WO2015125737A1 - Composition pour électrolyse cathodique en courant continu, et matériau métallique avec film de lubrification ainsi que procédé de fabrication de celui-ci - Google Patents

Composition pour électrolyse cathodique en courant continu, et matériau métallique avec film de lubrification ainsi que procédé de fabrication de celui-ci Download PDF

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WO2015125737A1
WO2015125737A1 PCT/JP2015/054150 JP2015054150W WO2015125737A1 WO 2015125737 A1 WO2015125737 A1 WO 2015125737A1 JP 2015054150 W JP2015054150 W JP 2015054150W WO 2015125737 A1 WO2015125737 A1 WO 2015125737A1
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Prior art keywords
metal material
metal
composition
film
ion
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PCT/JP2015/054150
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English (en)
Japanese (ja)
Inventor
亮助 川越
清水　大輔
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日本パーカライジング株式会社
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Priority to CN201580009607.9A priority Critical patent/CN106133201B/zh
Priority to JP2016504088A priority patent/JP6211678B2/ja
Priority to KR1020167022672A priority patent/KR101815412B1/ko
Priority to MX2016010837A priority patent/MX2016010837A/es
Priority to US15/120,400 priority patent/US20170073831A1/en
Publication of WO2015125737A1 publication Critical patent/WO2015125737A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • B21D22/201—Work-pieces; preparation of the work-pieces, e.g. lubricating, coating
    • 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
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/42—Electroplating: Baths therefor from solutions of light metals
    • C25D3/44—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/12—Electrolytic coating other than with metals with inorganic materials by cathodic processes on light metals

Definitions

  • the present invention relates to a composition for direct current cathode electrolysis, and more particularly to a composition for direct current cathode electrolysis containing a predetermined metal ion and an organic acid compound.
  • the present invention also relates to a metal material with a lubricant film obtained by using a composition for direct current cathode electrolysis and a method for producing the same.
  • Metal materials are used in many structures. For example, iron-based materials are roughly formed by creating structural parts by pressing, drawing, cutting, punching, and other parts from plates, wires, and rods that are profound, and joining them by welding and bonding. The shape is assembled. Then, after rust prevention treatment and various coatings (coating methods), the product is designed in consideration of design, and in some cases, electronic parts and interior parts are loaded and shipped. In the forging process of such materials, lubricity is required, and various techniques have been proposed.
  • Patent Document 1 as a method for forming a lubricating film, a chemical conversion film is formed by cathodic electrolysis using an electrolytic solution containing zinc ions, phosphate ions, and nitrate ions, and then a water-based or oil-based film is formed. A method of contacting a lubricant is disclosed.
  • the lubricating film is required to have both high lubricity and high chemical conversion after film removal treatment.
  • the film removal treatment is provided in the coating process and can be easily carried out by a degreasing treatment that is usually used in the preceding stage of the chemical conversion treatment.
  • the inventors of the present invention formed a lubricating film by carrying out the method described in Patent Document 1 and studied its properties (lubricity and chemical conversion after degreasing). It was found that the chemical conversion film was uneven and the lubricity and the chemical conversion property after degreasing were not sufficient.
  • the chemical conversion treatment applied thereafter is performed. Does not progress well.
  • An object of this invention is to provide the composition for direct current cathode electrolysis which can form the metal material with a lubrication film which is excellent in lubricity and the chemical conversion property after degreasing in view of the said situation.
  • Another object of the present invention is to provide a method for producing a metal material with a lubricant film using the composition for direct current cathode electrolysis, and a metal material with a lubricant film.
  • the present inventors have carried out cathodic electrolysis using a composition for direct current cathode electrolysis containing a predetermined metal ion or a complex thereof and a predetermined organic acid compound. It has been found that a lubricating film exhibiting properties can be obtained. That is, it has been found that the above object can be achieved by the following configuration.
  • the metal ion or complex (A) includes at least one metal ion selected from the group consisting of magnesium ion, calcium ion, aluminum ion, yttrium ion, and lanthanoid metal ion or a complex thereof ( The composition for direct-current cathode electrolysis as described in 1).
  • the organic acid compound (B) includes an aliphatic monocarboxylic acid containing a linear alkylene group having 4 or more carbon atoms or an aliphatic dicarboxylic acid containing a linear alkylene group having 4 or more carbon atoms (1) ) Or the composition for direct current cathode electrolysis according to (2).
  • a metal material is immersed in the composition for direct current cathode electrolysis according to any one of (1) to (4), and cathodic electrolysis using direct current is performed using the metal material as a cathode, and the metal material is lubricated on the surface.
  • the manufacturing method of the metal material with a lubricous film provided with the process of forming a film.
  • a metal material with a lubricant film produced by the method for producing a metal material with a lubricant film according to (5).
  • a metal material with a lubricant film comprising a metal material and a lubricant film disposed on the surface of the metal material,
  • the lubricating coating has at least one metal element selected from the group consisting of divalent or higher typical metal elements (excluding zinc element) and rare earth elements; An organic acid compound containing a carboxyl group and a linear alkylene group having 4 or more carbon atoms and / or a salt thereof in the molecule; In the analysis in the depth direction of the lubricating coating from the surface opposite to the metallic material of the lubricating coating to the metallic material side using the glow discharge optical emission spectrometry, the lubricating coating is measured on the side opposite to the metallic material.
  • the composition for direct current cathode electrolysis which can form the metal material with a lubricous film which is excellent in lubricity and the chemical conversion property after degreasing
  • the manufacturing method of the metal material with a lubricous film using the composition for direct-current cathode electrolysis, and the metal material with a lubricous film can also be provided.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a metal material with a lubricating film of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another embodiment of the metal material with a lubricating film of the present invention.
  • FIG. 3 is a schematic diagram of a high-speed deep drawing tester used in the lubricity evaluation (part 2) performed in the examples.
  • cathodic electrolysis is performed using a composition for direct current cathode electrolysis containing a predetermined metal ion or a complex thereof and a predetermined organic acid compound. It is done.
  • plating there is a surface treatment called plating in which metal is deposited on a workpiece by cathodic electrolysis.
  • a metal ion or a complex thereof which is treated as a cathode but hardly precipitates as a metal, is used as a component in the composition. That is, the metal ion or complex thereof used in the present invention is difficult to reduce as a metal in an aqueous system, and tends to be a hydroxide, hydrated oxide, and / or oxide containing the metal ion.
  • a film forming method by DC cathode electrolysis is employed. First, when cathodic electrolysis is performed, concentration of metal ions or complexes thereof in the vicinity of the metal material that is the object to be processed occurs by electrophoresis of each metal ion or complex thereof.
  • the organic acid compound since the organic acid compound has a carboxyl group, it is electrophoresed away from the metal material. Therefore, the organic acid compound hardly precipitates on the surface of the metal material. In particular, the higher the pH in the vicinity of the metal material, the stronger the ionicity, and the phenomenon becomes more remarkable. Therefore, in the initial stage of cathodic electrolysis, the organic acid compound is difficult to precipitate on the surface of the metal material, and as the electrolysis progresses, the organic acid compound becomes a metal ion or a complex thereof, an oxide containing the metal ion, a hydroxide, etc. It is thought that a salt is gradually formed and a composite salt of an organic acid compound and a metal ion is deposited on the surface of the metal material.
  • the organic acid compound is further concentrated on the exposed surface (surface opposite to the metal material side) side of the lubricant film. Therefore, many organic acid compounds having excellent lubricating properties are present on the surface of the lubricating film, and excellent lubricity is exhibited.
  • a water-based composition in which a metal ion or a complex thereof and an organic acid compound are mixed, an increase in the hydroxide ion concentration on the surface of the metal material occurs. The precipitation equilibrium between the metal ions and the organic acid compound is deviated, and the lubricating film is deposited.
  • Such a process for forming a lubricating film is greatly different from a conventional process for forming a lubricating film.
  • this composition when this composition is used, when manufacturing a lubricating film, since it is not necessary to perform a high temperature process and a process is completed in one process, it is preferable at the point of industrial productivity.
  • the formed lubricating film is preferable in terms of cost and productivity from the viewpoint that a desired effect can be obtained even if the thickness is small.
  • composition various components (metal ion or complex (A), organic acid compound (B), water (C), etc.) constituting the composition for direct current cathode electrolysis (hereinafter also simply referred to as “composition”). Then, the manufacturing method of the metal material with a lubricating film using the composition will be described in detail.
  • the composition includes a divalent or higher typical metal ion (excluding zinc ions) and at least one metal ion selected from the group consisting of rare earth element ions or a complex thereof (A) (hereinafter, both The concept including “metal ion (A)” is also included.
  • the metal ion (A) becomes a component constituting a lubricating film as a complex with a metal oxide, a metal hydroxide, or an organic acid compound (B) described later during cathodic electrolysis.
  • Typical metal ions include ions of group 2 elements of the periodic table (alkaline earth metal ions) such as beryllium, magnesium, calcium, strontium, barium, radium, cadmium, mercury, etc. Ions of group 12 elements in the periodic table (excluding zinc ions), ions of group 13 elements of the periodic table such as aluminum, gallium, indium and thallium, and periodic tables such as germanium, tin and lead And ions of Group 15 elements of the periodic table such as antimony and bismuth, and ions of Group 16 elements of the periodic table such as polonium.
  • group 2 elements of the periodic table alkaline earth metal ions
  • Ions of group 12 elements in the periodic table excluding zinc ions
  • ions of group 13 elements of the periodic table such as aluminum, gallium, indium and thallium
  • periodic tables such as germanium, tin and lead And ions of Group 15 elements of the periodic table such as antimony and bismuth
  • ions of Group 16 elements of the periodic table
  • the rare earth element ions are intended to be ions of rare earth elements, and include the concept including yttrium ions (ions of yttrium elements), scandinium ions (ions of scandinium elements), and lanthanoid metal ions.
  • a lanthanoid metal ion (an ion of a lanthanoid metal element) is intended to be an ion of a lanthanoid group metal element, more specifically, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprodium, Contemplates ions of elements such as holmium, erbium, thulium, ytterbium, or lutetium.
  • magnesium ion, calcium ion, aluminum ion, yttrium ion are more excellent in lubricity and / or chemical conversion after degreasing (hereinafter also referred to simply as “the effect of the present invention is more excellent”).
  • lanthanoid metal ions are preferable, and magnesium ions, calcium ions, and aluminum ions are more preferable.
  • a metal ion (A) may use only 1 type, or may use 2 or more types together.
  • the metal ion complex is intended to mean a complex (organic complex) containing the metal ion. It is preferable that a chelating agent (complexing agent) is contained in the complex.
  • the chelating agent does not include the organic acid compound (B) described later. Any chelating agent can be used as long as it has a function of chelating the metal ions and does not impair the effects of the present invention.
  • organic acids such as gluconic acid, citric acid and succinic acid and salts thereof, organophosphorus compounds, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) or salts thereof are used. be able to.
  • aminopolycarboxylic acid or a salt thereof is preferable in that the effect of the present invention is more excellent.
  • condensed phosphates such as sodium tripolyphosphate may be used as a chelating agent, it is preferable that they are not included in the composition because salt formation with metal ions is easy and control is difficult.
  • Aminopolycarboxylic acid is a general term for chelating agents having an amino group and a plurality of carboxyl groups in the molecule.
  • aminopolycarboxylic acid salt is not particularly limited, and examples thereof include ammonium salts, sodium salts, potassium salts, and the like of the compounds exemplified above.
  • the method for supplying the metal ion or complex thereof in the composition is not particularly limited, and a salt containing the metal ion (for example, carbonate, hydrogencarbonate, acetate, formate, nitrate, sulfate, borate) ), Oxides, hydroxides, halides (for example, fluorides) and the like, and a method of adding a complex (organic complex) containing the above metal ions to water.
  • a salt containing the metal ion for example, carbonate, hydrogencarbonate, acetate, formate, nitrate, sulfate, borate
  • Oxides for example, hydroxides, halides (for example, fluorides) and the like
  • a complex (organic complex) containing the above metal ions to water.
  • use chlorides in the composition to prevent rusting. It is desirable to refrain.
  • the concentration of the metal ion or complex thereof in the composition is not particularly limited, but is preferably 50 to 50000 mass ppm, more preferably 500 to 10000 mass ppm from the viewpoint that the effect of the present invention is more excellent.
  • the total concentration of metal ions (A) is in the above range.
  • the amount of metal ion contained in the complex is preferably within the above range.
  • Organic acid compound (B) is a compound containing a carboxyl group and a linear alkylene group having 4 or more carbon atoms in the molecule.
  • the organic acid compound (B) interacts with the metal ion (A) through a carboxyl group to form a complex, and is taken into the lubricating film.
  • the hydrocarbon skeleton in the organic acid compound (B) contributes to imparting lubricity.
  • the organic acid compound (B) contains a carboxyl group, and the number of carboxyl groups is not particularly limited.
  • the organic acid compound (B) contains a linear alkylene group having 4 or more carbon atoms.
  • the linear alkylene group means a group represented by the following formula (1).
  • n represents an integer of 4 or more.
  • Formula (1) *-(CH 2 ) n- * n represents an integer of 4 or more.
  • 4 to 17 is preferable and 4 to 8 is more preferable in that the effect of the present invention is more excellent.
  • the longer the straight chain in the alkylene group the closer to the higher fatty acid and the higher the lubricity.
  • * represents a bonding position.
  • Preferred examples of the organic acid compound (B) include aliphatic monocarboxylic acids containing a linear alkylene group having 4 or more carbon atoms or aliphatic dicarboxylic acids containing a linear alkylene group having 4 or more carbon atoms.
  • Preferable embodiments of the aliphatic monocarboxylic acid and the aliphatic dicarboxylic acid include an aliphatic monocarboxylic acid represented by the formula (1) and an aliphatic dicarboxylic acid represented by the formula (2), respectively.
  • R represents an alkyl group containing a linear alkylene group having 4 or more carbon atoms as a partial structure.
  • the number of carbon atoms in the alkyl group may be 4 or more, but 4 to 18 is preferable, 4 to 16 is more preferable, and 5 to 12 is even more preferable from the viewpoint that the effect of the present invention is more excellent.
  • a C4-C4 or more linear alkylene group should just be contained as a partial structure,
  • the following include compounds represented by formula (1-1).
  • Formula (1-1) R 1 -L-COOH R 1 represents an alkyl group.
  • L represents a linear alkylene group having 4 or more carbon atoms.
  • the alkyl group represented by R 1 may be linear or branched.
  • the total number of carbons in R 1 is not particularly limited, but the total number of carbons in R 1 and L is preferably in the above range (4 to 18).
  • the alkylene group represented by L preferably has 4 or more carbon atoms, more preferably 4 to 17 carbon atoms, and still more preferably 4 to 8 carbon atoms.
  • L represents a linear alkylene group having 4 or more carbon atoms. Although carbon number in an alkylene group should just be 4 or more, 5 or more are preferable and 7 or more are more preferable at the point which the effect of this invention is more excellent.
  • the upper limit is not particularly limited, but is preferably 16 or less from the viewpoint of handleability.
  • Examples of the aliphatic monocarboxylic acid include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid and the like.
  • Examples of the aliphatic dicarboxylic acid include hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), and undecane.
  • Examples include diacid, dodecanedioic acid, tridecanedioic acid (brassic acid), hexadecanedioic acid, and octadecanedioic acid.
  • the concentration of the organic acid compound (B) in the composition is not particularly limited, but is preferably 50 to 50,000 mass ppm, more preferably 500 to 10,000 ppm in terms of more excellent effects of the present invention. In addition, when 2 or more types of organic acid compounds (B) are used, it is preferable that the total density
  • the composition includes water as a solvent.
  • the content of water (C) in the composition is not particularly limited, but is preferably 65% by mass or more and 75% by mass with respect to the total mass of the composition in terms of excellent handleability and more excellent effects of the present invention. The above is more preferable.
  • the upper limit is not particularly limited, but is often 99% by mass or less.
  • the composition may contain other components other than the above components (metal ion or complex thereof (A), organic acid compound (B), water (C)).
  • the above-described chelating agent may be separately added to the composition.
  • the pH of the composition containing the above components is not particularly limited, but is preferably 3.5 to 12.5, more preferably 4.0 to 10.0, from the viewpoint that the effects of the present invention are more excellent.
  • the direct current cathode electrolysis of the present invention hardly causes etching of the metal material. The lower the value, the more likely there is corrosion of equipment and material corrosion in the water washing process. Further, if it remains as a contamination composition on the metal material, there is a possibility that it will have an adverse effect during storage of the steel material.
  • the pH of the composition is particularly preferably 6.0 to 9.0.
  • adjusting the pH of the composition known acids (hydrochloric acid, nitric acid, formic acid, acetic acid, sulfonic acid, hydrofluoric acid, etc.) and / or alkalis (sodium compound, potassium compound, ammonia, amine compound, etc.) are used. be able to.
  • the method for producing the composition is not particularly limited, and a known method can be adopted.
  • a known method can be adopted.
  • the method of adding the compound containing the said metal ion (A) and the organic acid compound (B) to water (C), and performing a stirring process etc. are mentioned.
  • the above composition is used for DC cathode electrolysis. That is, it is a composition used for performing a cathodic electrolysis treatment using direct current on a metal material to be treated.
  • a method for producing a metal material with a lubrication film comprises immersing a metal material in the above-described composition for direct current cathode electrolysis, performing a cathodic electrolysis treatment using direct current using the metal material as a cathode, and forming a lubrication film on the surface of the metal material.
  • a process is provided. By carrying out this step, a lubricating film having a component composition described later can be obtained on the metal material.
  • the type of metal material used in this step is not particularly limited.
  • cold rolled steel sheet SPC material
  • hot rolled steel sheet SPH material
  • general structural rolled steel SS material
  • carbon steel SC
  • various alloy steels stainless steel, Al or alloys thereof, Mg or alloys thereof, Cu or alloys thereof, Zn or alloys thereof, Ni-base alloys, Co-base alloys, and the like
  • the shape of the metal material is not particularly limited, such as a coil shape, a rod shape, a strip shape, a tubular shape, a cast forged product, and a bearing. Note that the surface of the metal material can be degreased and cleaned in advance if necessary.
  • the method of cathode electrolysis is not particularly limited as long as a metal material to be processed is used as a cathode, and a known method can be adopted. Usually, a method is adopted in which a metal material is immersed in the composition and a voltage is applied to the insoluble anode. A platinum electrode, a stainless steel electrode, a lead electrode, etc. can be used as an insoluble electrode. While current density is not particularly limited, in terms of the effect of the present invention is more excellent, preferably 0.01 ⁇ 100A / dm 2, more preferably 0.05 ⁇ 50A / dm 2.
  • Energizing quantity of electricity is not particularly limited, in terms of the effect of the present invention is more excellent, preferably 5 ⁇ 300C / dm 2, more preferably 15 ⁇ 180C / dm 2.
  • the temperature of the composition is not particularly limited, but is preferably 15 to 40 ° C., more preferably 20 to 35 ° C., from the viewpoint that the lubricating film is more efficiently precipitated.
  • a metal material may be removed from the composition, and a washing step of washing with water may be performed as necessary. Moreover, you may implement the drying process which performs a drying process after a washing
  • the metal material 10 with a lubricant film obtained by the above method includes a metal material 12 and a lubricant film 14 disposed on the surface thereof.
  • the kind of the metal material 12 is as described above.
  • the lubricating film is a film that is deposited by performing cathodic electrolysis in the composition.
  • the lubricating film has at least one metal element selected from the group consisting of divalent or higher-valent typical metal elements (excluding zinc element) and rare earth elements, a carboxyl group, and carbon in the molecule.
  • An organic acid compound containing a linear alkylene group having a number of 4 or more and / or a salt thereof is included.
  • the metal element contained in the lubricating film is an element derived from metal ions in the composition.
  • the metal element include each metal element described in the above metal ion.
  • the presence form of the metal element is not particularly limited, and examples thereof include forms such as metal oxide and metal hydroxide.
  • the content of the metal element in the lubricating film in is not particularly limited, in terms of the effect of the present invention is more excellent, 0.05 g / m 2 or more, more preferably 0.1 ⁇ 5g / m 2, 0.1 More preferred is ⁇ 3 g / m 2 .
  • the organic acid compound contained in the lubricating film is the organic acid compound in the composition described above.
  • the organic acid compound in the composition is precipitated in the lubricating film together with the metal element during the cathode electrolysis.
  • the salt of the organic acid compound includes a salt of the organic acid compound and the metal ion.
  • Organic acid compound in the lubricating film in and its content of salt is not particularly limited, in terms of the effect of the present invention is more excellent, preferably 0.05 ⁇ 3g / m 2, 0.1 ⁇ 1g / m 2 Gayori preferable. In the case of a salt of an organic acid compound, only the organic acid compound portion is used for the calculation of the content.
  • Carbon element-derived peak intensity (Is) and carbon element-derived peak intensity (Im) at an intermediate position between the surface opposite to the metal material of the lubricating film and a depth corresponding to 1/2 of the entire thickness of the lubricating film. ) (Im / Is) is less than 1.0.
  • the ratio (Im / Is) is preferably 0.5 or less, and more preferably 0.2 or less, in that the effect of the present invention is more excellent.
  • the lower limit is not particularly limited, but is often 0.05 or more in the production procedure. More specifically, as shown in FIG. 1, the peak intensity (Is) derived from the carbon element at the surface position 14 ⁇ / b> A of the lubricating film 14 and the peak intensity (Im) derived from the carbon element at the intermediate position 14 ⁇ / b> B of the lubricating film 14. ) (Im / Is) is less than 1.0. That is, the peak intensity (Is) is larger than the peak intensity (Im).
  • the carbon element-derived peak intensity (Is) at the surface position 14A is intended to be the size of the carbon element-derived peak obtained by glow discharge emission spectrometry on the surface of the lubricating coating 14.
  • the peak intensity (Is) derived from the carbon element at the intermediate position 14B is the lubricant film 14 from the surface (surface position 14A) opposite to the metal material 12 side of the lubricant film 14 toward the metal material 12 side.
  • the peak derived from the carbon element obtained by glow discharge emission spectrometry at a position corresponding to 1 ⁇ 2 of the total thickness in other words, a cross-sectional area at an intermediate position in the thickness direction of the lubricating coating 14. Intended.
  • the ratio (Im / Is) is 1.0 or more, the effect of the present invention is inferior.
  • the peak intensity derived from the carbon element can be measured by a Marcus type high-frequency glow discharge emission spectrometer (commonly known as GDS, JY-5000RF type manufactured by Horiba, Ltd.).
  • the reason why the concentration distribution of carbon element as described above occurs in the lubricating film is that, as described above, during cathode electrolysis, first, a metal oxide or hydroxide film derived from metal ions is used. It is expected that the organic acid compound is deposited on the metal material and then gradually deposited. As a preferred embodiment of the lubricating film, the carbon element content (based on the peak intensity ratio) gradually decreases from the surface of the lubricating film to a position corresponding to a depth corresponding to 1/2 of the entire thickness of the lubricating film. It is preferable.
  • the thickness of the lubricating film is not particularly limited, but is preferably 0.5 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m, from the viewpoint that the effect of the present invention is more excellent.
  • a metal material 100 with a lubricant film in which an oil layer 16 containing an oil component is disposed on the lubricant film 14 is preferably exemplified as shown in FIG.
  • the oil layer is preferably a lubricating oil layer using a lubricating oil containing a lubricating component, but may be a rust-preventing oil layer using a rust-preventing oil containing a lubricating component.
  • the oil layer may be the lubricating oil itself or the rust preventive oil itself.
  • the adhesion amount of the oil layer is not particularly limited, but is preferably from 0.1 to 3.0 g / m 2 , more preferably from 0.3 to 2.0 g / m 2 in terms of better lubricity and removability. 5 to 1.5 g / m 2 is more preferable.
  • the amount of adhesion can be measured using a surface carbon analyzer or the like.
  • the metal material with a lubricating film described above exhibits excellent lubricity and is provided for a coating process, and the lubricating film is easily removed by a degreasing process that is usually used in the previous stage of chemical conversion treatment.
  • Various chemical conversion treatments can be satisfactorily performed on the surface of the metal material subjected to the film removal treatment.
  • a metal material with a lubricating film can be subjected to severe forming processing such as deep drawing, ironing or stretch drawing, and then subjected to degreasing and various chemical conversion treatments such as painting. it can.
  • the surface of the wire and the SPC material was cleaned with a degreasing agent in order to remove oil and dust on the surface. More specifically, a degreasing agent (Fine Cleaner E2001 manufactured by Nihon Parkerizing Co., Ltd.) was heated to 43 ° C., and the wire rod and the cold-rolled steel plate were immersed for 3 minutes to remove oil and adhered dust on the surface. Subsequently, the degreasing agent components on the wire rod and the cold-rolled steel plate were washed away with Hiratsuka City water, and the moisture on the wire rod and the cold-rolled steel plate was removed by air blowing.
  • a degreasing agent Feine Cleaner E2001 manufactured by Nihon Parkerizing Co., Ltd.
  • the intensity of the metal element was measured with fluorescent X-ray (ZSX Primus 2 manufactured by Rigaku Corporation), and the adhesion amount (g / m 2 ) was calculated from the calibration curve composed of the intensity and the amount.
  • the organic acid compound it heated at 500 degreeC for 180 second using the carbon analyzer (LECO Co., Ltd. RC412), the organic acid compound adhering to the steel plate surface was burned as carbon dioxide, and the amount of adhering carbon was calculated
  • the adhesion amount (g / m 2 ) of the organic acid compound was calculated from the obtained carbon amount and the ratio of carbon element (carbon content) to the total molecular weight in the organic acid compound.
  • the test piece is cut into a shape of 2 cm ⁇ 5 cm ⁇ 0.8 mm (thickness) in an uncoated state. Moreover, the surface clean SPC material of the same dimension is handled as a blank, and the surface carbon amount of the blank is measured in advance to confirm that it is zero.
  • Sputtering was performed with argon in the depth direction from the surface of the lubricating coating obtained in Examples and Comparative Examples, and the strength of each component was determined from plasma emission specific to the carbon element.
  • the peak intensity (Is) derived from the carbon element on the surface of the lubricating film and the peak intensity (Im) derived from the carbon element at the intermediate position in the thickness direction of the lubricating film were respectively obtained and the ratio ( Im / Is) was calculated.
  • Example 1 Prepare calcium complex aqueous solution using calcium nitrate, EDTA (ethylenediaminetetraacetic acid disodium salt) and deionized water, then add isooctadecanoic acid and adjust pH to 5.0 with ammonia and nitric acid
  • a 1 L graduated cylinder was regarded as a treatment tank, filled with the composition for DC cathode electrolysis, and heated to 25 ° C. Inside the treatment tank, a SUS mesh was placed as an anode.
  • a wire rod subjected to surface cleaning treatment was immersed as a cathode in the center of the treatment tank, and an electrolysis operation was performed with a rectifier (ZX-1600LA, manufactured by Takasago Manufacturing Co., Ltd.) to obtain a current density of 10 A / dm 2 and an electric quantity of 20 C / dm 2 . . Since the current value was low, a non-resistance ammeter was installed in the middle of the wiring, and cathode electrolysis was performed while confirming that the current was a predetermined value. Next, the test piece was taken out from the treatment tank, washed with Hiratsuka water, air was removed by air blow, and a lubricating film was produced on the wire.
  • a rectifier ZX-1600LA, manufactured by Takasago Manufacturing Co., Ltd.
  • the adhesion amount in the lubricating film was 0.3 g / m 2 for calcium (calcium element) and 0.2 g / m 2 for isooctadecanoic acid.
  • the ratio (Im / Is) was 0.11.
  • the wire rod of Example 1 on which the lubricating film was formed was coated with rust preventive oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) while measuring the weight to 1.0 g / m 2 .
  • Example 2 Magnesium nitrate is added to deionized water to produce a magnesium aqueous solution, then nonanedioic acid is added, the pH is adjusted to 9.0 with ammonia and nitric acid, the concentration of magnesium ions is 3000 ppm by mass, A composition for direct current cathode electrolysis of Example 2 in which the acid was 2000 ppm by mass was obtained.
  • a 1 L graduated cylinder was regarded as a treatment tank, filled with the composition for DC cathode electrolysis, and heated to 25 ° C. Inside the treatment tank, a SUS mesh was placed as an anode.
  • a wire rod subjected to surface cleaning treatment was immersed as a cathode in the center of the treatment tank, and an electrolysis operation was performed with a rectifier (ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.) to obtain a current density of 10 A / dm 2 and an electric quantity of 50 C / dm 2 . . Since the current value was low, a non-resistance ammeter was installed in the middle of the wiring, and cathode electrolysis was performed while confirming that the current was a predetermined value. Next, the test piece was taken out from the treatment tank, washed with Hiratsuka water, air was removed by air blow, and a lubricating film was produced on the wire.
  • a rectifier ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.
  • Adhesion amount of lubricating film in the magnesium (magnesium element) is 0.6 g / m 2, nonane diacid was 0.2 g / m 2.
  • the ratio (Im / Is) was 0.11.
  • Anticorrosive oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) was applied to the wire of Example 2 on which the lubricating film was formed while measuring the weight to 1.0 g / m 2 .
  • Example 3 An aluminum complex aqueous solution was prepared using aluminum nitrate, NTA (nitrilotriacetic acid trisodium salt), and deionized water, then nonanedioic acid was added, and the pH was adjusted to 6.0 with ammonia and nitric acid.
  • a composition for direct current cathode electrolysis of Example 3 was obtained in which the concentration of aluminum ions was 3000 ppm by mass and the concentration of nonanedioic acid was 5000 ppm by mass.
  • a 1 L graduated cylinder was regarded as a treatment tank, filled with the composition for DC cathode electrolysis, and heated to 30 ° C. Inside the treatment tank, a SUS mesh was placed as an anode.
  • a wire rod subjected to surface cleaning treatment was immersed as a cathode in the center of the treatment tank, and an electrolysis operation was performed with a rectifier (ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.) to obtain a current density of 10 A / dm 2 and an electric quantity of 50 C / dm 2 . . Since the current value was low, a non-resistance ammeter was installed in the middle of the wiring, and cathode electrolysis was performed while confirming that the current was a predetermined value. Next, the test piece was taken out from the treatment tank, washed with Hiratsuka water, air was removed by air blow, and a lubricating film was produced on the wire.
  • a rectifier ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.
  • the adhesion amount in the lubricating film was 0.4 g / m 2 for aluminum (aluminum element) and 0.3 g / m 2 for nonanedioic acid.
  • the ratio (Im / Is) was 0.13.
  • Anticorrosive oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) was applied to the wire of Example 3 on which the lubricating film was formed while measuring the weight to 1.0 g / m 2 .
  • Example 4 An yttrium aqueous solution is prepared using yttrium nitrate and deionized water, hexane diacid is then added, pH is adjusted to 6.0 with ammonia and nitric acid, the concentration of yttrium ions is 3000 ppm by mass, A composition for direct current cathode electrolysis of Example 4 having an acid concentration of 5000 ppm by mass was obtained.
  • a 1 L graduated cylinder was regarded as a treatment tank, filled with the composition for DC cathode electrolysis, and heated to 30 ° C. Inside the treatment tank, a SUS mesh was placed as an anode.
  • a wire rod subjected to surface cleaning treatment was immersed as a cathode in the center of the treatment tank, and an electrolysis operation was performed with a rectifier (ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.) to obtain a current density of 20 A / dm 2 and an electric quantity of 50 C / dm 2 . . Since the current value was low, a non-resistance ammeter was installed in the middle of the wiring, and cathode electrolysis was performed while confirming that the current was a predetermined value. Next, the test piece was taken out from the treatment tank, washed with Hiratsuka water, air was removed by air blow, and a lubricating film was produced on the wire.
  • a rectifier ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.
  • Adhesion amount of lubricating film in the yttrium (yttrium element) is 0.7 g / m 2, nonane diacid was 0.3 g / m 2.
  • the ratio (Im / Is) was 0.13.
  • Anticorrosive oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) was applied to the wire of Example 4 on which the lubricating film was formed while measuring the weight to 1.0 g / m 2 .
  • Example 5 Prepare calcium complex aqueous solution using calcium nitrate, EDTA (disodium salt of ethylenediaminetetraacetic acid) and deionized water, then add isooctadecanoic acid and adjust pH to 6.0 with ammonia and nitric acid.
  • a 1 L graduated cylinder was regarded as a treatment tank, filled with the composition for DC cathode electrolysis, and heated to 30 ° C.
  • a SUS mesh was placed as an anode.
  • a wire rod subjected to surface cleaning treatment was immersed as a cathode in the center of the treatment tank, and an electrolysis operation was performed with a rectifier (ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.) to obtain a current density of 10 A / dm 2 and an electric quantity of 50 C / dm 2 . . Since the current value was low, a non-resistance ammeter was installed in the middle of the wiring, and cathode electrolysis was performed while confirming that the current was a predetermined value.
  • test piece was taken out from the treatment tank, washed with Hiratsuka water, air was removed by air blow, and a lubricating film was produced on the wire.
  • the adhesion amount in the lubricating film was 0.2 g / m 2 for calcium (calcium element) and 0.3 g / m 2 for isooctadecanoic acid.
  • the ratio (Im / Is) was 0.13.
  • the wire of Example 5 on which the lubricating film was formed was coated while measuring the weight so that the rust preventive oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) was 1.0 g / m 2 .
  • Example 6 A magnesium aqueous solution is prepared using magnesium acetate and deionized water, then nonanedioic acid is added, the pH is adjusted to 9.0 with ammonia and acetic acid, the concentration of magnesium ions is 5000 mass ppm, A composition for direct current cathode electrolysis of Example 6 having an acid concentration of 5000 ppm by mass was obtained.
  • a 5 L acrylic container (inner length 31 cm, width 12.6 cm, height 12.5 cm) was filled with the composition for direct current cathode electrolysis of Example 6 and heated to 35 ° C. in a hot water bath.
  • An insoluble anode (Permelec electrode oxygen generating DSE) was disposed inside the container in the longitudinal direction, and a cold-rolled steel sheet subjected to surface cleaning treatment was disposed as a cathode in the center of the container.
  • the distance between the anode and the cathode was 15 cm, and the area ratio was masked so that the anode area was 1/3.
  • An electrolysis operation was performed with a rectifier (ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.) to obtain a current density of 5 A / dm 2 and an electric quantity of 100 C / dm 2 .
  • the test piece was taken out from the treatment tank, washed with Hiratsuka water, water was removed by air blow, and a lubricating film was produced on the cold-rolled steel sheet.
  • Adhesion amount of lubricating film in the magnesium (magnesium element) is 0.8 g / m 2, nonane diacid was 0.2 g / m 2.
  • the ratio (Im / Is) was 0.11.
  • Anti-rust oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) was applied to the cold-rolled steel sheet of Example 6 on which the lubricating film was formed with a roll so as to be 1.0 g / m 2 .
  • Example 7 An aluminum complex aqueous solution is prepared using aluminum nitrate, NTA (nitrilotriacetic acid trisodium salt) and deionized water, then nonanedioic acid is added, and the pH is adjusted to 9.0 with ammonia and nitric acid.
  • concentration of aluminum ion is 2000 mass ppm and nonanedioic acid becomes 7000 mass ppm was obtained.
  • a 5 L acrylic container (inner length 31 cm, width 12.6 cm, height 12.5 cm) was filled with the composition for direct current cathode electrolysis of Example 7 and heated to 35 ° C. in a hot water bath.
  • An insoluble anode (Permelec electrode oxygen generating DSE) was disposed inside the container in the longitudinal direction, and a cold-rolled steel sheet subjected to surface cleaning treatment was disposed as a cathode in the center of the container.
  • the distance between the anode and the cathode was 15 cm, and the area ratio was masked so that the anode area was 1/3.
  • An electrolysis operation was performed with a rectifier (ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.) to obtain a current density of 5 A / dm 2 and an electric quantity of 100 C / dm 2 .
  • test piece was taken out from the treatment tank, washed with Hiratsuka water, water was removed by air blow, and a lubricating film was produced on the cold-rolled steel sheet.
  • the amount of adhesion in the lubricating film was 0.2 g / m 2 for aluminum (aluminum element) and 0.3 g / m 2 for nonanedioic acid.
  • the ratio (Im / Is) was 0.13.
  • Anti-rust oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) was applied to the cold-rolled steel sheet of Example 7 on which the lubricating film was formed with a roll so as to be 1.0 g / m 2 .
  • Example 8 An yttrium aqueous solution is prepared using yttrium nitrate and deionized water, then hexadiacid is added, the pH is adjusted to 9.0 with ammonia and nitric acid, the concentration of yttrium ions is 3000 ppm by mass, A composition for direct current cathode electrolysis of Example 8 in which the acid was 7000 ppm by mass was obtained. A 5 L acrylic container (inner length 31 cm, width 12.6 cm, height 12.5 cm) was filled with the composition for direct current cathode electrolysis of Example 8 and heated to 35 ° C. in a hot water bath.
  • An insoluble anode (Permelec electrode oxygen generating DSE) was disposed inside the container in the longitudinal direction, and a cold-rolled steel sheet subjected to surface cleaning treatment was disposed as a cathode in the center of the container.
  • the distance between the anode and the cathode was 15 cm, and the area ratio was masked so that the anode area was 1/3.
  • An electrolysis operation was performed using a rectifier (ZX-1600LA, manufactured by Takasago Seisakusho Co., Ltd.) to obtain a current density of 5 A / dm 2 and an electric quantity of 20 C / dm 2 .
  • the test piece was taken out from the treatment tank, washed with Hiratsuka water, water was removed by air blow, and a lubricating film was produced on the cold-rolled steel sheet.
  • Adhesion amount of lubricating film in the yttrium (yttrium element) is 0.2 g / m 2, nonane diacid was 0.5 g / m 2.
  • the ratio (Im / Is) was 0.15.
  • Anti-rust oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) was applied to the cold-rolled steel sheet of Example 8 on which the lubricating film was formed with a roll so as to be 1.0 g / m 2 .
  • the said embodiment corresponds to the aspect which did not implement cathode electrolysis.
  • Comparative Example 4 Calcium stearate was added to deionized water to make the composition of Comparative Example 4. This composition was cloudy and was a dispersion liable to settle. Using this, the composition was dip-coated on the wire and cold-rolled steel sheet so that the calcium stearate was 2 g / m 2 and carefully dried. After drying, the whole was white, but unevenness was observed. Further, it was easily expected that the white powder would fall off each time the wire rod and the cold rolled steel plate were handled, and the adhesion with the wire rod or the cold rolled steel plate would be poor.
  • the said embodiment corresponds to the aspect which did not implement cathode electrolysis.
  • Example 5 A 1 L graduated cylinder was regarded as a treatment tank, filled with the composition of Example 1 of Patent Document 1 (Japanese Patent Laid-Open No. 2000-144494), and heated to 80 ° C. Inside the treatment tank, a SUS mesh was placed as an anode. After preparing an aqueous solution containing 3% by mass of a colloidal titanium-based surface conditioner (preparene Z) manufactured by Nihon Parkerizing Co., Ltd. described in Patent Document 1 at room temperature, the surface-treated wire is subjected to immersion treatment for 1 minute.
  • a colloidal titanium-based surface conditioner preparene Z
  • an electrolysis operation was performed using a rectifier (ZX-1600LA manufactured by Takasago Seisakusho Co., Ltd.) with a wire rod as a cathode to obtain a current density of 20 A / dm 2 and an electric quantity of 50 C / dm 2 . Since the current value was low, a non-resistance ammeter was installed in the middle of the wiring, and cathode electrolysis was performed while confirming that the current was a predetermined value. Next, the test piece was taken out from the treatment tank, washed with Hiratsuka water, air was removed by air blowing, and a zinc phosphate coating was produced on the wire.
  • a rectifier ZX-1600LA manufactured by Takasago Seisakusho Co., Ltd.
  • the amount of zinc phosphate coating was calculated by dissolving and peeling the zinc phosphate coating with an aqueous chromic acid solution heated to 75 ° C., and calculating the amount of deposition from the weight difference before and after.
  • the amount of adhesion was 3.5 g / m 2 as zinc phosphate.
  • the same wire material was coated with a rust preventive oil (NOX-RUST530F manufactured by Parker Kosan Co., Ltd.) at 1.0 g / m 2 .
  • Comparative Example 6 By the same operation as that of Comparative Example 5, a wire having a zinc phosphate coating of 3.5 g / m 2 as zinc phosphate was obtained. Next, the wire was immersed in a reactive soap treatment liquid (Nippon Parkerizing Co., Ltd., PALOVE 235, 70 g / L) heated to 80 ° C. for 3 minutes. Due to the reaction of the reactive soap treatment generated by this operation, the aforementioned zinc phosphate was slightly dissolved to 3.0 g / m 2 . The total amount of metal soap and unreacted soap taken out from the liquid was 3.0 g / m 2 .
  • a reactive soap treatment liquid Nippon Parkerizing Co., Ltd., PALOVE 235, 70 g / L
  • the upper gripping portion was moved upward at a speed of 1 m / min, and the wire was passed through the die and drawn.
  • the pulling load when passing through the die was monitored with a personal computer.
  • the evaluation of Comparative Example 1 was “x”. “X”: When the pull-out load is the same as or larger than the pull-out load of Comparative Example 1, “ ⁇ ”: When smaller than the pull-out load of Comparative Example 1 and more than half of the pull-out load of Comparative Example 1, “ ⁇ ” ": When smaller than half of the drawing load of Comparative Example 1 It is preferable that no residue is generated at the entrance of the die during drawing. The case where no residue was generated at the entrance of the die was evaluated as “O”, and the case where residue was generated at the entrance of the die was evaluated as “ ⁇ ”.
  • the die 24 and the die 28 are fixed, and a load (wrinkle pressing load) is applied to the die 22 and the die 26 from the direction of the white arrow, so that both ends of the test piece 30 are between the die 22 and the die 24, and , Fixed between the die 26 and the die 28.
  • a load is applied to the punch 20 from the direction of the black arrow, and a wrinkle presser load for fixing the test piece 30 is scanned.
  • the load at which 30 led to breakage was investigated.
  • the wrinkle presser load value of Comparative Example 2 was evaluated according to the following evaluation criteria. The evaluation of Comparative Example 2 was “x”.
  • a degreasing agent (Fine Cleaner E2001 manufactured by Nihon Parkerizing Co., Ltd.) was heated to 43 ° C., and each test piece was immersed for 3 minutes to remove the lubricating film and the oil layer on the surface of the test piece.
  • the degreasing agent component on the test piece was washed away with Hiratsuka City water.
  • a surface conditioner (preparene X manufactured by Nihon Parkerizing Co., Ltd.), which is 2 g / L, was adjusted with Hiratsuka Water, and the test piece was immersed in the surface condition liquid for 30 seconds.
  • the ratio (Is / Im) indicates the peak intensity (Is) derived from the carbon element on the surface opposite to the metal material of the lubricant film and the surface of the lubricant film from the surface opposite to the metal material of the lubricant film.
  • the ratio (Im / Is) with the peak intensity (Im) derived from the carbon element at the intermediate position of the depth corresponding to 1/2 of the total thickness is intended.
  • the ratio (Is / Im) of the lubricating film in Comparative Example 6 in Table 1 is intended to be the ratio (Is / Im) in the film formed by the reactive metal soap treatment, and the zinc phosphate film is considered. Not.
  • metal element column of Comparative Examples 5 and 6 in Table 1 intends the amount of zinc phosphate
  • organic acid compound intends the amount of the film formed by the reactive metal soap treatment.
  • - means not implemented.
  • the lubricating film obtained by cathodic electrolysis using the composition of the present invention showed excellent lubricity and chemical conversion after degreasing.
  • Comparative Examples 1 and 2 in which only the oil layer is arranged Comparative Examples 3 and 4 in which the cathodic electrolysis treatment is not performed, and Comparative Examples 5 and 6 corresponding to the embodiment of Patent Document 1, the desired effect is obtained. It was not obtained.

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Abstract

L'invention fournit une composition pour électrolyse cathodique en courant continu qui permet de former un matériau métallique avec film de lubrification excellent en termes de propriétés lubrifiante et de propriétés de formation après dégraissage. La composition pour électrolyse cathodique en courant continu de l'invention comprend : au moins une sorte d'ion métal choisi dans un groupe constitué d'un ion métal typique divalent ou plus (à l'exclusion d'un ion zinc), et d'un ion des terres rares, ou un complexe de cet ion métal (A) ; un composé acide organique (B) contenant dans chaque cellule un groupe carboxyle et un groupe alkylène linéaire de 4 atomes de carbone ou plus ; et une eau (C).
PCT/JP2015/054150 2014-02-21 2015-02-16 Composition pour électrolyse cathodique en courant continu, et matériau métallique avec film de lubrification ainsi que procédé de fabrication de celui-ci WO2015125737A1 (fr)

Priority Applications (5)

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CN201580009607.9A CN106133201B (zh) 2014-02-21 2015-02-16 直流阴极电解用组成物、带有润滑皮膜的金属材料及其制造方法
JP2016504088A JP6211678B2 (ja) 2014-02-21 2015-02-16 直流陰極電解用組成物、潤滑皮膜付き金属材料およびその製造方法
KR1020167022672A KR101815412B1 (ko) 2014-02-21 2015-02-16 직류 음극 전해용 조성물, 윤활 피막이 형성된 금속 재료 및 그 제조 방법
MX2016010837A MX2016010837A (es) 2014-02-21 2015-02-16 Composicion para material equipado con pelicula lubricante, electrolisis catodica de corriente directa, y metodo para produccion de la misma.
US15/120,400 US20170073831A1 (en) 2014-02-21 2015-02-16 Composition for direct-current cathodic electrolysis, lubrication-film-equipped metal material, and production method therefor

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JP6211678B2 (ja) 2017-10-11
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TW201536963A (zh) 2015-10-01
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