US20150329797A2 - Water-soluble lubricating agent for plastic working, metal material for plastic working, and worked metal article - Google Patents

Water-soluble lubricating agent for plastic working, metal material for plastic working, and worked metal article Download PDF

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Publication number
US20150329797A2
US20150329797A2 US14/374,088 US201314374088A US2015329797A2 US 20150329797 A2 US20150329797 A2 US 20150329797A2 US 201314374088 A US201314374088 A US 201314374088A US 2015329797 A2 US2015329797 A2 US 2015329797A2
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Prior art keywords
component
film
test
lubricating
water
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US20150147581A1 (en
Inventor
Keita Shiihashi
Shigehiro Yamane
Yoshihiko Kita
Masafumi Kuroda
Mamoru Kita
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Kobe Steel Ltd
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Kobe Steel Ltd
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Assigned to KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, LTD.) reassignment KABUSHIKI KAISHA KOBE SEIKO SHO (KOBE STEEL, LTD.) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SHIIHASHI, KEITA, YAMANE, Shigehiro, KITA, Mamoru, KITA, Yoshihiko, KURODA, MASAFUMI
Publication of US20150147581A1 publication Critical patent/US20150147581A1/en
Publication of US20150329797A2 publication Critical patent/US20150329797A2/en
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
    • 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
    • C10M2201/087—Boron 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/14—Synthetic waxes, e.g. polythene waxes
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • 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
    • C10N2010/04—Groups 2 or 12
    • 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
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • 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
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31714—Next to natural gum, natural oil, rosin, lac or wax

Definitions

  • the present invention relates to a water-soluble lubricating agent for plastic working, a metal material for plastic working, and a worked metal article. More particularly, the present invention relates to a water-soluble lubricating agent for plastic working being capable of forming a lubricating film having excellent film characteristics such as lubricity, seizure resistance, corrosion resistance, adhesion, and the like without including phosphorus in the film, and a metal material for plastic working and a worked metal article including such a lubricating film.
  • the metal material of the present invention is suitably used to manufacture worked metal articles such as, for example, machine parts such as bolts, nuts, springs and the like, and wire drawing products such as steel cords, bead wires, PC (prestressed concrete) steel wires and the like, which are obtained by plastic working such as drawing, pressing, forging, heading and the like.
  • worked metal articles such as, for example, machine parts such as bolts, nuts, springs and the like
  • wire drawing products such as steel cords, bead wires, PC (prestressed concrete) steel wires and the like, which are obtained by plastic working such as drawing, pressing, forging, heading and the like.
  • a metal material for plastic working is subjected to various plastic workings such as drawing, wire drawing, heading and forging according to its applications.
  • plastic working a high pressure is applied between a working tool (a die, plug, punch or the like) and a material to be worked (a meal material), and seizure is likely to occur with accompanying sliding between each other. Therefore, in order to decrease the friction on the surface of the metal material and prevent seizure, a lubricating film is usually formed on the surface of the metal material.
  • a composite film composed of a phosphate film and a soap layer
  • This chemical conversion treatment film is obtained in the following manner, for example. First, a phosphate film is formed on a metal material by performing a phosphate treatment. Then, by performing a reactive soap lubricating treatment, the phosphate film is reacted with sodium stearate that is a main component of the soap to form a soap layer including zinc stearate (metal soap) having good adhesion and sodium stearate (hot water bath soap), so that the chemical conversion treatment film can be obtained.
  • This chemical conversion treatment film has excellent lubricity and excellent seizure resistance, and also good corrosion resistance. Therefore, the metal material provided with such a chemical conversion treatment film is suitably used for severe working such as cold forging working.
  • Patent Document 1 discloses a lubricant for plastic working of metallic material containing a water soluble inorganic salt (A) and a wax (B), and further a metallic salt of fatty acid (C) at the prescribed ratio. It is described that, according to this method, excellent lubricative properties can be obtained by adjusting the ratio of (B)/(A) to the range of 0.3 to 1.5 and the ratio of (C)/(A) to the range of 0.01 to 0.4.
  • Patent Document 2 discloses a lubricant for plastic working of metallic material containing a water soluble inorganic salt (A) and a lubricating agent (B) (molybdenum disulphide and/or graphite), and further a wax (C) at the prescribed ratio. It is described that, according to this method, excellent lubricative properties can be obtained by adjusting the ratio of (B)/(A) to the range of 1.0 to 5.0 and the ratio of (C)/(A) to be in the range of 0.1 to 1.0.
  • B water soluble inorganic salt
  • B molybdenum disulphide and/or graphite
  • Patent Document 1 Japanese Patent No. 3984159
  • Patent Document 2 Japanese Patent No. 3984158
  • non-phosphorus lubricating films formed by the above-mentioned methods have insufficient adhesion between the lubricating film and the metal material, the lubricating film was peeled off during strong working such as cold forging and cold high strength wire drawing, and the working became difficult to be carried out. It was also founded that problems such as scattering of dust formed from the peeling lubricating film or the like have occurred. Therefore, excellent lubricity, seizure resistance and corrosion resistance, and higher adhesion have been demanded for non-phosphorus lubricating films.
  • the present invention was made in view of the above problems and an object of the present invention is to provide a water-soluble lubricating agent for plastic working being capable of forming a lubricating film having lubricity and seizure resistance equal to or greater than a phosphorus-containing chemical conversion treatment film, having excellent corrosion resistance, and also having good film adhesion, without containing phosphorus in the film, and a metal material for plastic working and a worked metal article provided with such a lubricating film.
  • a water-soluble lubricating agent for plastic working according to the present invention which can solve the problems as described above, includes an inorganic solid lubricant as component A, a wax as component B, and a water-soluble inorganic metal salt as component C, wherein mass ratio (component A/component B) of solid content for component A to solid content for component B is 0.1 to 5, and mass percentage (component C/(component A+compound B+component C)) of solid content for component C to total solid content for components A, B, and C is 1% to 30%.
  • the inorganic solid lubricant is preferably at least one selected from the group consisting of calcium compounds, magnesium compounds, barium compounds, zinc compounds, boron compounds (in which, however, borates are not included), and silicate compounds.
  • the water-soluble inorganic metal salt is preferably at least one selected from the group consisting of borates, molybdates, and tungstates.
  • mass ratio (component B/component C) of solid content for the component B to solid content for the component C is higher than 1.5.
  • a metal material for plastic working according to the present invention which can solve the problems as described above, includes a lubricating film on the surface thereof, wherein the lubricating film includes an inorganic solid lubricant as component A, an organic wax as component B, and a water-soluble inorganic metal salt as component C, mass ratio (component A/component B) of solid content for component A to solid content for component B is 0.1 to 5, and mass percentage (component C/(component A+component B+component C)) of solid content for component C to total solid content for components A, B, and C is 1% to 30%.
  • the lubricating film includes an inorganic solid lubricant as component A, an organic wax as component B, and a water-soluble inorganic metal salt as component C
  • mass ratio (component A/component B) of solid content for component A to solid content for component B is 0.1 to 5
  • the present invention includes a worked metal article obtained by plastic working of a metal material for plastic working as described above.
  • the lubricating agent of the present invention is suitable for strong working such as cold forging and cold high strength wire drawing and the like.
  • the metal material since a metal material on which the above lubricating film was formed has excellent adhesion, the metal material not only can fully cope with strong working but also can be processed without the occurrence of seizure under even severer working conditions (for example, the working without the addition of lubricating agents such as dried powders as in Example described later). Furthermore, peeling of the lubricating film accompanying working or transportation is suppressed and the occurrence of powder dust caused by the peeled-off lubricating film can be suppressed owing to low scattering property of the peeled-off film.
  • FIG. 1 is a schematic view showing an outline of a Bowden friction test used in the present Example
  • FIG. 2 is a schematic view showing an outline of a ball passing test used in the present Example
  • FIG. 3 is a schematic view showing an outline of a film adhesion test used in the present Example.
  • FIG. 4 is a schematic view showing an outline of a headability test used in the present Example.
  • the lubricating agent of the present invention is different in that an inorganic solid lubricant such as calcium compounds, magnesium compounds or the like that is not described in Patent Document 1 is used as a component of the lubricating agent in the present invention, in that a metallic salt of fatty acid is not used in the present invention while a metallic salt of fatty acid is used in Patent Document 1, and in that the preferable ratio of a wax and a water soluble inorganic metal salt used in the present invention exceeds the upper limit (1.5) of Patent Document 1.
  • an inorganic solid lubricant such as calcium compounds, magnesium compounds or the like that is not described in Patent Document 1
  • a metallic salt of fatty acid is not used in the present invention while a metallic salt of fatty acid is used in Patent Document 1
  • the preferable ratio of a wax and a water soluble inorganic metal salt used in the present invention exceeds the upper limit (1.5) of Patent Document 1.
  • the present invention is significantly different in that the excellent properties (corrosion resistance, adhesion, seizure resistance, and working under particularly severe working conditions), which the above Patent Document 1 could not achieve, can be exhibited.
  • the lubricative properties were evaluated only using a rear punching test and a spike test, the seizure resistance was not evaluated, and any properties during strong working or working under severe working conditions were not evaluated.
  • Component A Inorganic Solid Lubricant
  • the inorganic solid lubricant (component A) is a useful component that reduces the friction coefficient of a lubricating film, increases in lubricity of the lubricating film, and prevents the occurrence of seizure during plastic working.
  • the lubricating film containing the component A with the component B has the further improved adhesion (particularly, film strength), so that the excellent effects on seizure resistance, adhesion and the like during strong working or working under severe working conditions can be exerted.
  • the inorganic solid lubricant is solid and yet has lubricity. Accordingly, even if the temperature of the contact portion (metal-to-metal contact) between a working tool (tools, dies or the like) and a metal material (materials to be worked) rises to about 150° C. to 400° C., the inorganic solid lubricant does not melt and the direct contact between the working tool and the metal material is prevented, whereby the occurrence of seizure during working can be prevented.
  • the inorganic solid lubricant used in the present invention is not particularly restricted insofar as it is an inorganic compound that is usually used as a water-soluble lubricating agent for plastic working and contains no phosphorus.
  • the inorganic solid lubricant stably exists in the lubricating film and has characteristics that manifest lubricity even under high load during working.
  • Examples of the inorganic solid lubricant include calcium compounds such as calcium hydroxide, calcium carbonate and calcium oxide (preferably, calcium salt such as calcium carbonate), magnesium compounds such as magnesium hydroxide and magnesium carbonate (preferably, magnesium salt such as magnesium carbonate), barium compounds such as barium hydroxide and barium carbonate (preferably, barium salt such as barium carbonate), boron compounds such as boron nitride (however, borate salt is excluded from the compound A), zinc compounds such as zinc oxide and zinc phosphate (preferably, zinc salt such as zinc oxide), and silicate compounds such as silicate mineral (for example, mica) (preferably silicate, however, alkali metal silicate is excluded).
  • calcium compounds and zinc compounds are preferable, and calcium compounds are particularly preferable.
  • any of the above-mentioned components A may be used either alone or in combination of two or more components.
  • black molybdenum disulfide and graphite are known as an inorganic solid lubricant, it is preferable not to use these compounds in view of working environment because the adherence (coloring) of these compounds to clothes or the periphery of an apparatus leads to the deterioration in working environment.
  • the content of the component A in all essential components is preferably 20 mass % or more, more preferably 50 mass % or more.
  • the content of the component A is preferably 85 mass % or less, more preferably 80 mass % or less.
  • the wax (component B) is a useful component that reduces the friction coefficient of a lubricating film, increases in lubricity of the lubricating film, and improves seizure resistance, and also that increases in adhesion between the lubricating film and the metal material, and enhances the followability of the lubricating film during plastic working, whereby peeling of the lubricating film is prevented.
  • the wax in view of increasing in lubricity during working, it is recommended that the wax has a property of being melted by heat by plastic working.
  • the wax is melted by heat by plastic working whereby the friction between the working tool and the metal material can be reduced. Therefore, the melting point of the wax is preferably 50° C. or higher, more preferably 70° C. or higher and preferably 160° C. or lower, more preferably 140° C. or lower.
  • the wax in view of increasing in coating properties of the wax, the wax preferably has dispersibility in water (for example, dispersion or emulsion).
  • wax used in the present invention various natural waxes and synthetic waxes can be used insofar as the wax is an organic wax that is solid at ordinary temperature and has a property of being liquefied at the prescribed temperature by heating.
  • natural waxes include plant-based waxes such as carnauba wax, petroleum-based waxes such as paraffin wax and microcrystalline wax, animal waxes such as beeswax, and mineral waxes such as montan wax.
  • synthetic waxes include polyethylene waxes and polypropylene waxes. In the present invention, these waxes (component B) may be used either alone or in combination of two or more waxes.
  • the content of the component B in all essential components is preferably 10 mass % or more, more preferably 20 mass % or more, and preferably 50 mass % or less, more preferably 40 mass % or less.
  • the content of 10 mass % or more is preferable in order to exert the above effects of the component B.
  • the content of the component B is preferably 50 mass % or less.
  • the water-soluble inorganic metal salt (component C) is a film making agent (film forming agent) and a useful component that improves the adhesion to a metal material and seizure resistance.
  • a film is formed from the component C so as to coat the surface of the metal material and therefore it is a useful component for improving corrosion resistance (rust-proof property).
  • the water-soluble inorganic metal salt of the present invention is not particularly restricted insofar as the water-soluble inorganic metal salt contains no phosphorus and is generally used as an additive of a water-soluble lubricating agent for plastic working.
  • the water-soluble inorganic metal salt used in the present invention borate, molybdate and tungstate can be given.
  • the preferable water-soluble inorganic salt is borate. They may be used either alone or in combination of two or more.
  • boric acid forming the above borate examples include orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, and octaboric acid.
  • borate examples include metal salts such as alkali metal salt (Li salt, Na salt, K salt or the like) and alkaline-earth metal salt (Mg salt, Ca salt or the like).
  • the preferable borates are metaborate and tetraborate, and as specific examples, sodium metaborate, potassium metaborate, sodium tetraborate (Na 2 B 4 O 5 (OH) 4 .8H 2 O called as borax), potassium tetraborate, ammonium tetraborate, and the like can be given.
  • molybdate is also useful as a rust-proofing agent.
  • molybdic acid forming molybdate include orthomolybdic acid, metamolybdic acid and paramolybdic acid.
  • molybdate include alkali metal salt (Li salt, Na salt, K salt or the like) and alkaline-earth metal salt (Mg salt, Ca salt or the like).
  • the preferable molybdate is metamolybdate, and specifically, sodium metamolybdate is preferred.
  • tungstic acid forming the above tungstate examples include orthotungstic acid, metatungstic acid and paratungstic acid.
  • examples of tungstate include alkali metal salt (Li salt, Na salt, K salt or the like) and alkaline-earth metal salt (Mg salt, Ca salt or the like).
  • the preferable tungstate is metatungstate and specifically, sodium metatungstate is preferred.
  • the component C of the present invention does not include alkali metal silicate as described in Patent Document 1.
  • the water-soluble lubricating agent for plastic working of the present invention is characterized by including the combination of the above components A, B and C, and the effects possessed by each component as described above can be exhibited effectively through the inclusion of these components at the specific ratio.
  • the ratios of each of component are described below.
  • the compounding ratio of the component A (inorganic solid lubricant) and the component B (wax) (component A/component B: mass ratio of solid content, the same shall apply hereinafter) is below 0.1, the above effects of the component A are not exhibited effectively and the seizure resistance of the lubricating film decreases. Moreover, when the content of the component A is insufficient, the adhesion of the wax (component B) during working may decrease and the film may peel off easily. On the other hand, when the compounding ratio (component A/component B) excesses 5, the adhesion between the metal material and the lubricating film decreases and the followability of the lubricating film during plastic working decrease. In addition, if the adhesion or followability decreases, a sufficient dust depression effect cannot be exhibited. Therefore, the compounding ratio of the component A and the component B is 0.1 or higher, preferably 1 or higher, and 5 or lower, preferably 3 or lower.
  • the compounding ratio of the component C in the total content of the components A, B and C (component C/(component A+component B+component C): mass percentage of solid content, the same shall apply hereinafter) is below 1%, the seizure resistance or adhesion of the lubricating film decreases.
  • the compounding ratio (component C/(components A+B+C)) excesses 30% since the lubricity decreases and the friction coefficient increases (decreasing of friction coefficient reduction effect), the seizure resistance decreases or the resistance during working increases and thus the lubricating film may peel off.
  • the compounding ratio of the component C in the total content of the components A to C is 1% or higher, preferably 5% or higher and 30% or lower, preferably 20% or lower.
  • the compounding ratio of the component B (wax) and the component C (water-soluble inorganic metal salt) is preferably higher than 1.5. If the ratio of component B to component C is 1.5 or lower, the balance between the adhesion and the lubricity becomes inferior, and the adhesion and the lubricity decrease and the seizure resistance of the lubricating film may decrease. On the other hand, the compounding ratio (component B/component C) excesses 9, the adhesion between the metal material and the lubricating film might decrease. Therefore, the compounding ratio of the components B and C is preferably higher than 1.5, more preferably 1.8 or higher and preferably 9 or lower, more preferably 8 or lower.
  • the water-soluble lubricating agent for plastic working of the present invention includes the above components A, B and C at the specific ratio as active constituents, other components that are usually included in a lubricating agent can be added within the scope not impairing the actions of the present invention and these are also included within the scope of the present invention.
  • a surface active agent is a component that is added during forming process of the lubricating film, if need arises.
  • a surface active agent is a useful component for improving dispersibility of the above component A (inorganic solid lubricant) and the above component B (wax).
  • the above lubricating film is formed by dipping a metal material in an aqueous solution (treatment solution) containing the components as described above (a dipping method). At this time, the addition of the surface active agent allows the above component A and the above component B to be dispersed homogeneously in the treatment solution and the above effects can be exhibited more homogeneously.
  • the surface active agent adsorbed on the surface of the metal material has a rust-proofing action, the corrosion resistance is also improved. Furthermore, the surface active agent ensures the homogeneous wettability on the surface of the metal material and also has the improvement action of the coating property of the lubricating film.
  • a non-ionic surface active agent As examples of the surface active agent used in the present invention, a non-ionic surface active agent, anionic surface active agent, ampholytic surface active agent, cationic surface active agent and the like can be given.
  • non-ionic surface active agent examples include polyoxyethylene alkyl ether, polyoxyalkylene (ethylene and/or propylene) alkylphenyl ether, polyoxyethylene alkyl ester composed of polyethylene glycol (or ethylene oxide) and higher fatty acid (having 12 to 18 carbon atoms, for example), polyoxyethylene sorbitan alkyl ester composed of sorbitan, polyethylene glycol and higher fatty acid (having 12 to 18 carbon atoms, for example) and the like.
  • examples of the non-ionic surface active agent include fatty acid salt, sulfate ester salt, sulfonate, dithiophosphoric acid ester salt, and the like.
  • ampholytic surface active agent examples include carboxylates either in amino acid configuration or in betaine configuration, sulfate ester salt, sulfonate, and the like.
  • examples of the cationic surface active agent include amine salt of fatty acid, quaternary ammonium salt, and the like. These surface active agents may be used either alone or in combination of two or more of them.
  • the content of the surface active agent contained in the lubricating agent of the present invention varies depending on the components constituting the lubricating agent or the kind of surface active agent used, and it is generally preferred that the content of the surface active agent be within the range of 0.01% to 5% relative to the basic components (the total content of the components A, B and C) constituting the lubricating agent. If the content of the surface active agent is lower than 0.01%, desired effects such as dispersibility or wettability cannot be obtained sufficiently. On the other hand, if the content of the surface active agent is higher than 5%, these actions are saturated, which just leads to the increased cost.
  • the content of the surface active agent is preferably 0.05% or higher, more preferably 0.3% or higher and preferably 3% or lower.
  • a rust-proofing agent is a component that is added during forming process of the lubricating film, if need arises.
  • a rust-proofing agent is a useful component for improving corrosion resistance.
  • the kinds of the rust-proofing agent are not particularly restricted and the rust-proofing agent usually contained in a lubricating film may be used either alone or in combination of two or more.
  • Examples of the rust-proofing agent include alkenyl succinic acid amine salt, vanadate, polyacrylic acid, benzotriazole, and the like.
  • the content of the rust-proofing agent contained in the lubricating agent of the present invention varies depending on the components constituting the lubricating agent or the kind of the rust-proofing agent used, and it is generally preferred that the content of the rust-proofing agent be within the range of 0.1% to 5% relative to the basic components (the total content of the components A, B and C) constituting the lubricating agent. More preferably, it is 1% or higher and 4% or lower.
  • the lubricating film can be formed using the lubricating agent containing the components A to C as described above and other components that are added if need arises.
  • the mixture solution sometimes referred to as a preparation solution or treatment solution
  • an aqueous solvent is made to contact with the metal material and then dried if need arises, thereby forming a lubricating film (dry method).
  • the contact method is not particularly restricted and methods usually used for forming a lubricating film using a lubricating agent can be appropriately employed.
  • a method in which the metal material is dipped in the above mixture solution and dried it, a method in which the above mixture solution is applied to the metal material (with a spray, shower or the like), or the like can be given.
  • the dry method used in the present invention is explained here.
  • Methods for forming a lubricating film using an aqueous lubricating agent can be roughly classified into a wet method and a dry method.
  • the wet method is applied in the case where a lubricating agent containing a mineral oil, an animal or plant oil, or the like as a base oil is used, and in this method the lubricating agent is poured directly on the metal material (material to be processed) to form a liquid film.
  • This method is widely used to mainly obtain materials having a relatively low degree of processing.
  • a metal material is treated by dipping it in a lubricating agent or by doing anything, and subsequently, if need arises, water is evaporated in a drying step to form a solid film.
  • the method for forming a lubricating film in the present invention problems such as unevenness of adhesion which are caused by the dry method can be avoided. That is, in the dry method using an aqueous lubricating agent, a large quantity of metal materials are subjected to dipping treatment at the same time and then the aqueous solvent is dried, thereby forming films. In this case, unevenness of adhesion due to partial contact with the metal materials are often generated and this leads to the problems such as seizure is likely to occur when drawing. According to the present invention, since the lubricating agent containing the above components A to C in combination at the specific ratio is used, the lubricating agent homogeneously dissolves or disperses in the treatment solution.
  • the lubricating agent when the lubricating agent is made to contact with the metal material to form a lubricating film, the strong lubricating film with no film defect can be obtained. Moreover, the adhesion between the lubricating film and the metal material or the followability of the lubricating film to the metal material is significantly improved and thus the problems such as deterioration in seizure or the like caused by unevenness of adhesion as describe above are resolved. Furthermore, since water is evaporated by drying, the component composition of the lubricating agent in the film after drying can be made nearly equal to the component composition in the lubricating agent.
  • a mixture solution is prepared by mixing the components A to C at the specific ratio described above, and in addition, if need arise, other components with an aqueous solvent.
  • aqueous solvent used in the present invention water and a mixture of water with a water-soluble solvent can be given.
  • the water-soluble solvent include alcohol such as methanol, ethanol and ethylene glycol; ketone such as acetone; ether such as tetrahydrofuran and ethylene glycol dimethyl ether; and nitrile such as acetonitrile.
  • the preferable aqueous solvent is water. In this case, water is ion-exchange water, tap water, groundwater, industrial water, or the like and is particularly not restricted.
  • the concentration of the lubricating agent when being mixed with the aqueous solvent is, generally, preferably 5% or higher, more preferably 7% or higher, and further preferably 10% or higher. If the concentration of the lubricating agent is too low, the film may be inhomogeneously formed.
  • the upper limit of the concentration of the lubricating agent is not particularly restricted insofar as the lubricating agent can dissolve in the aqueous solvent, but it is, generally, preferably 70% or lower, more preferably 60% or lower. However, if the concentration of the lubricating agent is too high, the lubricating agent does not homogeneously dissolve or disperse in the aqueous solvent and thus unevenness of adhesion may be generated. In the light of the above, the concentration of the lubricating agent is, generally, preferably 50% or lower, more preferably 45% or lower.
  • a method for preparing a water-soluble lubricating agent for plastic working of the present invention is not particularly restricted.
  • the water-soluble lubricating agent can be prepared by adding the above component B (wax), an additive agent such as a surface active agent if need arises, and an aqueous solvent to an aqueous solution (aqueous solvent) containing the above component C (water-soluble inorganic metal salt) and stirring them, and further adding the above component A (inorganic solid lubricant) and, if need arises, an additive agent such as a surface active agent or an aqueous solvent thereto and stirring them.
  • a metal material is dipped in the above mixture solution.
  • the specific dipping condition is not particularly restricted, but it is generally preferred that the dipping be conducted at a temperature of about 30° C. to 80° C. (more preferably 40° C. to 70° C.) for 5 seconds or longer (more preferably 10 seconds or longer). If the dipping temperature falls below the above range, it is inconvenient to need to strictly control the dipping temperature under high-temperature environment in the summer season or the like. On the other hand, if the dipping temperature exceeds the above range, the amount of evaporation of the mixture solution may increase and thus the concentration of the lubricating agent is likely to fluctuate. In addition, if the dipping time falls below the above range, the adhesion decreases. Note that the upper limit of the dipping time is not particularly restricted, but adhesion improving action cannot be obtained by dipping for a long time and thus the dipping time is preferably for 15 minutes or shorter.
  • drying may be conducted if need arises, so that the desired lubricating film can be obtained.
  • the drying method is not particularly restricted, and natural drying, drying by hot or cold air, or drying in a greenhouse (a calm state) may be conducted after dipping.
  • a cleaning process may be conducted for the purpose of cleaning treatment of the surface of the metal material.
  • the cleaning treatment descaling, degreasing or the like can be given.
  • common methods such as a mechanical descaling method (a blast method such as a shot blasting, bending, or the like) or a chemical descaling method (acid-pickling or the like) can be used.
  • the mechanical descaling method is a preferred method for descaling. By the mechanical descaling method, descaling can be conducted by in-line process not by batch process and this method is suitable for the present invention in which a film is physically formed in a short time.
  • the lubricating film formed by using the water-soluble lubricating agent for plastic working according to the present invention contains the components A to C in the mass ratio of solid content for components A/component B of 0.1 to 5 (the preferable mass ratio of solid content is the same as the mass ratio of solid content of the water-soluble lubricating agent for plastic working according to the present invention as described above) and in the mass percentage of solid content for component C/(components A+B+C) of 1% to 30% (the preferable mass percentage of solid content is the same as the mass percentage of solid content of the water-soluble lubricating agent for plastic working according to the present invention as described above).
  • the preferable compounding ratios of the components B and C and the preferable contents of each of the component A to C are the same as those of the above-described lubricating film.
  • the lubricating film contains these components at concentrations corresponding to the concentrations of other components contained in the lubricating agent.
  • the ratios of the components A to C (and further added other components) in the lubricating film does not completely correspond to the ratios of the composition of the water-soluble lubricating agent for plastic working used for forming the lubricating film.
  • the ratios within the range of about ⁇ 10% may be acceptable. Therefore, it is desirable to adjust appropriately the ratios of the components in the water-soluble lubricating agent for plastic working as necessary in such a way that the ratios of the components in the lubricating film falls within the ranges as prescribed before.
  • the adhesion amount of the above lubricating film be generally within the range of from 0.5 g/m 2 to 30 g/m 2 . If the adhesion amount is less than 0.5 g/m 2 , it is difficult to conduct a large number of continuous wire drawings because of shortage of film thickness. If the adhesion amount is more than 30 g/m 2 , the above actions exerted by the lubricating film are saturated, and this only causes an increase in cost and is economically ineffective. More preferably, the adhesion amount of the lubricating film is generally within the range of 2 g/m 2 or more and 20 g/m 2 or less.
  • a general-purpose base layer (silica-containing layer) may be interposed between the lubricating film and the metal material.
  • films containing silica or the like may be coated on the above lubricating film in order to give rust-proof property and the like. These other films may be formed in a single layer or in two or more stacked layers.
  • a metal material of the present invention has the above lubricating film on the surface and is used for plastic working (the details will be described later).
  • the composition of the metal material used in the present invention is not particularly restricted insofar as the metal material is used for plastic working.
  • various metal materials such as steel (iron steel, stainless steel, chrome steel, molybdenum steel, titanium steel, or the like) and non-ferrous metal materials (aluminum material, titanium material or copper material or the like) are used.
  • the preferred metal material is steel.
  • the configuration of the above metal material is not particularly restricted insofar as the metal material is used for plastic working.
  • various metal materials such as wire rods, rods, cutting materials of the wire rods or rods (blank materials), steel plates or the like can be used.
  • the preferable metal materials are wire rods, rods, blank materials or the like.
  • the wire rods and rods the wire rods and rods for producing bolts, nuts, springs, PC (prestressed concrete) steels, steel cords, bead wires, or the like can be given.
  • the blank material blank materials for producing forward or backward extrusion parts can be given.
  • the present invention includes a worked metal article obtained by plastic working of a metal material provided with the above lubricating film.
  • the worked metal article include bolts, nuts, springs, PC steels, steel cords, bead wires, forward or backward extrusion parts, rolled steel plates, or the like.
  • plastic working includes cold drawing or wire drawing, heading or forging, rolling, or the like.
  • Heading or forging includes, for example, cold heading, warm heading, or the like.
  • the type of plastic working can be selected appropriately depending on the application of the metal material.
  • a plurality of plastic workings may be conducted depending on the application of the metal material. For example, when producing bolts, nuts and the like, heading is conducted after drawing.
  • wire materials or rod materials are subjected to drawing, cutting and then forging.
  • wire drawing is performed in a plurality of steps of a first wire drawing, a second wire drawing and so on.
  • the aforementioned lubricating film formation process may be conducted before at least one plastic working or before each plastic working.
  • the film adhesion amount on the surface of the worked metal article may be almost equal to the film adhesion amount on the surface of the metal material as described above, but is usually less than the film adhesion amount on the surface of the metal material and for example, preferably 0.2 g/m 2 or more and 20 g/m 2 or less (more preferably 1 g/m 2 or more and 15 g/m 2 or less).
  • the steel grade SCM435 JIS G4053: 2008; manufactured by Nippon Testpanel Co., Ltd.
  • the obtained hot rolling wire rod (diameter 12.5 mm, 860 kg) was spherodizing annealed at a temperature of 760° C., subjected to a descaling treatment by pickling (dipping in a pickling solution of 20% sulfuric acid of a temperature of 75° C. for 13 minutes and then dipping in a pickling solution of 15% hydrochloric acid of a temperature of 30° C. for 13.5 minutes), and then washed with water, and the resulting test piece was used as a sample.
  • the lubricating agents of Nos. 1 to 17 shown in Table 1 were prepared.
  • the details of the components A to E in Table 1 are as follows. Industrial water was used as “water” shown in the Table.
  • A1 calcium hydroxide
  • A2 calcium carbonate
  • B1 carnauba wax (the melting point of about 80° C.)
  • Component C Water-Soluble Inorganic Metal Salt
  • test pieces By dipping the above samples (test pieces) in the above lubricating film treatment solution under the following conditions and subsequently drying them, the test pieces of Nos. 1 to 17 provided with each of the various lubricating films were obtained.
  • the lubricating films were produced by the dry method, and it was confirmed in the manner of Example 2 as described later that the component compositions of the lubricating films were almost equal to the component compositions (A to E) of the lubricating agents in the lubricating film treatment solutions (see Table 3).
  • each test material on which a lubricating film was formed by dipping the sample in the lubricating film treatment solution (Nos. 1 to 17, 65° C.) for one minute and then naturally drying was used.
  • each test material on which a lubricating film was formed by dipping the sample in the lubricating film treatment solution (Nos. 1 to 17, 65° C.) for one minute and then drying (temperature: 60° C., time: 30 minutes) was used.
  • each test piece on which a lubricating film was formed by dipping the sample in the lubricating film treatment solution (Nos. 1 to 17, 65° C.) for five minutes and then drying (temperature: 60° C., time: 30 minutes) was used.
  • a lubricating film was formed on each test material under the condition of each of the above tests except that the sample was dipped in a lime lubricating agent for wire drawing (“MAC B20” manufactured by Inoue Calcium Corporation, concentration 4%, 65° C.) as a lubricating film treatment solution, and the resulting test material was used.
  • MAC B20 lime lubricating agent for wire drawing
  • each test material on which a chemical conversion treatment film including zinc phosphate and a soap layer was formed was used. Specifically, the sample was dipped in an aqueous solution (80° C.) containing 150 g/L of a zinc phosphate chemical conversion treatment agent (“PALBOND 421X” manufactured by Nihon Parkerizing Co., Ltd.) for 7 minutes and then washed with water to form a zinc phosphate film.
  • a zinc phosphate chemical conversion treatment agent (“PALBOND 421X” manufactured by Nihon Parkerizing Co., Ltd.
  • the sample was dipped in a treatment solution (80° C.) containing 70 g/L of a soap lubricating agent (“PALUBE 235” manufactured by Nihon Parkerizing Co., Ltd.) for two minutes and then dried (temperature: 90° C., time: 10 minutes) after conducting a soap treatment to form a chemical conversion treatment film.
  • a treatment solution 80° C.
  • 70 g/L of a soap lubricating agent (“PALUBE 235” manufactured by Nihon Parkerizing Co., Ltd.
  • the Bowden friction test is a test for evaluating seizure resistance, film adhesion and lubricity of the lubricating film. Referring to FIG. 1 , the outline of the Bowden friction test is explained. Bowden friction tester manufactured by Shinko Engineering Co., Ltd. was used for the Bowden friction test.
  • the Bowden friction test is a test to determine a friction coefficient ⁇ when the test piece slides reciprocatively in the longitudinal direction of the test piece as the sliding direction with load being applied by means of a steel ball, and the number of reciprocative slidings [torsion (strain)] when the friction coefficient ⁇ exceeds 0.1 due to film break.
  • the larger number of slidings (sliding frequency) means that the test piece is excellent in seizure resistance, excellent film adhesion and excellent lubricity.
  • the test pieces that the number n of reciprocative slidings (sliding frequency) exceeded 100 were evaluated as having excellent seizure resistance and excellent film adhesion.
  • the ball passing test is a test to evaluate seizure resistance in relation to film strength (anti-film break property under high-load condition).
  • the Bowden friction test is also for evaluating seizure resistance of the lubricating film, but is different in that seizure resistance is evaluated mainly in relation to film adhesion.
  • A cross-sectional area of the test piece before the test
  • Seizure resistance was evaluated for seizure on the inner peripheral surface of the test piece after the test as follows. A case in which no seizure was observed was evaluated as “ ⁇ ” (Excellent in seizure resistance and film strength), a case in which seizure was partly observes was evaluated as “ ⁇ ” (Slightly Poor in seizure resistance and film strength), and a case in which seizure was wholly observed was evaluated as “X” (Poor in seizure resistance and film strength). The test pieces evaluated as “ ⁇ ” were judged as being acceptable.
  • the adhesion test is a test for comparative evaluation of film adhesion by quantifying the adhesion between a sample and each lubricating film as shown in Table 1 as a remaining ratio (%).
  • the film adhesion is also evaluated in the Bowden friction test, but it is different in that the film adhesion was evaluated in relation to the seizure resistance.
  • the outline of the film adhesion test is explained.
  • the lubricating film was removed from only one surface of the test piece which the lubricating films were formed on the both surface, and the mass of the removed lubricating film and the mass of the test piece after removal of the lubricating film were each measured (mass before the test). Subsequently, as shown in FIG.
  • an abrasive paper 12 (#360 emery paper, 50 mm ⁇ 200 mm) and a weight 13 (200 gf) were placed on a surface 11 on which the lubricating film was formed, the opposite end of the abrasive paper was pulled straight in the horizontal direction at the prescribed speed (20 mm/sec), and then the mass of the test piece was measured (mass after the test).
  • the film remaining ratio (%) was calculated from mass difference between the test pieces before and after the test, and the test pieces having the remaining ratio of 65% or more were evaluated as being excellent in adhesion.
  • No. 19 (chemical conversion treatment film) was a chemical reaction film and it was difficult to precisely evaluate the adhesion, and therefore the film adhesion test of No. 19 was not conducted.
  • the films that were peeled off from the test pieces, which is referred to as “dropped films”, during the above lubricating film adhesion test were observed to evaluate the dust resistance.
  • the dust resistance was evaluated as follows. A case in which dropped films that can be a factor for scattering (namely, films evaluated as “X” or “ ⁇ ”) could not almost be confirmed was evaluated as “ ⁇ ”, a case in which almost no powdery dropped films were confirmed, but granular dropped films that are hard to scatter were confirmed was evaluated as “ ⁇ ”, and a case in which dropped films in fine powder form that easily scatter were confirmed was evaluated as “X”. In the present invention, “ ⁇ ” and “ ⁇ ” were evaluated as being acceptable.
  • No. 19 (chemical conversion treatment film) was a chemical reaction film and it was difficult to precisely evaluate the dust resistance, and therefore the dust test of No. 19 was not conducted.
  • test piece having a length of 100 mm cut out of a test material (diameter: 12.5 mm) obtained by forming a lubricity film on a sample was left in a thermo-hygrostat testing machine (“TABAI ESPEC PL-3SP” manufactured by ESPEC Corp., temperature: 40° C., humidity: 90%) for two weeks, and then the test piece was taken out and an area ratio of rust (rusting ratio) generated on the surface (39.3 cm 2 ) of the lateral side of the test piece was calculated to evaluate the corrosion resistance.
  • TABAI ESPEC PL-3SP manufactured by ESPEC Corp., temperature: 40° C., humidity: 90%
  • the corrosion resistance was evaluated as follows. A case in which the area ratio of rust was 0% was evaluated as “ ⁇ ” (Particularly Excellent in corrosion resistance), a case in which the area ratio of rust was more than 0% and 5% or less was evaluated as “ ⁇ ” (Excellent in corrosion resistance), and a case in which the area ratio of rust was more than 5% was evaluated as “X” (Poor in corrosion resistance). In the present invention, the area ratio of rust of 5% or less were evaluated as being acceptable.
  • Each test material (diameter: 12.5 mm, 860 kg) was subjected to a wire drawing by means of a single die until the diameter reached 10.85 mm (reduction of area: 24.7%).
  • a dried powder lubricating agent was not used.
  • the drawing rate of the wire drawing was adjusted to 53 m/min using a single block drawing machine. Note that although in a usual wire drawing process, a dried powder lubricating agent is added to reduce friction resistance (seizure resistance) between a workpiece and a wire drawing machine, it has been pointed out that scattering of the dried powder lubricating agent due to vibration or the like of the machine during working is one of factors deteriorating a working environment.
  • the surface state (surface skin) of each of the test materials when conducting the wire drawing was observed.
  • the test material that could be drawn without the occurrence of seizure on the surface was evaluated as being excellent in seizure resistance (“ ⁇ ” in the table). Note that the wire drawing was stopped once the seizure occurred on the surface (“X”: in the table). The results are shown in Table 2.
  • the heading is extrusion to be conducted in order to work the materials after wire drawing into a shape of a product.
  • the headability was evaluated by the presence or absence of the occurrence of seizure when the test materials after wire drawing were worked by heading. Specifically, the above test materials after wire drawing were cut into 23.1 g/piece to produce 1000 cut pieces (test pieces: diameter: about 10.85 mm, length: about 31.9 mm) and subsequently the test pieces were subjected to forward extrusion with a heading machine. At this time, the heading was performed in two steps as shown in FIG. 4 , and the shaft was reduced at the reduction of area of 50% to produce a worked article.
  • the headability was evaluated as follows.
  • Each of Nos. 1 to 11 is an example in which the lubricating film using the lubricating agent satisfying the requirements of the present invention is formed, has good results in any tests of the above (1) to (7), and is superior to No. 18 (lime film) in seizure resistance, lubricity, adhesion (dust resistance), and corrosion resistance. In addition, these are also superior to No. 19 (chemical conversion treatment film) in seizure resistance. Particularly, Nos.
  • No. 12 is an example in which the lubricating agent containing the component B (wax) and the component C (water-soluble inorganic metal salt) was used (it is an example in which the component A (inorganic solid lubricant) was not contained and the content ratio of the wax of the above Patent document 1 was increased).
  • the results of (1) the Bowden friction test and (3) the adhesion test of No. 12 were good and it is considered that this is due to the addition of a large amount of wax (B1) having a relatively high adhesion. Since this lubricating film did not contain the component A, the film strength under a high load was low and thus the seizure resistance was poor in (2) the ball passing test. Since No.
  • No. 13 had the same effect as Nos. 1 to 11 with regard to only the corrosion resistance, but seizure resistance, adhesion, lubricity, and dust resistance were poor.
  • No. 14 is an example in which the lubricating agent containing the component A (inorganic solid lubricant) and the component B (wax) was used (the component C (water-soluble inorganic metal salt) being not contained). Since the wax (B1) having a relatively high adhesion was used in No. 14, the results of (1) the Bowden friction test and (3) the adhesion test were good. However, since the component C was not contained, the result of (5) the corrosion resistance was poor. The film strength under a high load was low and thus the seizure resistance was poor in (2) the ball passing test.
  • No. 15 is an example in which the lubricating agent containing the component A (inorganic solid lubricant), the component B (wax), and the component C (water-soluble inorganic metal salt) was used.
  • the corrosion resistance was also good due to the high content of the component C, but the seizure resistance was poor in (1) the Bowden friction test because of the too high content ratio of the component C, and the seizure occurred during (6) the wire drawability test under the severe processing conditions, and accordingly No. 15 could not be processed by wire drawing.
  • No. 16 is an example in which the lubricating agent containing the component A (inorganic solid lubricant) and the component C (water-soluble inorganic metal salt) was used (the component B (wax) being not contained). Since No. 16 did not contain the component B, the seizure resistance, adhesion (dust resistance), and lubricity were poor.
  • No. 17 is an example in which the lubricating agent containing the component B (wax) and the component C (water-soluble inorganic metal salt) was used (the component A (inorganic solid lubricant) being not contained), and it is an example simulating the above Patent Document 1.
  • the seizure resistance, adhesion (dust resistance), lubricity, and corrosion resistance of No. 17 were poor. It is considered that the lubricating film had the low adhesion because of not containing the component A, and this led to the state where the lubricating film was floating, and the corrosion resistance and the like deteriorated.
  • the component A was not contained, the lubricating film was peeled off and the seizure occurred during (6) the wire drawability test under the severe working conditions, and accordingly No. 17 could not be processed.
  • No. 18 is a conventional example (a lime film) and the adhesion of the film itself is low and therefore any of the test results of the above (1) to (7) were poor and the adhesion, seizure resistance, lubricity and corrosion resistance were poor. Particularly during (6) the wire drawability test, the lubricating film was peeled off when introducing the test material to the die and since the sufficient lubricating film did not remained at the time of wire drawing, the seizure occurred, and accordingly No. 18 could not be processed.
  • No. 19 is a reference example using a chemical conversion treatment film and mostly showed good results even though the result of (1) the Bowden friction test was poor.
  • the criteria for evaluation are as follows.
  • ⁇ (1) the Bowden test evaluation: the average friction coefficient of 0.06 or less and the number of slidings of more than 100; (2) the ball passing test: the seizure resistance evaluation of “ ⁇ ”; (3) the adhesion: the remaining ratio of 65% or more; (4) the dust resistance: the evaluation of “ ⁇ ” or better; (5) the corrosion resistance: the area ratios of rust of 5% or less; (6) the wire drawability: the evaluation of “ ⁇ ”; and (7) the headability: the evaluation of “ ⁇ ”. “ ⁇ ”: In the above tests, a case in which even one item did not meet the evaluation criterion of “ ⁇ ” was evaluated as “ ⁇ ”.
  • Nos. 1 to 11 formed from the lubricating agent containing the components A to C at the specific ratio exhibited excellent properties in any of the tests (the comprehensive evaluation: “ ⁇ ”.
  • Nos. 1 to 11 have the superior properties to No. 18 (lime film), and further exhibited the similar properties as compared with No. 19 (chemical conversion treatment film) in (2) the ball passing test, (5) the corrosion resistance test, (6) the wire drawability test and (7) the headability test, and also have the superior property to No. 19 in (1) the Bowden friction test.
  • the lubricating films of Nos. 12 to 17 could not meet the evaluation criteria (the comprehensive evaluation: “X” and particularly, any of the test materials could not be worked due to the occurrence of seizure in (6) the wire drawability test.
  • test materials Nos. 1 to 11 provided with each of the various lubricating films obtained by dipping a sample (test piece) in each of the lubricating film treatment solutions of Nos. 1 to 11 in Table 1 and subsequently drying, the components in the lubricating film formed on each of the test material were examined in the manner describe below.
  • the sample (SCM435: diameter: 12.5 mm, length: 200 mm) was dipped in the lubricating film treatment solution (Nos. 1 to 11) as shown in Table 1 for one minute and subsequently dried (temperature: 60° C., time: 30 minutes), to prepare each five of the test materials on which the lubricating film was formed.
  • the mass of each test materials on which the lubricating film was formed was measured and subsequently the test materials were washed with a cleaning solution (distilled water) to completely remove the lubricating films.
  • the cleaning solution containing the lubricating film removed from the above test materials was filtered with a membrane filter (pore diameter: 0.45 ⁇ m).
  • the filtrate obtained by filtering was dried to remove water and the mass of the remaining filtered substance (the substance that had passed through the filter) was measured (“Filtered substance 1” of the column of “Measured value” in Table 3).
  • the filtered substance 1 contains the component C (water-soluble inorganic metal salt), the component D (surface active agent), and the component E (rust-proofing agent), and the mass of the component C (filtered substance 4) was calculated based on the addition percentage of the components C to E added to the lubricating film treatment solution in the following manner.
  • Mass (g) of component C (filtered substance 4) mass (g) of filtered substance 1 ⁇ addition percentage (%) of the components C+(addition percentage (%) of components C+addition percentage (%) of components D+addition percentage (%) of components E)
  • the residue collected on the filter after filtering in the above (1) was dried to remove water, and then the remaining filtered substance (the substance that had not passed through the filter) together with the filter was added to a container containing a mineral oil (“Super Oil M46” manufactured by JX Nippon Oil & Energy Corporation, 200 ml) heated to 190° C. and dipped for five minutes, and subsequently was filtered with a membrane filter (pore diameter: 0.45 ⁇ m) without being cooled.
  • a mineral oil (190° C.) was further supplied to the membrane filter so as to be washed sufficiently. After being cooled to a room temperature, the residue on the filter was sufficiently washed with diethyl ether, and then dried to remove water and diethyl ether, and the mass of the remaining filtered substance was measured (filtered substance 2 (component A)).
  • the filtrate after being washed with the mineral oil and diethyl ether (room temperature; the filtrate containing the mineral oil and diethyl ether) in the above (2) was filtered with a membrane filter (pore diameter: 0.45 ⁇ m), the residue collected on the filter was sufficiently washed with diethyl ether, and then dried to remove water and diethyl ether, and the mass of the remaining filtered substance (the substance that had not passed through the filter) was measured (filtered substance 3 (component B)).
  • the theoretical value is a value that the content for each component was calculated based on the content ratio of the components A to E contained in the lubricating film treatment solution as shown in Table 1 from the above-described lubricating film adhesion amount.
  • the content of each component contained in the lubricating film showed approximate values within ⁇ 10% of the theoretical values (including measurement errors).
  • the ratios ([A/B], [C/(A+B+C)], [B/C]) of the components A to C in the lubricating film also showed approximate values to the ratios of the components A to C in each lubricating film treatment solution as shown in Table 1.
  • the lubricating film having a component composition approximately corresponding to the component composition in the lubricating film treatment solution could be formed on the metal material by appropriately adjusting the component composition in the lubricating film treatment solution.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
US14/374,088 2012-02-27 2013-02-22 Water-soluble lubricating agent for plastic working, metal material for plastic working, and worked metal article Abandoned US20150329797A2 (en)

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JP2012040520 2012-02-27
JP2012-040520 2012-02-27
JP2013029282A JP2013209625A (ja) 2012-02-27 2013-02-18 塑性加工用水溶性潤滑剤、塑性加工用金属材および金属加工品
JP2013-029282 2013-02-18
PCT/JP2013/054621 WO2013129268A1 (ja) 2012-02-27 2013-02-22 塑性加工用水溶性潤滑剤、塑性加工用金属材および金属加工品

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WO2013129268A1 (ja) 2013-09-06
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TW201402803A (zh) 2014-01-16
MX2014010350A (es) 2015-03-09
CN104136592A (zh) 2014-11-05

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