solid lubricant - in a dispersed form, typically by creating a continuous phase matrix. This agent may further function to modify the drying characteristics of the composition.
  • a thixotrope is a substance which
  • said at least one rheological agent should be selected from the group consisting of: clays, such as smectite clays, synthetic hectorite clays, colloidal montmorillonites, silicoaluminate clays and collidal magnesium aluminium silicate derived from natural smectic clay; fumed silica (pyrogenic silica); carboxyl vinyl polymers; polyvinylpyrrolidone (PVP) polymers and copolymers, such as PVP/vinyl acetate co-polymers; polyacrylates; cellulose derivatives, such as carboxymethycellulose (CMC), carboxyhydroxymethylcellulose, ethoxymethylcellulose, hydroxyethylcellulose and hydroxypropylcellulose; natural thickeners, such as alginate, guar gum, starch, gum tragacanth and locust bean gum; polysaccharides, such as xanthan gum; and, proteins, such as caseine, collagen and albumin.
  • clays such as s
  • particulate rheological control agents When particulate rheological control agents are included in the composition, these should preferably be initially provided in a micronized form characterized by a d 50 particle size of less than 5 microns, in particular less than 2 microns, as measured by laser diffraction.
  • fumed silicas, natural clays and synthetic clays should - as provided for inclusion in the composition - be characterized by a dso particle size of from 5 to 100 nm, for example from 5 to 40 nm, as measured by laser diffraction.
  • cellulose derivatives and / or polysaccharides as the rheological control agent.
  • the aqueous composition comprises at least one of, and preferably both of, carboxymethycellulose (CMC) and xanthan gum.
  • the aqueous lubricating composition of the present disclosure comprises from 0.1 to 5 wt.%, based on the weight of the composition of d) at least one base.
  • the aqueous lubricating composition may preferably comprise from 0.1 to 2.5 wt.%, for example from 0.1 to 2 wt.% of d) said least one base.
  • the added amount of base should be such that the aqueous lubricating composition has a pH of from 7 to 10, for example from 7 to 9.
  • each base included in the composition will be selected from the group consisting of:
  • Suitable alkali metal alkoxides will conventionally be selected from aliphatic, aromatic or araliphatic alkoxides of lithium, sodium or potassium.
  • Non-limiting examples thereof are lithium, sodium or potassium methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, sec-butoxide, tert-butoxide, n-pentoxide, isopentoxide, hexoxide, amyl alkoxide, 3,7-dimethyl-3-octoxide, phenoxide, 2,4-di-tert-butylphenoxide, 2,6-di-tert-butylphenoxide, 3,5-di-tert-butylphenoxide and 2,4-di-tert-butyl-4-methylphenoxide.
  • aliphatic (C 1 -C 4 )alkoxides in particular methoxides, ethoxides, n-propoxides, isopropoxides, n-butoxides, sec-butoxides and tert-butoxides of sodium, potassium or lithium.
  • the composition may optionally comprise ammonia (NH 3 ) as a base, either independently or in combination with other of the listed bases.
  • NH 3 ammonia
  • the constituent weight of ammonia included in the composition is to be calculated on the basis of NH 3 .
  • the ammonia will be present in the aqueous compositions of the present invention as an ammonia solution NH 3 (aq) which encompasses weakly basic solutions of ammonia in water which may referred to in the art as ammonium hydroxide, ammonia water, ammonia liquor, aqua ammonia, aqueous ammonia, or simply ammonia.
  • ammonium hydroxide suggests a base with the composition [NH 4 + ][OH - ], it is virtually impossible to isolate samples of NH 4 OH, insomuch as these ions do not comprise a significant fraction of the total amount of ammonia in an ammonia solution, except in the case of extremely dilute ammonia solutions.
  • suitable basic amines - which may be included alone or in combination in the aqueous lubricating compositions - include: methyl amine; dimethylamine; trimethylamine; ethyl amine; diethylamine; triethylamine; cyclohexylamine; dimethylcyclohexylamine; ethanolamine; 2-(diethylamino)ethanol; N,N-dimethylethanolamine, 2,2'-dihydroxydiethylamine (diolamine); N-methylpiperidine; pyridine; 2,6-dimethylpyridine; 2,4,6-trimethylpyridine; quinoline; piperazine; pyrrolidone; 1-(2-hydroxylethyl)pyrrolidine; morpholine; N-methylmorpholine; 4-(2-hydroxyethyl)morpholine; bis(2-(N,N'-dimethylamino)ethyl)ether; bis-(t-butylaminoethyl)ether
  • composition comprises at least one base selected from the group consisting of: bis(2-(N,N'-dimethylamino)ethyl)ether; bis-(t-butylaminoethyl)ether, 1,2-bis-(t-butylaminoethoxy)ethane; 1,2-bis-(t-butylaminoethoxyethoxy)ethane; bis[2-(isopropylamino)propyl]ether; 1,2-[2-isopropylamino)-propoxy]ethane.
  • a particular preference for the use of bis(2-(N,N'-dimethylamino)ethyl)ether may be acknowledged.
  • the aqueous lubricating composition comprises from 0.1 to 5 wt.%, based on the weight of the composition, of e) at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants.
  • the composition may comprise from 0.1 to 2.5 wt.%, for example from 0.1 to 2 wt.%, of e) said at least one surfactant, based on the weight of the composition.
  • Suitable nonionic surfactants having utility in the present disclosure include: the condensation products of C 5 to C 25 aliphatic alcohols with from 1 to 25 moles of ethylene oxide per mole of said alcohol, wherein the alkylene chain of the aliphatic alcohol can either be straight or branched, primary or secondary; alkylpolyglycosides; alkyl glycerol ethers; sorbitan esters; and, fatty acid amide surfactants.
  • Neodol TM 91-5, Neodol TM 91-8 and Neodol TM 23-5 available from Shell International Research Maatschappij BV;, Lutensol A7N, Lutensol XP 50, Lutensol XL150, Lutensol TM XL70, Lutensol TM T07 and Lutensol TM ON50, available from BASF; Novel 1412-7, Isalchem TM , Lial TM and Marlipal TM O13/70 available from Sasol.
  • Suitable amphoteric and zwitterionic surfactants include: amine oxides of the general formula (R m R n R o N-O), wherein R m is C 1 -C 18 alkyl and R n and R° are independently selected from C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl and C 1 -C 6 alkoxyalkyl; and, betaines such as alkyl betaines, carbobetaines, alkyl amidobetaines, amidazoliniumbetaines, sulfobetaines and phosphobetaines.
  • betaines includes: Examples of suitable betaines include but are not limited to: behenamidopropyl betaines; canolamidopropyl betaines; capramidopropyl betaines; cocamidoethyl betaine; cocamidopropyl betaine; cocamidopropyl hydroxysultaine; oleamidopropyl betaine; isostearamidopropyl betaine; lauramidopropyl betaine; lauryl betaine; lauryl hydroxysultaine; lauryl sultaine; myristamidopropyl betaine; myristyl betaine; oleamidopropyl betaine; oleamidopropyl hydroxysultaine; oleyl betaine; oleylamidopropyl betaine; palmamidopropyl betaine; palmitamidopropyl betaine; ricinoleamidopropyl betaine; stearamidopropyl
  • Suitable anionic surfactants are sulphates, sulphosuccinates, sulphoacetates and / or sulphonates.
  • Exemplary sulphonate surfactants include: C 6 -C 18 alkyl sulphonates (paraffin sulphonates); C 6 -C 18 alkyl benzene sulphonates; C 6 -C 18 alkyl glyceryl sulphonates; methyl ester sulphonate (MES); and, alpha-olefin sulphonate (AOS).
  • anionic surfactants a preference may however be mentioned, either for use alone or in combination, for the water-soluble salts of C 6 -C 18 alkyl sulfates, C 6 -C 18 hydroxyalkyl sulphates and alkyl ethoxy sulfates a degree of ethyoxylation of from 1 to 5.
  • Suitable cationic surfactants are commonly quaternary ammonium surfactants and, in particular, quaternary ammonium surfactants selected from the group consisting of mono N-C 6 -C 18 alkyl or N-C 6 -C 18 alkenyl ammonium surfactants, wherein the remaining N positions are substituted by C 1 -C 3 alkyl or C 1 -C 3 hydroxyalkyl groups. Mention might also be made of C 6 -C 18 alkyl or C 6 -C 18 alkenyl esters of quaternary ammonium alcohol.
  • the aqueous lubricating compositions of the present disclosure may further comprise adjuvants and additives that can impart improved properties to these compositions.
  • the adjuvants and additives may, for instance, impart one or more of: enhanced boundary lubrication; reduced drying time; reduced corrosiveness; improved stability; and, longer shelf-life of the compositions.
  • Such adjuvants and additives can be used in such combination and proportions as desired, provided they do not adversely affect the nature and essential properties of the composition. While exceptions may exist in some cases, these adjuvants and additives should not in toto comprise more than 5 wt.% of the total weight of the aqueous lubricating composition.
  • oils include: oils; anti-wear additives; corrosion inhibitors; antioxidants; free fatty acids, which may act to create a reacted layer for boundary lubrication; optical brighteners, in particular where confirmation of deposition of the solid lubricants under illumination may be required; and, tackifiers.
  • oils may serve to form an oily surface on the substrate surface after drying of the aqueous compositions and can compensate for reduced lubricating performance in those regions of the workpieces that are characterized by non-uniform film deposition of the solid lubricant. Further, in those embodiments of the composition where the aqueous lubricating composition is applied at an elevated temperature, this is typically effected by heating the lubricant with steam tubes: the addition of oil to the aqueous lubricating composition can inhibit adhesion of the solid particulate lubricant to the heating tubes.
  • the oils may be used alone or in combination and may be selected from mineral oils, animal oils, animal fats, plant oils and synthetic oils. However, the or each added oil should typically be characterized by at least one of and preferably all of: a flash point in the range from 150 to 300°C; a melting point of from -20 to 20°C; and, a viscosity of from 5 to 100 centistokes stokes as determined at 40°C.
  • a melting point in excess of 20°C can lead to a diminished emulsifiability and re-emulsifiability by the oil in the waterborne lubricant and thus to a tendency for treatment bath stability to be reduced.
  • An oily component having a melting point below -20°C will typically have a reduced flash point.
  • a viscosity below 5 centistokes will typically be associated with a low flash point, which leads to the post-working generation of large amounts of gas and hence an ignition risk.
  • slip between solid lubricant particles is diminished and the lubrication performance tends to decline.
  • a viscosity in excess of 100 centistokes usually leads to a diminished emulsifiability and re-emulsifiability of the oily component in the waterborne lubricant.
  • Tackifiers are utilized to improve transfer rates of the lubricant and ensure the applied and dried lubricating composition remains in place to provide the needed lubrication.
  • the or each tackifying resin included in the composition is preferably characterized by: a softening point of from 70 to 150°C.; and, a viscosity at 150°C of less than 2000 Pa ⁇ s.
  • Exemplary tackifying resins which may be used alone or in combination in the present invention include: aliphatic and cycloaliphatic petroleum hydrocarbon resins; aromatic petroleum hydrocarbon resins and the hydrogenated derivatives thereof; aliphatic / aromatic petroleum derived hydrocarbon resins and the hydrogenated derivatives; polycyclopentadiene resins, hydrogenated polycyclopentadiene resins and aromatic modified hydrogenated polycyclopentediene resins; terpenes, aromatic terpenes and hydrogenated terpenes; polyterpenes, aromatic modified polyterpenes and terpene phenolics; copolymers of ⁇ -methylstyrene and a further vinyl aromatic monomer; and, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters and hydrogenated rosin esters.
  • the aqueous lubricating compositions are formulated by simple mixing of the various components as well as any adjunct ingredients. Whilst the order of mixing of the components is not intended to be limited, it may be prudent to first form an aqueous dispersion of the rheological control agent(s) (c), to which dispersion is then added the inorganic salt (a), the solid lubricants (b) and the further components under agitation.
  • the solid lubricants (b) should desirably be added after both the rheological control agent (c) and the inorganic salt to ensure a stable, homogeneous dispersion is formed.
  • particulate components and polymeric components may be pre-prepared as aqueous dispersions - at a solids contents of from 45 to 60 wt.%, for example - to facilitate their admixture with other components of the compositions.
  • the inorganic salts a) may also be added as a pre-prepared solution or may be added in solid form but under mixing conditions which ensure that the salts are in dissolved form in the final aqueous lubricating composition.
  • the aqueous lubricating compositions may be prepared well in advance of their application.
  • a concentrated composition may first be obtained by mixing components with only a fraction of the water that would be present in the composition as applied: the concentrated composition may then be diluted with the remaining water shortly before its application.
  • the concentrated compositions may be prepared and stored as either single-package concentrates - that can be converted by dilution with water only - or as multi-part concentrates, two or more of which must be combined and diluted to form a complete working composition according to the invention. Any dilution can be effected simply by the addition of water, in particular deionized and / or demineralized water, under mixing.
  • the aqueous lubricating composition might equally be prepared within a rinse stream whereby one or more streams of the concentrate(s) is injected into a continuous stream of water.
  • the aqueous lubricating compositions may contain from 60 to 90 wt.%, preferably from 65 to 85 wt.% and more preferably from 65 to 80 wt.%, based on the weight of the composition, of water.
  • the aqueous lubricating composition may be defined by a viscosity of from 0.005 to 1 Pa ⁇ s (50 cps to 1000 cps), as measured using a Brookfield viscometer at 25°C.
  • this step can, if applicable, facilitate the subsequent adhesion of the compositions thereto.
  • Such treatments are known in the art and can be performed in a single or multi-stage manner constituted by, for instance, the use of one or more of: an etching treatment with an acid suitable for the substrate and optionally an oxidizing agent; sonication; plasma treatment, including chemical plasma treatment, corona treatment, atmospheric plasma treatment and flame plasma treatment; immersion in a waterborne alkaline degreasing bath; treatment with a waterborne cleaning emulsion; treatment with a cleaning solvent, such as acetone, carbon tetrachloride or trichloroethylene; and, water rinsing, preferably with deionized or demineralized water.
  • any of the degreasing agent remaining on the surface should desirably be removed
  • the aqueous lubricating composition is applied to the substrate.
  • the composition may be applied at ambient temperature or the temperature of the aqueous compositions may be elevated prior to application to, for instance, a temperature in the range from 30°C to 90°C, for instance from 30°C to 70°C.
  • an operating bath as hereinbefore described is prepared and the aqueous lubricating composition is applied to the substrate by, without limitation, immersion and dipping.
  • the contact time of the aqueous lubricating composition is not critical but should be sufficient to allow the temperature of the substate to equilibrate with the temperature of the composition in the operating bath. Exemplary contact times are from 1 minute to 15 minutes, for instance from 2 to 10 minutes.
  • Alternative techniques which may be used to apply the aqueous lubricating composition to either a singular surface or multiple surfaces of a substrate include but are not limited to: painting; brushing; flow coating; roll coating; wiping; air-atomized spraying; air-assisted spraying; airless spraying; high-volume low-pressure spraying; and, air-assisted airless spraying.
  • the article is dried using, for instance, ambient air drying, circulating warm air, forced air drying or infrared heating.
  • the surface temperature of the substrate is controlled during drying: the peak metal temperature (PMT) need not exceed 150°C and should, more particularly, be in the range from 100 to 125°C, for example 100 to 120°C.
  • the above-described treatment should yield a protective film over the metal substrate, said film preferably having a film weight of from 1 to 50 g/m 2 , preferably from 1 to 40 g/m 2 or from 5 to 40 g/m 2 .
  • the type of metal working to be performed, the degree of working and the substrate surface roughness will be determinative of the optimal thickness of the dried coating. Generally, however, when the dried film is too thin, contact can occur between the working tools and the substrate itself and seizure will then be prone to occur. When the dried film is too thick, a fraction of the film may not be drawn into the interface between the working tool and the substrate: this fraction would thus constitute a waste of the waterborne lubricant.
  • suitable base metal substrates may include but not be limited to: iron; titanium; nickel; zinc; copper; aluminium; tin; cobalt; and, alloys thereof.
  • Substrates comprising or consisting of steel may be mentioned in particular, of which examples include: galvanized and galvanneal steel meeting the requirements of ASTM Designation A653; GALVALUME ® , a 55% Al / 43.4% Zn / 1.6% Si alloy coated sheet steel available from Bethlehem Steel Corporation; and, GALFAN ® , a 5% Al/ 95% Zn alloy coated sheet steel available from Weirton Steel Corporation.
  • the initial form of the substrate to which the aqueous lubricating composition is applied also need not be limited, save to say that the form must be appropriate for tools to be utilized and the target shape or form to be attained after cold-working.
  • conventional stock forms in which the metal and alloy substrates may be provided include: sheets; plates; cuboids; spheres; annuli; solid cylinders; tubes; and, wires.
  • the present disclosure also provides for the use of the aqueous waterborne lubricant composition or the dried film obtained therefrom in the plastic cold working of metallic substrates.
  • the present disclosure further provides a process for the plastic cold working of a solid metallic substrate by mechanically forcing said solid metallic substrate through an aperture bounded by at least one solid surface of at least one metal working tool, said process comprising the steps of:
  • the above-described method may include the following further steps:
  • step iv) comprises the treatment of the residual film with an alkaline degreaser. It is particularly preferred that step iv) does not comprise the treatment of the residual film with an acidic pickling liquor.
  • step iii) In the event that the residual lubricating film attained after step iii) is not removed prior to annealing, carbon, sulphur, phosphorus and other components of the lubricant film may infiltrate into the metallic substrate, thereby impairing the corrosion resistance and mechanical strength of that substrate. Further, the residual lubricating film would not present a surface to which the aqueous lubricating composition would adhere in the second (and further) iterations of step i) above.
  • Example 1 represents a composition in accordance with the present invention: the remaining ingredients mentioned hereinbelow are obtainable from Sigma Aldrich.
  • An aqueous lubricating composition was prepared by mixing the ingredients given in Table 1 herein below.
  • a solution of the inorganic salts (a) in water was prepared to which was added the rheological control agents (c), base (d) and surfactants and, subsequently, the solid lubricants (b).
  • the solid lubricants (b) were added as pre-prepared dispersions in water.

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EP21204637.9A 2021-10-26 2021-10-26 Borfreies wasserbasiertes schmiermittel für die plastische verarbeitung Withdrawn EP4174155A1 (de)

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GB2003923A (en) 1977-09-07 1979-03-21 Foseco Int Metal working lubricants
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