WO2002086038A1 - Lubricating agent for use in working of metal material, and method for treatment thereof - Google Patents

Lubricating agent for use in working of metal material, and method for treatment thereof Download PDF

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Publication number
WO2002086038A1
WO2002086038A1 PCT/JP2002/003813 JP0203813W WO02086038A1 WO 2002086038 A1 WO2002086038 A1 WO 2002086038A1 JP 0203813 W JP0203813 W JP 0203813W WO 02086038 A1 WO02086038 A1 WO 02086038A1
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WO
WIPO (PCT)
Prior art keywords
lubricant
metal material
processing
group
metal
Prior art date
Application number
PCT/JP2002/003813
Other languages
French (fr)
Japanese (ja)
Inventor
Masayuki Yoshida
Yasuo Imai
Hidehiro Yamaguchi
Original Assignee
Nihon Parkerizing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nihon Parkerizing Co., Ltd. filed Critical Nihon Parkerizing Co., Ltd.
Publication of WO2002086038A1 publication Critical patent/WO2002086038A1/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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C9/00—Cooling, heating or lubricating drawing material
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • 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
    • C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/22—Compounds containing sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/24—Compounds containing phosphorus, arsenic or antimony
    • C—CHEMISTRY; METALLURGY
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    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26—Carboxylic acids; Salts thereof
    • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
    • C—CHEMISTRY; METALLURGY
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
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    • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
    • C10M143/02—Polyethene
    • C—CHEMISTRY; METALLURGY
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    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
    • C10M145/08—Vinyl esters of a saturated carboxylic or carbonic acid
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    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C—CHEMISTRY; METALLURGY
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    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/40—Polysaccharides, e.g. cellulose
    • C—CHEMISTRY; METALLURGY
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    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/02—Natural products
    • C10M159/06—Waxes, e.g. ozocerite, ceresine, petrolatum, slack-wax
    • C—CHEMISTRY; METALLURGY
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
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    • C10M2201/06—Metal compounds
    • C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
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    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/041—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction
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    • C10M2223/061—Metal salts
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    • 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
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    • C10N2040/243—Cold working
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    • C10N2040/245—Soft metals, e.g. aluminum
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    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
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    • C10N2040/247—Stainless steel
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

Definitions

  • the present invention relates to a lubricant for processing a metal material and a processing method thereof.
  • the present invention relates to a lubricant for metal material processing capable of imparting excellent lubricity to a surface of a metal material such as steel, stainless steel, titanium, and aluminum without being subjected to a chemical conversion treatment, and a method for treating the lubricant.
  • a lubricous film suitable for forging, drawing, drawing, and other metal materials such as steel, stainless steel, titanium, and aluminum can be formed without chemical conversion.
  • TECHNICAL FIELD The present invention relates to an aqueous lubricant for plastic working of a metal material that can be formed, and a technique related thereto. Background art
  • a lubricating film is provided on the surface of the metal material to prevent seizure and galling caused by metal contact between the work material and the tool. I have.
  • the film of the above (X) type is inferior in adhesion to the film of the above (Y) type, so that it is generally used only for light machining. If there is a carrier on the metal material surface A phosphate film or an oxalate film, which has the role of a lubricant, is generated, and a slippery lubricant is provided on the film.
  • This type of coating has a very high seizure resistance because it has a two-layer structure consisting of a chemical conversion coating as a carrier coating and a lubricant. For this reason, it has been used in a very wide range in the field of plastic working such as drawing, drawing, and forging.
  • a method of forming a base film such as a phosphate film or an oxalate film on a metal surface and applying a lubricant thereon is often used.
  • the lubricant applied on the chemical conversion coating can be divided into two types depending on the method of use.
  • One type is a type (Y1) in which a lubricant is physically attached to a chemical conversion coating.
  • the other type is a type (Y 2) in which a lubricant reacts and adheres to a chemical conversion coating.
  • Examples of the former (Y1) lubricant include mineral oils, vegetable oils, and synthetic oils as base oils, to which extreme pressure agents are added, and solid lubricants such as graphite and molybdenum disulfide. And those dissolved in water together with a single component. These lubricants can be easily used by spray coating and dip coating. Therefore, there is an advantage that liquid management is almost unnecessary. However, since lubricity is low, it can be used only when lubricity is relatively light.
  • examples of the latter (Y 2) lubricant include reactive stones such as sodium stearate.
  • a reactive conversion stone is used after forming a chemical conversion coating.
  • a lubricant composition comprising a water-soluble polymer or an aqueous emulsion thereof as a base material and a solid lubricant and a chemical conversion film forming agent is proposed (Japanese Patent Laid-Open No. No. 52-20967).
  • a water-soluble inorganic salt (b) solid lubricant; (c) at least one oil component selected from mineral oil, animal and plant fats and oils, and (d) surface activity.
  • a water-based lubricant for cold plastic working of a metal consisting of an agent and (e) water has been proposed (Japanese Patent Application Laid-Open No. 10-85085).
  • an object of the present invention is to solve the above-mentioned problems of the prior art.
  • An object of the present invention is to provide a technology related to a lubricant for metal material processing that does not require chemical conversion treatment (particularly, an aqueous lubricant for plastic working of metal material).
  • the object is to reduce the amount of divalent or trivalent metal selected from the group of Zn, Fe, Mn, Ni, Co, Ca, Mg and A1.
  • a dispersant (B) A dispersant (B),
  • At least one lubricant selected from the group of waxes and metal salts of fatty acids (C)
  • Phosphate (A) used in the present invention has good followability during processing and a lubricant.
  • Carrier properties are provided. Therefore, it is important that they have the property of being uniformly dispersed or dissolved in a solution and of forming a strong film when dried.
  • a phosphate having such characteristics divalent or divalent selected from the group consisting of Zn, Fe, ⁇ , Ni, Co, Ca, Mg and Al Phosphate (A) containing at least one trivalent metal is mentioned. These may be used alone or in combination of two or more. For example, there are the phosphates listed below. Note that phosphate exists as a hydrate such as dihydrate or tetrahydrate. However, there is not much difference in the effect depending on the number of hydration waters, and therefore, examples are given below in the form of anhydrous salts.
  • phosphate (A) used in the present invention it is preferable to use particles having an average particle size of 3 m or less. This is because the use of too large a phosphate (A) reduces the dispersion stability.
  • phosphate There is no particular limitation on the lower limit of the size of (A), but the lower limit of the size that can be practically obtained is about 0.3.
  • Dispersant (B) used in the present invention that is, dispersant for phosphate (A)
  • At least one selected from the group consisting of orthophosphoric acid, polyphosphoric acid, organic phosphonic acid compounds and derivatives thereof can be used.
  • at least one selected from the group of polymers obtained using unsaturated carboxylic acids and / or esters thereof can also be used.
  • at least one selected from the group consisting of monosaccharides, polysaccharides, and derivatives thereof can also be used.
  • at least one selected from the group consisting of biel acetate acetate polymers can be used.
  • at least one kind selected from the group of urethane-based polymers can be used.
  • the dispersant (B) of the present invention has a function of enhancing the dispersion stability of the phosphate particles and fixing the phosphate to the metal surface. Adsorbs on the surface of the phosphate particles and prevents repulsion and steric hindrance by the charge to prevent collisions between the phosphates in the surface treatment agent, thereby preventing coagulation and sedimentation. Further, the dispersant (B) has a structure capable of adsorbing to the surface of the metal material because of its structure, so that the phosphate can be fixed to the surface of the metal material. An excellent film can be obtained only by applying and drying the agent of the present invention on the metal surface.
  • the phosphate (A), the dispersant (B) and the lubricant (C) are used in combination.
  • the lubricant (C) used in this combination is at least one lubricant selected from the group consisting of waxes and metal salts of fatty acids. It is. Above all, it is a synthetic wax dispersed in water. Alternatively, it is a reaction product of at least one selected from the group consisting of Zn, Ca, Ba, A1, Mg and Li with a fatty acid having 12 to 26 carbon atoms.
  • the agent of the present invention further contains at least one inorganic salt (D) selected from the group consisting of sulfates, silicates, borates, molybdates, and tungstates. This is preferred. This improves the strength and adhesion of the film.
  • the agent of the present invention contains a known viscosity improver, if necessary, for the purpose of assisting film formation.
  • the above object is also achieved by a surface-treated metal material characterized in that the metal material processing lubricant having the above characteristics is provided on a metal material surface having a thickness of 0.5 to 40 g Zm 2. Achieved.
  • the above object is also achieved by a method for forming a lubricating film of a metal material, which comprises contacting the metal material with the lubricant for processing a metal material having the above characteristics, and then drying the metal material.
  • the above-mentioned object is achieved by at least one cleaning selected from the group consisting of shot blast, sand blast, alcohol degreasing, and acid cleaning.
  • the metal material is brought into contact with the lubricant for processing a metal material having the above characteristics, and then dried. Is also achieved.
  • the metal material heated to 60 to 100 is brought into contact with the metal material processing lubricant.
  • Figure 1 is a schematic diagram of the test material.
  • Figure 2 is a schematic diagram of the posterior drill test.
  • Figure 3 is a schematic diagram of the molded product.
  • Figure 4 is a schematic diagram of the spike test.
  • Figure 5 is a schematic diagram showing the deformation before and after the spike test.
  • Lubricants for metal material processing according to the present invention are subjected to plastic processing such as forging, wire drawing, and pipe drawing.
  • Metallic materials that can form a suitable lubricating film without chemical conversion treatment when carrying out a water-based lubricant for plastic working are Zn, Fe, ⁇ , ⁇ i, CoCa, M g and A 1, a phosphate (A) containing at least one divalent or trivalent metal selected from the group consisting of a divalent or trivalent metal, a dispersant (B), a wax, and It contains at least one lubricant (C) selected from the group of fatty acid metal salts.
  • phosphoric acid (A) particles having an average particle diameter of 3 m or less are particularly used.
  • Dispersants (B) include orthophosphoric acid, polyphosphoric acid, organic phosphonic acid compounds, and the like. Or at least one selected from the group of polymers obtained using unsaturated carboxylic acids and / or esters thereof, or at least one selected from the group of derivatives of At least one selected from the group of saccharides, polysaccharides and derivatives thereof, or at least one selected from the group of vinyl acetate polymers, or within the group of urethane polymers Particularly, at least one kind selected from among them is used.
  • the lubricant (C) is particularly used in combination.
  • This lubricant (C) is at least one lubricant selected from the group of waxes and metal salts of fatty acids. Above all, it is a synthetic resin dispersed in water. One is a reaction product of at least one selected from the group consisting of Zn, Ca, Ba, A1, Mg and Li with a fatty acid having 12 to 26 carbon atoms. .
  • the present invention further comprises at least one inorganic salt (D) selected from the group consisting of sulfates, silicates, borates, molybdates and ungstenates.
  • D inorganic salt
  • the present invention contains a known viscosity improver, if necessary, for the purpose of assisting film formation.
  • the surface-treated metal material according to the present invention is one in which the lubricant for metal material processing having the above characteristics is provided on the surface of a metal material having a thickness of 0.5 to 40 g / m 2 .
  • the method for forming a lubricating film of a metal material according to the present invention is a method of bringing a metal material into contact with a lubricant for processing a metal material having the above characteristics, and then drying the metal material. It is. In particular, after cleaning the surface of the metal material by at least one cleaning means selected from the group consisting of shot blast, sand blast, alkaline degreasing, and acid cleaning, Is brought into contact with the above-mentioned lubricant for processing a metal material and then dried. It is preferable that the metal material heated to 60 to 100 ° C. is brought into contact with the metal material processing lubricant.
  • the phosphate (A) used in the water-based lubricant for plastic working of metal materials of the present invention imparts followability during working and carrier properties of the lubricant. It is for doing. For this reason, it is important that the phosphate (A) has the property of being uniformly dispersed or dissolved in a solution and of forming a strong film when dried.
  • a divalent material selected from the group consisting of Zn, Fe, Mn, Ni, Co, Ca, Mg, and Al may be used.
  • Is a phosphate (A) containing at least one trivalent metal may be used alone or in combination of two or more. Specific examples are given below.
  • the particle size of the phosphate (A) is preferably an arithmetic mean particle size of 3 or less. This is because the dispersion stability of the treatment liquid is deteriorated when the particle diameter is large.
  • the inventors of the present invention have prepared the gold of the present invention containing any of the dispersants described below. It has been found that a film provided by applying a lubricant for processing a metal material exhibits excellent conformability, carrier properties, and adhesiveness.
  • the dispersant (B) of the present invention has a function of improving the dispersion stability of the phosphate particles and fixing the phosphate to the surface of the metal material.
  • the dispersant (B) is adsorbed on the surface of the phosphate particles, and the repulsion and steric hindrance of the charge prevent the phosphates from colliding with each other in the surface treatment agent, thereby preventing aggregation and sedimentation. .
  • the dispersant (B) has an adsorption ability to a metal surface due to its structure. For this reason, it becomes possible to fix the phosphate on the metal surface. Therefore, an excellent film can be obtained only by applying and drying the lubricant for processing a metal material of the present invention on the surface of the metal to be treated.
  • dispersant (B) of the present invention at least one selected from the group consisting of orthophosphoric acid, polyphosphoric acid, organic phosphonic acid compounds, and derivatives thereof is preferably used.
  • Orthophosphoric acid is orthophosphoric acid.
  • polyphosphoric acid include pyrrolic acid, triphosphoric acid, trimethacrylic acid, tetramethylphosphoric acid, hexametaphosphoric acid, and metal salts thereof and alcohols thereof.
  • Monmonium salt can be used.
  • the organic phosphonic acid compound include aminotrimethylenephosphonic acid, 1-hydroxyxethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and alkali alcohols thereof.
  • Metal salts can be used.
  • One type of orthophosphoric acid, polyphosphoric acid or organic phosphonic acid compound may be used, or a combination of several types may be used.
  • the dispersant (B) other than the above at least one selected from the group of polymers obtained using unsaturated carboxylic acids and Z or esters may be used. More specifically, the group of monomers of acrylic acid (or methacrylic acid) ester represented by the following general formula (I) and a // 3 unsaturated carboxylic acid monomer A polymer composed of at least one monomer selected from the group consisting of at least one monomer, or a copolymer composed of a monomer (50% by weight or less) copolymerizable with the monomer. Coalescing is preferably used.
  • Monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate.
  • Unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, and maleic acid.
  • Examples of the monomer copolymerizable with the above monomer include vinyl acetate, styrene, biel chloride, vinyl sulfonic acid, and the like.
  • dispersant (B) other than the above at least one selected from the group consisting of monosaccharides, polysaccharides and derivatives thereof may be used.
  • the basic constituent saccharides of the monosaccharides, polysaccharides and derivatives thereof used in the present invention include, for example, fructos, evening gatose, psicose sulfose, erythrose, threose, reportose, arabinose, and the like.
  • a monosaccharide is used, the basic constituent saccharide itself can be used.
  • a polysaccharide a homopolysaccharide or a heteropolysaccharide of the basic constituent saccharides can be used.
  • a monosaccharide, a homopolysaccharide or a heteropolysaccharide containing a monosaccharide substituted with the substituent in the structure can be used.
  • Several types of monosaccharides, polysaccharides, and derivatives thereof may be used in combination.
  • When classifying saccharides they may be classified as monosaccharides, small saccharides, and polysaccharides depending on the degree of hydrolysis.
  • polysaccharides that generate two or more monosaccharides by hydrolysis are referred to as polysaccharides, and saccharides that themselves are not further hydrolyzed are referred to as monosaccharides.
  • the use of the present invention is independent of biochemical reactions. Therefore, the effect depends on the steric configuration and optical rotation of the basic constituent saccharides. No. Therefore, any combination of D-monosaccharide, L-monosaccharide and optical rotation (10,1) can be used. Further, in order to increase the water solubility of the monosaccharide, the polysaccharide, and the derivative thereof, an alkali metal salt or an ammonium salt of the monosaccharide, the polysaccharide, and the derivative thereof may be used. Further, when it is difficult to make water soluble with the above-mentioned structure, it may be used after previously dissolving it in an organic solvent compatible with water.
  • At least one selected from the group of vinyl acetate polymers may be used.
  • Examples of the vinyl acetate-based polymer include an aqueous polymer compound such as a vinyl acetate polymer, a copolymer of vinyl acetate and a monomer copolymerizable with vinyl acetate, and a derivative thereof.
  • polyvinyl alcohol which is a saponified product of biel acetate, and cyanoethylated poly (vinyl alcohol) and polyvinyl alcohol, which are obtained by cyanoethylating polyvinyl alcohol with acrylonitrile Of formalized polyvinyl alcohol obtained by acetalizing with formalin, urethanized polyvinyl alcohol obtained by urethanizing polyvinyl alcohol with urea, and urepoxyl group and sulfone of polyvinyl alcohol And an aqueous polymer compound into which a amide group or the like is introduced.
  • Examples of the monomer copolymerizable with vinyl acetate in the present invention include acrylic acid, crotonic acid, maleic anhydride, and ethylene. If the vinyl acetate polymer, or a copolymer of vinyl acetate and a monomer copolymerizable with vinyl acetate and biel acetate, or a derivative thereof is aqueous, the effects of the present invention can be sufficiently exerted. Therefore, impeachment does not depend on the degree of polymerization or the rate of introduction of functional groups. In addition, the monomer It is permissible to use one type of copolymer or a combination of several types.
  • At least one selected from the group of urethane polymers may be used.
  • urethane-based polymer examples include a urethane resin, a copolymer of urethane and a monomer copolymerizable with urethane, and a water-soluble polymer compound such as a derivative thereof.
  • the present inventors have found that, when the lubricant (C) is present together with the phosphate (A) and the dispersant (B), the friction coefficient during plastic working is reduced, and good lubricity is exhibited. .
  • the lubricant (C) of the present invention having such features is at least one kind of lubricant selected from the group consisting of waxes and metal salts of fatty acids.
  • the wax a synthetic wax is preferable. Wax is melted by the heat generated during plastic working, improving the lubricity of the film. For this reason, it is desirable that the material has a melting point of 70 to 150 ° C, is stable in an aqueous solution, and does not reduce the film strength so that the effect is exerted at the initial stage of processing. Examples thereof include microcrystalline wax, polyethylene wax, polypropylene wax, and karenenaunox. These components are preferably mixed with other components in the form of a water dispersion / water emulsion.
  • Any metal salt of a fatty acid may be used.
  • Metal salts of fatty acids obtained by reacting with a kind of metal are preferred.
  • calcium stearate, zinc stearate, barium stearate, magnesium stearate, and lithium stearate are preferred.
  • the fatty acid metal salt of the present invention exists in a form dispersed in the aqueous lubricant of the present invention.
  • a known surfactant is used, if necessary, to disperse and exist.
  • any of a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, and a cationic surfactant may be used. . These surfactants may be used alone or in combination of two or more. These surfactants are not particularly limited. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyalkylene (ethylene and / or propylene) alkyl phenyl ether, and polyethylene glycol (or ethylene oxide).
  • Polyoxyethylene alkyl esters composed of fatty acids (for example, having 12 to 18 carbon atoms), and polyoxyethylenes composed of sorbitan, polyethylene glycol, and higher fatty acids (for example, having 12 to 18 carbon atoms). And rensorbin alkyl esters.
  • the anionic surfactant include a fatty acid salt, a sulfate, a sulfonate, a phosphate, a dithiophosphate, and the like.
  • Examples of the amphoteric surfactant include amino acid type and betaine type carboxylate, sulfate, sulfonate, phosphate and the like.
  • Examples of the cationic surfactant include a fatty acid amine salt and a quaternary ammonium salt.
  • a fatty acid amine salt and a quaternary ammonium salt.
  • the inorganic salt (D) is used.
  • these inorganic salts include sodium sulfate, potassium sulfate, potassium gayate, sodium borate (sodium tetraborate), and sodium borate ( Examples thereof include ammonium tetraborate, ammonium borate (ammonium tetraborate, etc.), ammonium molybdate, sodium molybdate, sodium tungstate, and the like. These may be used alone or in combination of two or more.
  • a known viscosity improver is used as needed for the purpose of assisting film formation.
  • a viscosity improver is effective for improving smoothness and suppressing film unevenness.
  • examples of viscosity improvers include smectite-based viscosity minerals (montmorillonite, sauconite, paiderite, hectrite, etc.). There are no particular restrictions on the amount or type of the composition.
  • (B) / (A) is 0.01 to 5.0 of the solid content weight ratio of the phosphate (A), the dispersant (B), and the lubricant (C).
  • the ratio is in the range of 0.1 to 2 If the ratio is less than 0.01, the dispersion stability is poor. Exceeding 5 does not adversely affect stability, but increases costs.
  • (C) / (A) is preferably in the range of 0 ′ ⁇ 1 to 5. More preferably, it is in the range of 0.5 to 2.5. If it is less than 0, the sliding property is poor. If it exceeds 5, more scum will be generated during plastic working, which may cause mold stagnation.
  • the weight ratio of solid content (D) / (A) of the salt (D) is preferably in the range of 0.01 to L 0. A more preferred range is from 0.1 to 4.
  • the inorganic salt is added for the purpose of improving the adhesion. If the weight ratio is less than 0.01, the effect is difficult to sufficiently exert. Even if the weight ratio exceeds 10, there is no problem in performance, but there may be a problem in the stability of the processing solution.In case of severe processing, the plastic working for the metal material of the present invention Oil and solid lubricants are further added to the water-based lubricant as lubrication aids.
  • the water-based lubricant for plastic working of the present invention is applied to metal materials such as iron or steel, stainless steel, copper or copper alloy, aluminum or aluminum alloy, titanium or titanium alloy.
  • the shape of the metal material is not particularly limited, because not only materials such as a bar material and a block material but also a forged shape (gear, shaft, etc.) can be processed.
  • the coating treatment method of the present invention is a method in which a cleaned metal material is brought into contact with the lubricant and then dried. As a result, a lubricating film is formed on the surface of the metal material. This lubricating film is of the unreacted type. Adhesion amount of the lubricant film to be formed on the metal surface, but is then appropriate Control
  • This setup rolls Ri by the degree of work, in the range of 0. 5 ⁇ 4 0 g Z m 2. More preferably, it is in the range of 2 to 20 g / m 2 . If the amount is less than 0.5 g / m 2 , lubricity tends to be insufficient.
  • the amount of adhesion can be calculated from the weight difference and the surface area of the metal material before and after the treatment.
  • the weight (concentration) of the solid content of the aqueous lubricant is appropriately adjusted.
  • high concentrations of Lubricants are often diluted and used in their processing solutions.
  • the water for dilution adjustment is not particularly limited, but deionized water or distilled water is preferable.
  • the metal material is cleaned by at least one method selected from the group consisting of shot blasting, sand blasting, alkaline degreasing and acid cleaning when treating the lubricating coating on the metal material.
  • the purpose of cleaning is to remove oxide scales and various stains (oil, etc.) grown by annealing or the like. It is hoped that this will be reduced.
  • the surface of the metal material is cleaned with a shot blast, and then the lubricant and the treatment method of the present invention are used, whereby zero wastewater can be approached.
  • the method for bringing the aqueous lubricant of the present invention into contact with a metal material is not particularly limited.
  • an immersion method, a flow coat method, a spray method, or the like can be used.
  • the coating may be performed as long as the surface is covered with the aqueous lubricant of the present invention.
  • the metal material In order to enhance the drying property, it is preferable to heat the metal material to 60 to 100 ° C and bring it into contact with an aqueous lubricant.
  • the metal material may be brought into contact with an aqueous lubricant heated to 50 to 90 ° C.
  • the drying property is greatly improved, and drying can be performed at room temperature in some cases, thereby reducing heat energy loss.
  • Posterior drilling specimen The material subjected to the posterior drilling test was a commercially available S45C spheroidized annealed material. The shape of the test piece was changed from 30 mm in diameter and 16 to 40 mm in 2 mm increments.
  • the material tested was a commercially available S45C spheroidized annealed material.
  • the shape of the test specimen is 25 mm in diameter and 30 mm in height.
  • the cylindrical test material 1 shown in Fig. 1 is formed by a die 2 and a punch 3 of the 200 t crank press shown in Fig. 2 to produce a cup-shaped molded product shown in Fig. 3.
  • a die 2 has SKD 11
  • the punch 3 has HAP 40 land diameter 21.2 1 ⁇
  • the processing speed is 30 strokes Z.
  • the height in the cup of the test piece with no scratches on the inner surface shall be the good drilling depth (mm). The deeper the hole, the better. The good drilling depth of 56 mm obtained with the conventional technology is used as a guide.
  • the spike test was performed according to Japanese Patent Application Laid-Open No. 5-7969. That is, as shown in FIG. 4, a columnar specimen 5 is placed on a die 6 having a funnel-shaped inner surface, a load is applied by a platen 7, and the specimen 5 is pushed into the die 6. Molding.
  • the phosphate (A) used in the examples was prepared as follows.
  • Hopai Doo ( ⁇ 3 ( ⁇ 0 4) 2 ⁇ 4 ⁇ 2 0) was used reagents.
  • the orthophosphoric acid and polyphosphoric acid organic phosphonic acid compound of the dispersant (II) used in Examples 1 to 3 were selected from reagents and commercial products (for example, manufactured by Nippon Monsanto Industry Co., Ltd.). The structure was selected based on the structure.
  • the ⁇ ⁇ of the processing solution does not affect the effect of the present invention. However, if the ⁇ ⁇ of the aqueous solution of orthophosphoric acid, polyphosphoric acid or organic phosphonic acid compound is remarkably low, sodium hydroxide is added in advance to prevent dissolution of phosphate. The pH of the aqueous solution was adjusted to neutral with a system.
  • Dispersant Example 4 is wherein R 1 in the general formula (I) is Eta R was used monomers C 2 Eta 4.
  • a polymer (copolymer) polymerized using i8 unsaturated carboxylic acid (acrylic acid) and ammonium persulfate as a catalyst was used.
  • polymerization was carried out after emulsification using a commercially available surfactant. If the ⁇ ⁇ of the polymer (copolymer) is extremely low, the ⁇ ⁇ of the polymer (copolymer) solution must be adjusted with sodium hydroxide in advance to prevent dissolution of phosphate. It was adjusted to sex.
  • Monosaccharides, polysaccharides and derivatives thereof of the dispersant (B) used in Examples 6 to 9 are commercially available products, for example, Daicel Chemical Industries, Daiichi Kogyo Pharmaceutical Co., Ltd., Asahi Kasei Kogyo Co., Ltd. Pharmaceuticals Co., Ltd. and others were selected based on the type, degree of polymerization, substituents, and degree of substitution of the basic constituent sugars.
  • the substituent is exemplified by glucose which is one of the basic constituent sugars in the chemical formula (II).
  • the hydroxyl groups at three sites, R 3 , R 4 , and R 5 can be etherified.
  • the type and degree of substitution (the number of substitutions of hydroxyl groups per unit of the basic constituent sugar by the substituent) were changed, and the effect was investigated.
  • sodium salts were used for low water-soluble monosaccharides, polysaccharides, and their derivatives.
  • the substituents CH 2 COOH, NO 2 , the degree of substitution of 8 or more, and the degree of polymerization of 300 or more were used.
  • Example 8 one having a substituent of CH 2 COOH, a degree of substitution of 0.7, and a degree of polymerization of 100 or more was used.
  • the vinyl acetate polymer or the derivative of the dispersant (B) used in Examples 10 and 11 a commercially available polyvinyl alcohol was used in Example 10.
  • Example 11 a commercially available copolymer of vinyl acetate and ethylene was used.
  • the surface treatment agent 1 was prepared by using this solution and a dispersion solution of microcrystalline wash (lubricant (C)).
  • (B) / (A) of this treating agent 1 is 1.0, and (C) / (A) is 1.0.
  • step A a treatment was carried out in step A so that the amount of coating film became 8 g nom 2 .
  • phosphophyllite (phosphate (A)) 1 kg of a 10 wt% shark phosphate solution (dispersant (B)) was added. This was followed by grinding for about 1 hour with a pole mill using 0.5 mm diameter zirconia beads. After pulverization, the arithmetic average particle diameter of the fine particles in the liquid was measured with LA-920. The arithmetic mean particle size was 0.5 m.
  • the surface treatment agent 2 was prepared by using this solution and a dispersion solution of calcium stearate (lubricant (C)).
  • (B) / (A) of this treating agent 2 is 2.0, and (C) / (A) is 4.0.
  • step A a treatment was carried out in step A so that the amount of the coating film became 10 g / m 2 .
  • the surface treatment agent 3 was prepared by using this solution and a dispersion solution of polyethylene wax (lubricant (C)).
  • (B) / (A) of this treating agent 3 is 1.0, and (C) / (A) is 0.5.
  • step A Using this treating agent, a treatment was performed in step A so that the amount of coating film became 10 g / m 2 .
  • phosphophyllite (phosphate (A) For 20 g of phosphophyllite (phosphate (A)), a polymer prepared from a monomer (R 1 is H and R 2 is C 2 H 4 ) in the formula of chemical formula (I) is 10 1 kg of a wt% diluted solution (dispersant (B)) was added. This Thereafter, the mixture was ground for about 1 hour with a pole mill using 0.5 mm-diameter zirconia beads. After pulverization, the suspension was adjusted with tap water so that the concentration of phosphoric acid in the suspension was 1%. The arithmetic average particle size of the fine particles in the solution was measured with LA-920. The arithmetic mean particle size was 0.5 am.
  • the surface treatment agent 4 was prepared by adjusting this solution, a dispersion solution of calcium stearate, and a dispersion solution of crystal mouth wax (lubricant (C)).
  • the weight ratio of calcium stearate to microcrystalline detergent was 1: 1.
  • (B) / (A) of this treating agent 4 is 5.0, and (C) / (A) is 2.5.
  • step A Using this treating agent, a treatment was performed in step A so that the amount of coating film became 10 g / m 2 .
  • the surface treatment agent 6 was prepared by adjusting the arithmetic mean particle size of the solution having a diameter of 0.5 m and a dispersion solution of microcrystalline detergent (lubricant (C)). (B) / (A) of this treating agent 6 is 2.0, and (C) / (A) is 1.0.
  • step B Using this treating agent, a treatment was performed in step B so that the amount of coating film became 15 g / m 2 .
  • a surface treatment agent 7 was prepared.
  • (B) / (A) of this treating agent 7 is 5.0, and (C) / (A) is 3.0.
  • step B the coating weight was reduced to 20 g Z m 2
  • the treatment was performed as follows.
  • the surface treatment agent 8 was prepared by using this solution and a dispersion solution of polyethylene wax (lubricant (C)).
  • (B) / (A) of this treating agent 8 is 5.0, and (C) / (A) is 0.5.
  • step B Using this treating agent, a treatment was performed in step B so that the amount of coating film became 10 g Zm 2 .
  • the surface treatment agent 9 was prepared by using this solution, a dispersion solution of zinc stearate, and a dispersion solution of micro-crosslinking solution (lubricant (C)).
  • the weight ratio of zinc stearate to microcrystalline wax was 1: 1.
  • (B) / (A) of this treating agent 9 is 5.0, and (C) / (A) is 2.5.
  • step B the coating weight was reduced to 20 g Z m 2 Processing was performed as follows.
  • phosphophyllite phosphate (A)
  • lkg of a solution (dispersant (B)) obtained by diluting and dissolving polyvinyl alcohol in 10 wt% was added. Thereafter, the mixture was ground for about 1 hour with a pole mill using zirconia beads having a diameter of 0.5 mm. After pulverization, the arithmetic average particle diameter of the fine particles in the solution was measured by LA-920. The arithmetic mean particle size was 0.5 m.
  • Preparation was performed using this solution, a dispersion of sodium stearate and a dispersion of paraffin wax (lubricant (C)).
  • the weight ratio between sodium stearate and paraffin wax was set to 1: 2.
  • step B treatment was performed in step B so that the amount of coating film became 5 g / m 2 .
  • potassium silicate inorganic salt (D) was added to the solution to prepare a surface treatment agent 11.
  • (B) / (A) of this treating agent 11 is 1.0
  • (C) / (A) is 1.0
  • (D) / (A) is 2.0.
  • the treatment was performed so that the coating amount became 15 g Zm 2 .
  • step A Using this treating agent, a treatment was performed in step A so that the amount of coating film became 5 g Zm 2 .
  • the concentration of the dispersant (B) was adjusted to 5%, and the concentration of the lubricant (C) was adjusted to 5%.
  • step B Using this treating agent, a treatment was performed in step B so that the amount of coating film became 10 g / m 2 .
  • step A treatment was performed so that the coating amount became 10 g / m 2 .
  • Water-soluble inorganic salt sodium tetraborate 10%
  • Solid lubricant Calcium stearate 10%
  • Oil component palm oil 0.5%
  • aqueous lubricant 15 shown below (based on the invention of Japanese Patent Application Laid-Open No. 2000-0-6380), in the process A, the coating amount becomes 10 g Zm 2 in the process A. Processed. [Water-based lubricant 15]
  • Water-soluble inorganic salt sodium tetraborate 6%
  • Fatty acid metal salt Calcium stearate 9%
  • Example 14 4 Coating type 60.13.1 Example 2 4 6 0 13.2 Example 3 4 Coating type 60.13.3 Example 4 4 Coating type 60.13.1 Example 5 4 coating type 6 0 1 3 4 Example 6 4 coating type 6 0 1 3 4 Example 7 4 coating type 6 0 1 3 2 Example 8 4 coating type 6 0 1 3 2 2 Example 9 4 Coating type 6 1 1 3 4 Example 1 0 4 Coating type 6 0 1 3 .5 Example 1 1 4 6 0 1 3 .5 Comparative example 1 4 Coating type 3 6 Burn-in Comparative example 2 4 Coating type 4 0 1 1.
  • Comparative Example 1 containing no component (C) had poor lubricity.
  • the spike test caused seizure and could not be formed.
  • Comparative Example 2 containing no component (A) also had poor lubricity.
  • Comparative Example 3 using a phosphate film and a reaction stone / lubricant has relatively good lubricity, but is somewhat inferior to that of the present invention.
  • wastewater treatment and liquid management are required, and it cannot be used with simple equipment.
  • waste is generated due to the reaction, resulting in a large environmental burden.
  • Comparative Example 4 corresponding to the invention of JP-A-10-85085, and Comparative Example in which the main component is a synthetic resin corresponding to the invention of JP-A-2000-6380. 5 has poor lubricity in spike test and posterior drill test. Industrial applicability
  • the production yield is high due to good lubricity.
  • global environmental preservation is considered. That is, the amount of waste is small and the working environment is good.
  • it can be performed by a simple treatment such as no chemical conversion treatment is required.

Abstract

A lubricating agent which comprises a phosphate salt (A) containing at least one divalent or trivalent metal selected from the group consisting of Zn, Fe, Mn, Ni, Co, Ca, Mg and Al, a dispersant (B), and at least one lubricant (C) selected from the group consisting of a wax and a metal salt of a fatty acid. The lubricating agent is an aqueous agent and can be used for forming a lubricating coating film suitable for a plastic working, such as forging, wire drawing or pipe drawing, of a metal material such as steel, stainless steel, titanium or aluminum, without a chemical treatment of the metal material.

Description

明 細 書 金属材料加工用潤滑剤、 及びその処理方法 技術分野  Description Lubricants for processing metal materials and their processing methods
本発明は金属材料加工用潤滑剤及びその処理方法に関する。 特 に、 鉄鋼、 ステンレス、 チタ ン、 アルミニウム等の金属材料の表 面に、 化成処理を施さなく ても、 優れた潤滑性を付与できる金属 材料加工用潤滑剤及びその処理方法に関する。 更に詳し く述べる ならば、 鉄鋼、 ステンレス、 チタン、 アルミニウム等の金属材料 を鍛造、 伸線、 伸管のような塑性加工を行う際に好適な潤滑性の 皮膜を、 化成処理を施さなく ても、 形成できる金属材料塑性加工 用水系潤滑剤、 並びにこれに関連した技術に関する。 背景技術  The present invention relates to a lubricant for processing a metal material and a processing method thereof. In particular, the present invention relates to a lubricant for metal material processing capable of imparting excellent lubricity to a surface of a metal material such as steel, stainless steel, titanium, and aluminum without being subjected to a chemical conversion treatment, and a method for treating the lubricant. More specifically, a lubricous film suitable for forging, drawing, drawing, and other metal materials such as steel, stainless steel, titanium, and aluminum can be formed without chemical conversion. TECHNICAL FIELD The present invention relates to an aqueous lubricant for plastic working of a metal material that can be formed, and a technique related thereto. Background art
一般に、 鉄鋼、 ステンレス等の金属材料を塑性加工する際、 被 加工材と工具との金属接触によ り 生ずる焼き付きやカジ リ を防 止する 目的で、 金属材料表面に潤滑性の皮膜を設けている。  Generally, when plastically processing a metal material such as steel or stainless steel, a lubricating film is provided on the surface of the metal material to prevent seizure and galling caused by metal contact between the work material and the tool. I have.
このような皮膜と しては、  As such a film,
( X ) 金属材料表面に潤滑剤を物理的に付着させたタイ プの皮膜 (X) A type of film in which a lubricant is physically attached to the metal material surface
( Y ) 金属材料表面に化成処理皮膜を設け、 その上に潤滑剤を設 けたタイ プの皮膜 (Y) A chemical conversion coating on the surface of a metal material, and a lubricant coating on top
がある。 There is.
上記 （ X ) タイ プの皮膜は、 上記 （ Y ) タイ プの皮膜に比べ、 密着性が劣る為、 一般に、 軽加工用と して使用される程度である 上記 （ Y ) タイ プの皮膜にあっては、 金属材料表面にキャ リ ア と しての役割を有する リ ン酸塩皮膜や蓚酸塩皮膜を生成させ、 そ の上に滑り性のある潤滑剤を設けたものである。 このタイ プの皮 膜は、 キャ リ ア皮膜と しての化成皮膜と潤滑剤との二層構造を有 している こ とから、 非常に高い耐焼き付き性を示す。 この為、 伸 線、 伸管、 鍛造などの塑性加工分野において、 非常に広い範囲で 使用されて来た。 そして、 塑性加工の中でも加工が特に厳しい分 野では、 金属表面にリ ン酸塩皮膜や蓚酸塩皮膜のような下地皮膜 を形成させ、 その上に潤滑剤を塗布する方法が多用されている。 化成処理皮膜上に塗布される潤滑剤は、 使用方法によ り大き く 分けると、 二つに分けられる。 The film of the above (X) type is inferior in adhesion to the film of the above (Y) type, so that it is generally used only for light machining. If there is a carrier on the metal material surface A phosphate film or an oxalate film, which has the role of a lubricant, is generated, and a slippery lubricant is provided on the film. This type of coating has a very high seizure resistance because it has a two-layer structure consisting of a chemical conversion coating as a carrier coating and a lubricant. For this reason, it has been used in a very wide range in the field of plastic working such as drawing, drawing, and forging. In the field of plastic working, where processing is particularly severe, a method of forming a base film such as a phosphate film or an oxalate film on a metal surface and applying a lubricant thereon is often used. The lubricant applied on the chemical conversion coating can be divided into two types depending on the method of use.
一つは、 化成処理皮膜に潤滑剤を物理的に付着させるタイ プ ( Y 1 ) のものである。 もう一つは、 化成処理皮膜に潤滑剤を反 応させて付着させるタイプ （Y 2 ) のものである。  One type is a type (Y1) in which a lubricant is physically attached to a chemical conversion coating. The other type is a type (Y 2) in which a lubricant reacts and adheres to a chemical conversion coating.
前者 （ Y 1 ) の潤滑剤としては、 鉱油、 植物油及び合成油を基 油と して、 その中に極圧剤を添加したものとか、 黒鉛、 二硫化モ リ ブデン等の固体潤滑剤をパイ ンダ一成分と共に水に溶か した もの等が挙げられる。 これらの潤滑剤はスプレー塗布ゃ浸漬塗布 によ り簡便に使用できる。 この為、 液管理も殆ど必要が無い等の 利点がある。 しかしながら、 潤滑性が低い為、 潤滑性が比較的軽 い場合にしか使用できない。  Examples of the former (Y1) lubricant include mineral oils, vegetable oils, and synthetic oils as base oils, to which extreme pressure agents are added, and solid lubricants such as graphite and molybdenum disulfide. And those dissolved in water together with a single component. These lubricants can be easily used by spray coating and dip coating. Therefore, there is an advantage that liquid management is almost unnecessary. However, since lubricity is low, it can be used only when lubricity is relatively light.
一方、 後者 （ Y 2 ) の潤滑剤としては、 ステア リ ン酸ナ ト リ ウ ムのような反応型石鹼が挙げられる。 特に高い潤滑性が必要な場 合には、 化成処理皮膜を形成させた上に反応型石鹼を使用してい る。  On the other hand, examples of the latter (Y 2) lubricant include reactive stones such as sodium stearate. When particularly high lubricity is required, a reactive conversion stone is used after forming a chemical conversion coating.
しかしながら、 化学反応を伴う化成処理や反応型石鹼を使用す ると、 液の管理、 化学反応を制御する為の温度管理、 液の劣化に よる廃棄 · 更新が必要となる。 However, the use of chemical conversion treatments and reaction stones involving chemical reactions can lead to liquid management, temperature control for controlling chemical reactions, and deterioration of liquids. Disposal · Renewal is required.
と ころで、 近年、 地球環境保全を目的に、 産業廃棄物の低減が 大きな課題となっている。 この為、 廃棄物が生じない潤滑剤ゃ処 理方法が望まれている。  In recent years, however, reducing industrial waste has become a major issue for the purpose of preserving the global environment. For this reason, there is a demand for a lubricant treatment method that does not generate waste.
更には、 従来技術は工程や処理液の管理が複雑である。 この為 簡便な処理が望まれている。  Furthermore, in the prior art, the management of the process and the processing solution is complicated. For this reason, simple processing is desired.
このような問題点を解決する手段と して、 水溶性高分子または 'その水性ェマルジヨ ンを基材とし、 固体潤滑剤および化成皮膜形 成剤を配合した潤滑剤組成物が提案 （特開昭 5 2 - 2 0 9 6 7 号 公報） されている。  As a means for solving such problems, a lubricant composition comprising a water-soluble polymer or an aqueous emulsion thereof as a base material and a solid lubricant and a chemical conversion film forming agent is proposed (Japanese Patent Laid-Open No. No. 52-20967).
しかしながら、 特開昭 5 2 - 2 0 9 6 7 号公報の技術では、 ィ匕 成皮膜処理に匹敵するようなものが得られていない。  However, the technology disclosed in Japanese Patent Application Laid-Open No. 52-20967 has not been able to obtain a material that is comparable to the treatment of the delaminated film.
又、 （ a ) 水溶性無機塩、 （ b ) 固体潤滑剤、 （ c ) 鉱油、 動植 物油脂およ び合成油か ら選ばれる少な く と も 1 種の油成分、 ( d ) 界面活性剤、 及び （ e ) 水か らなる金属の冷間塑性加工用 水系潤滑剤が提案 （特開平 1 0 — 8 0 8 5号公報） されている。  (A) water-soluble inorganic salt; (b) solid lubricant; (c) at least one oil component selected from mineral oil, animal and plant fats and oils, and (d) surface activity. A water-based lubricant for cold plastic working of a metal consisting of an agent and (e) water has been proposed (Japanese Patent Application Laid-Open No. 10-85085).
しかしながら、 こ の特開平 1 0 — 8 0 8 5 号公報の技術は、 潤 滑剤は油成分を乳化している為、 工業的に使用するには適してお らず、 高い潤滑性を安定的に発揮でき難い。  However, the technology disclosed in Japanese Patent Application Laid-Open No. H10-80585 is not suitable for industrial use because the lubricant emulsifies the oil component, and the high lubricity is stable. It is difficult to demonstrate.
又、 （ a ) 合成樹脂、 （ b ) 水溶性無機塩、 及び水を含有し、 こ の固形分重量比 （ b ) / ( a ) が 0 . 2 5 Z 1 〜 9 / 1 の金属材 料の塑性加工用潤滑剤組成物が提案 （特開 2 0 0 0 - 6 3 8 8 0 号公報） されている。  Further, a metal material containing (a) a synthetic resin, (b) a water-soluble inorganic salt, and water, and having a solid content weight ratio (b) / (a) of 0.25Z1 to 9/1. (Japanese Patent Application Laid-Open No. 2000-63080) has been proposed.
しかし、 この特開 2 0 0 0 — 6 3 8 8 0号公報の技術は、 合成 樹脂を主成分と してお り、 厳しい加工条件では充分な潤滑性を安 定的に発揮でき難い。 発明の開示 However, the technique disclosed in Japanese Patent Application Laid-Open No. 2000-68380 uses a synthetic resin as a main component, and it is difficult to stably exhibit sufficient lubricity under severe processing conditions. Disclosure of the invention
従って、 本発明は、 上記従来技術が抱える問題を解決する こ と を目的とする。  Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art.
特に、 地球環境保全を考慮し、 各種金属材料に使用でき、 且つ 簡便な処理が可能、 つま り化成処理を不要とする金属材料加工用 潤滑剤 （特に、 金属材料塑性加工用水系潤滑剤） に関連した技術 を提供する こ とを目的とする。  In particular, in consideration of global environmental protection, it can be used for various metal materials and can be easily treated, that is, it is a lubricant for metal material processing that does not require chemical conversion treatment (particularly, an aqueous lubricant for plastic processing of metal material). It aims to provide related technologies.
中でも、 鉄鋼、 ステンレス、 チタン、 アルミニウム等の金属材 料を鍛造、 伸線、 伸管のような塑性加工を行う際に、 地球環境保 全を考慮し、 且つ、 簡便な処理が可能、 つま り化成処理を不要と する金属材料加工用潤滑剤 （特に、 金属材料塑性加工用水系潤滑 剤） に関連した技術を提供する ことを目的とする。  In particular, when performing metal forming such as steel, stainless steel, titanium, and aluminum in plastic processing such as forging, wire drawing, and pipe drawing, it is possible to consider the preservation of the global environment and to perform simple processing. An object of the present invention is to provide a technology related to a lubricant for metal material processing that does not require chemical conversion treatment (particularly, an aqueous lubricant for plastic working of metal material).
本発明者ら は上記課題を解決する為の研究を鋭意推し進めて 行く うちに、 特定の リ ン酸塩 （ A) と分散剤 （ B ) と滑剤 （ C ) とを用いた場合、 優れた潤滑性能が発揮される ことを見出し、 本 発明を完成するに至った。  As the inventors of the present invention intensively studied to solve the above-mentioned problems, it was found that when a specific phosphate (A), a dispersant (B) and a lubricant (C) were used, excellent lubrication was obtained. They found that performance was exhibited, and completed the present invention.
即ち、 前記の目的は、 Z n， F e , M n , N i , C o , C a , M g及び A 1 の群の中か ら選ばれる二価も し く は三価の金属の 少なく とも一種を含有する リ ン酸塩 （ A ) と、  That is, the object is to reduce the amount of divalent or trivalent metal selected from the group of Zn, Fe, Mn, Ni, Co, Ca, Mg and A1. A phosphate (A) containing both
分散剤 （ B ) と、  A dispersant (B),
ワックス、 及び脂肪酸の金属塩の群の中か ら選ばれる少なく と も一種の滑剤 （ C )  At least one lubricant selected from the group of waxes and metal salts of fatty acids (C)
とを含有する こ と を特徴とする金属材料加工用潤滑剤によっ て 達成される。 This is achieved by a lubricant for processing a metal material characterized by containing:
本発明で用いる リ ン酸塩 （ A) は、 加工時の追従性、 及び滑剤 のキャ リ ア性を付与する。 その為、 溶液中では均一に分散あるい は溶解し、 乾燥時に強固な皮膜を形成する性質を持つこ とが大事 である。 Phosphate (A) used in the present invention has good followability during processing and a lubricant. Carrier properties are provided. Therefore, it is important that they have the property of being uniformly dispersed or dissolved in a solution and of forming a strong film when dried.
このよ うな特徴を有する リ ン酸塩と して、 Z n , F e , Μ η , N i ， C o， C a , M g及び A l の群の中から選ばれる二価も し く は三価の金属の少なく とも一種を含有する リ ン酸塩 （ A) が挙 げられる。 これらは単独で用いても良いし、 二種以上組み合わせ ても良い。 例えば、 下記に示すリ ン酸塩がある。 尚、 リ ン酸塩は 2水塩、 4水塩等の水和物と して存在する。 しかし、 水和水の数 による効果の差は余り無い為、 以下では無水塩の形で例示する。  As a phosphate having such characteristics, divalent or divalent selected from the group consisting of Zn, Fe, Μη, Ni, Co, Ca, Mg and Al Phosphate (A) containing at least one trivalent metal is mentioned. These may be used alone or in combination of two or more. For example, there are the phosphates listed below. Note that phosphate exists as a hydrate such as dihydrate or tetrahydrate. However, there is not much difference in the effect depending on the number of hydration waters, and therefore, examples are given below in the form of anhydrous salts.
Zn3(P04)2 Zn 3 (P0 4) 2
Zn2Fe(P04)2 Zn 2 Fe (P0 4) 2
Zn2Ni(P04)2 Zn 2 Ni (P0 4) 2
Ni3(P04)2 Ni 3 (P0 4) 2
Zn2Mn(P04)2 Zn 2 Mn (P0 4) 2
Mn3(P04)2 Mn 3 (P0 4 ) 2
Mn2Fe(P04)2 Mn 2 Fe (P0 4) 2
Ca3(P04)2 Ca 3 (P0 4) 2
Zn2Ca(P04)2 Zn 2 Ca (P0 4) 2
FeP04 FeP0 4
A1P04 A1P0 4
Co3(P04)2 Co 3 (P0 4) 2
Mg3(P04)2 Mg 3 (P0 4) 2
本発明で用いる リ ン酸塩 （ A ) は、 平均粒径が 3 m以下の粒 子を用いる こ とが好ま しい。 これは、 大き過ぎる リ ン酸塩 （A ) を用いた場合、 分散安定性が低下するから による。 尚、 リ ン酸塩 ( A ) の大きさの下限値に格別な制約は無いが、 現実的に得られ る大きさの下限値は、 0 . 3 程度である。 As the phosphate (A) used in the present invention, it is preferable to use particles having an average particle size of 3 m or less. This is because the use of too large a phosphate (A) reduces the dispersion stability. In addition, phosphate There is no particular limitation on the lower limit of the size of (A), but the lower limit of the size that can be practically obtained is about 0.3.
本発明で用いる分散剤 （ B )、 即ち、 リ ン酸塩 （ A ) の分散剤 Dispersant (B) used in the present invention, that is, dispersant for phosphate (A)
( B ) と しては、 正リ ン酸、 ポリ リ ン酸、 有機ホスホン酸化合物 及びその誘導体の群の中か ら選ばれる少なく と も一種を用 いる こ とが出来る。 又、 不飽和カルボン酸及び/又はそのエステルを 用いて得 られた重合体の群の中か ら選ばれる少な く と も一種を 用いる こ と も出来る。 又、 単糖類、 多糖類、 及びその誘導体の群 の中か ら選ばれる少なく と も一種を用いる ことも出来る。 又、 酢 酸ビエル系重合体の群の中か ら選ばれる少なく と も一種を用い る こ と も出来る。 又、 ウレタン系重合体の群の中か ら選ばれる少 なく とも一種を用いる こ とも出来る。 As (B), at least one selected from the group consisting of orthophosphoric acid, polyphosphoric acid, organic phosphonic acid compounds and derivatives thereof can be used. In addition, at least one selected from the group of polymers obtained using unsaturated carboxylic acids and / or esters thereof can also be used. In addition, at least one selected from the group consisting of monosaccharides, polysaccharides, and derivatives thereof can also be used. Further, at least one selected from the group consisting of biel acetate acetate polymers can be used. Further, at least one kind selected from the group of urethane-based polymers can be used.
これらの分散剤の使用によ り 、 優れた追従性、 キャ リ ア性、 接 着性が発現する。  By using these dispersants, excellent follow-up properties, carrier properties and adhesive properties are exhibited.
即ち、 本発明の分散剤 （ B ) は、 リ ン酸塩粒子の分散安定性を 高め、 且つ、 リ ン酸塩を金属表面へ定着させる働きを有している つま り 、 分散剤 （ B ) は、 リ ン酸塩粒子の表面に吸着し、 その電 荷による反発力および立体障害作用 によって表面処理剤中での リ ン酸塩同士の衝突を妨げ、 凝集沈降を防止する。 更に、 分散剤 ( B ) は、 その構造上、 金属材料表面への吸着能力を有している この為、 リ ン酸塩の金属材料表面への定着が可能となる。 そして 本発明の剤を金属表面に塗布乾燥するだけで優れた皮膜が得ら れる。  That is, the dispersant (B) of the present invention has a function of enhancing the dispersion stability of the phosphate particles and fixing the phosphate to the metal surface. Adsorbs on the surface of the phosphate particles and prevents repulsion and steric hindrance by the charge to prevent collisions between the phosphates in the surface treatment agent, thereby preventing coagulation and sedimentation. Further, the dispersant (B) has a structure capable of adsorbing to the surface of the metal material because of its structure, so that the phosphate can be fixed to the surface of the metal material. An excellent film can be obtained only by applying and drying the agent of the present invention on the metal surface.
本発明は、 上記リ ン酸塩 （A ) と分散剤 （ B ) と滑剤 （ C ) と を併用する。 この併用に用い られる滑剤 （ C ) は、 ワッ クス、 及 び脂肪酸の金属塩の群の中か ら選ばれる少な く と も一種の滑剤 である。 中でも、 水に分散した合成ワ ッ クスである。 或いは、 Z n , C a , B a , A 1 , M g及び L i の群の中から選ばれる少な く とも一種と、 炭素数 1 2〜 2 6 の脂肪酸との反応物である。 In the present invention, the phosphate (A), the dispersant (B) and the lubricant (C) are used in combination. The lubricant (C) used in this combination is at least one lubricant selected from the group consisting of waxes and metal salts of fatty acids. It is. Above all, it is a synthetic wax dispersed in water. Alternatively, it is a reaction product of at least one selected from the group consisting of Zn, Ca, Ba, A1, Mg and Li with a fatty acid having 12 to 26 carbon atoms.
これらの滑剤 （ C ) の併用によ り 、 塑性加工時の摩擦係数が低 減し、 良好な潤滑性が発揮される。  By using these lubricants (C) together, the coefficient of friction during plastic working is reduced, and good lubricity is exhibited.
上記リ ン酸塩 （ A )、 分散剤 （ B )、 滑剤 （ C ) の好ま しい割合 (固形分重量比率） は、 （ B ) / ( A ) - 0 . 0 1〜 5 (更に好 ましく は、 0 . 1〜 2 )、 ( C ) / ( A ) = 0 . 1〜 5 (更に好ま しく は、 0 . 5〜 2 . 5 ) である。 即ち、 このような併用割合と する こ とによって、 上記特長が一層発揮される。  The preferred ratio (solid content weight ratio) of the above-mentioned phosphate (A), dispersant (B) and lubricant (C) is (B) / (A) -0.01 to 5 (more preferably). Are 0.1 to 2) and (C) / (A) = 0.1 to 5 (more preferably, 0.5 to 2.5). That is, the above-mentioned characteristics are further exhibited by setting such a combined ratio.
又、 本発明の剤は、 硫酸塩、 ケィ酸塩、 ホウ酸塩、 モリ ブデン 酸塩、 及びタングステン酸塩の群の中か ら選ばれる少なく とも一 種の無機塩 （ D ) を更に含有する こ とが好ましい。 これによつて 皮膜の強度や密着性が向上する。 無機塩 （ D ) の好ましい割合 （固 形分重量比率） は、 （ D ) / ( A ) = 0 . 0 1〜； 1 0 (更に好ま しく は、 0 . 1〜 4 ) である。  Further, the agent of the present invention further contains at least one inorganic salt (D) selected from the group consisting of sulfates, silicates, borates, molybdates, and tungstates. This is preferred. This improves the strength and adhesion of the film. A preferred ratio (solid content weight ratio) of the inorganic salt (D) is (D) / (A) = 0.01 to 10; more preferably, 0.1 to 4.
又、 本発明の剤は、 皮膜形成を補助する 目的で、 必要に応じて 公知の粘度向上剤を含有する。  Further, the agent of the present invention contains a known viscosity improver, if necessary, for the purpose of assisting film formation.
そして、 前記の目的は、 上記特徴の金属材料加工用潤滑剤が 0 , 5〜 4 0 g Zm2 の厚さ金属材料表面に設けられてなる こ とを特 徵とする表面処理金属材料によっても達成される。 The above object is also achieved by a surface-treated metal material characterized in that the metal material processing lubricant having the above characteristics is provided on a metal material surface having a thickness of 0.5 to 40 g Zm 2. Achieved.
又、 前記の目的は、 上記特徴の金属材料加工用潤滑剤に金属材 料を接触させ、 次いで乾燥させる こ とを特徴とする金属材料の潤 滑皮膜形成方法によっても達成される。  The above object is also achieved by a method for forming a lubricating film of a metal material, which comprises contacting the metal material with the lubricant for processing a metal material having the above characteristics, and then drying the metal material.
又、 前記の目的は、 ショ ッ トブラス ト、 サン ドブラス ト、 アル カ リ脱脂、 及び酸洗浄の群の中から選ばれる少なく とも一つの清 浄化手段によ り金属材料の表面を清浄化した後、 この金属材料を 上記特徴の金属材料加工用潤滑剤に接触させ、 次いで乾燥させる こ とを特徴とする金属材料の潤滑皮膜形成方法によっ ても達成 される。 In addition, the above-mentioned object is achieved by at least one cleaning selected from the group consisting of shot blast, sand blast, alcohol degreasing, and acid cleaning. After the surface of the metal material is cleaned by the purifying means, the metal material is brought into contact with the lubricant for processing a metal material having the above characteristics, and then dried. Is also achieved.
尚、 6 0 〜 1 0 0 に加温した金属材料を金属材料加工用潤滑 剤に接触させるよう にする ことが好ま しい。 図面の簡単な説明  It is preferable that the metal material heated to 60 to 100 is brought into contact with the metal material processing lubricant. BRIEF DESCRIPTION OF THE FIGURES
第 1 図は供試材の概略図である。  Figure 1 is a schematic diagram of the test material.
第 2 図は後方せん孔試験の概略図である。  Figure 2 is a schematic diagram of the posterior drill test.
第 3 図は成形品の概略図である。  Figure 3 is a schematic diagram of the molded product.
第 4 図はスパイ ク試験の概略図である。  Figure 4 is a schematic diagram of the spike test.
第 5 図はスパイ ク試験前後の変形を示す概略図である。 発明を実施するための最良の形態  Figure 5 is a schematic diagram showing the deformation before and after the spike test. BEST MODE FOR CARRYING OUT THE INVENTION
本発明になる金属材料加工用潤滑剤 （特に、 金属材料塑性加ェ 用水系潤滑剤。 中でも、 鉄鋼、 ステンレス、 チタン、 アルミニゥ ム等の金属材料を鍛造、 伸線、 伸管のよ うな塑性加工を行う際に 好適な潤滑性の皮膜を、 化成処理を施すこ となく形成できる金属 材料塑性加工用水系潤滑剤） は、 Z n , F e , Μ η , Ν i ， C o C a , M g及び A 1 の群の中から選ばれる二価も しく は三価の金 属の少な く と も一種を含有する リ ン酸塩 （ A ) と、 分散剤 （ B ) と、 ワッ クス、 及び脂肪酸の金属塩の群の中か ら選ばれる少なく とも一種の滑剤 （ C ) とを含有する。 本発明では、 平均粒径が 3 m以下のリ ン酸塩 （ A ) の粒子を特に用いる。 分散剤 （ B ) と しては、 正リ ン酸、 ポリ リ ン酸、 有機ホスホン酸化合物、 及びそ の誘導体の群の中か ら選ばれる少なく とも一種、 若しく は、 不飽 和カルボン酸及び/又はそのエステルを用いて得られた重合体 の群の中から選ばれる少なく とも一種、 或いは、 単糖類、 多糖類 及びその誘導体の群の中か ら選ばれる少なく とも一種、 又は、 酢 酸ビニル系重合体の群の中から選ばれる少なく とも一種、 又は、 ウ レタ ン系重合体の群の中か ら選ばれる少な く と も一種のもの を特に用いる。 本発明では、 滑剤 （ C ) が特に併用される。 この 滑剤 （ C ) は、 ワッ クス、 及び脂肪酸の金属塩の群の中から選ば れる少なく とも一種の滑剤である。 中でも、 水に分散した合成ヮ ッ クスである。 或レ は、 Z n， C a , B a , A 1 , M g及び L i の群の中から選ばれる少なく とも一種と、 炭素数 1 2 〜 2 6 の脂 肪酸との反応物である。 上記リ ン酸塩 （ A )、 分散剤 （ B )、 滑剤 ( C ) の好ま しい割合 （固形分重量比率） は、 （ B ) / ( A ) = 0 . 0 1 〜 5 (更に好ましく は、 0 . 1 〜 2 )、 ( C ) / ( A ) = 0 . 1 〜 5 (更に好ましく は、 0 . 5 〜 2 . 5 ) である。 又、 本 発明は、 硫酸塩、 ケィ酸塩、 ホウ酸塩、 モリ ブデン酸塩、 及び夕 ングステン酸塩の群の中か ら選ばれる少な く と も一種の無機塩 ( D ) を更に含有する場合がある。 無機塩 （ D ) の好ましい割合 (固形分重量比率） は、 （ D ) / ( A ) = 0 . 0 1 〜 1 0 (更に 好ましく は、 0 . 1 〜 4 ) である。 又、 本発明は、 皮膜形成を補 助する 目的で、 必要に応じて、 公知の粘度向上剤を含有する。 Lubricants for metal material processing according to the present invention (particularly, water-based lubricants for metal material plasticity processing, in particular, metal materials such as steel, stainless steel, titanium, and aluminum are subjected to plastic processing such as forging, wire drawing, and pipe drawing. Metallic materials that can form a suitable lubricating film without chemical conversion treatment when carrying out a water-based lubricant for plastic working) are Zn, Fe, Μη, Νi, CoCa, M g and A 1, a phosphate (A) containing at least one divalent or trivalent metal selected from the group consisting of a divalent or trivalent metal, a dispersant (B), a wax, and It contains at least one lubricant (C) selected from the group of fatty acid metal salts. In the present invention, phosphoric acid (A) particles having an average particle diameter of 3 m or less are particularly used. Dispersants (B) include orthophosphoric acid, polyphosphoric acid, organic phosphonic acid compounds, and the like. Or at least one selected from the group of polymers obtained using unsaturated carboxylic acids and / or esters thereof, or at least one selected from the group of derivatives of At least one selected from the group of saccharides, polysaccharides and derivatives thereof, or at least one selected from the group of vinyl acetate polymers, or within the group of urethane polymers Particularly, at least one kind selected from among them is used. In the present invention, the lubricant (C) is particularly used in combination. This lubricant (C) is at least one lubricant selected from the group of waxes and metal salts of fatty acids. Above all, it is a synthetic resin dispersed in water. One is a reaction product of at least one selected from the group consisting of Zn, Ca, Ba, A1, Mg and Li with a fatty acid having 12 to 26 carbon atoms. . The preferred ratio (solid content weight ratio) of the above-mentioned phosphate (A), dispersant (B) and lubricant (C) is (B) / (A) = 0.01 to 5 (more preferably, 0.1 to 2) and (C) / (A) = 0.1 to 5 (more preferably 0.5 to 2.5). Further, the present invention further comprises at least one inorganic salt (D) selected from the group consisting of sulfates, silicates, borates, molybdates and ungstenates. There are cases. A preferable ratio (solid content weight ratio) of the inorganic salt (D) is (D) / (A) = 0.01 to 10 (more preferably, 0.1 to 4). Further, the present invention contains a known viscosity improver, if necessary, for the purpose of assisting film formation.
本発明になる表面処理金属材料は、 上記特徴の金属材料加工用 潤滑剤が 0 . 5 〜 4 0 g / m 2 の厚さ金属材料表面に設けられた ものである。 The surface-treated metal material according to the present invention is one in which the lubricant for metal material processing having the above characteristics is provided on the surface of a metal material having a thickness of 0.5 to 40 g / m 2 .
本発明になる金属材料の潤滑皮膜形成方法は、 上記特徴の金属 材料加工用潤滑剤に金属材料を接触させ、 次いで乾燥させる方法 である。 特に、 ショ ッ トブラス ト、 サン ドブラス 卜、 アルカ リ脱 脂、 及び酸洗浄の群の中から選ばれる少なく とも一つの清浄化手 段によ り金属材料の表面を清浄化した後、 この金属材料を上記特 徵の金属材料加工用潤滑剤に接触させ、 次いで乾燥させる方法で ある。 尚、 6 0〜 1 0 0 °Cに加温した金属材料を金属材料加工用 潤滑剤に接触させるよう にする こ とが好ましい。 The method for forming a lubricating film of a metal material according to the present invention is a method of bringing a metal material into contact with a lubricant for processing a metal material having the above characteristics, and then drying the metal material. It is. In particular, after cleaning the surface of the metal material by at least one cleaning means selected from the group consisting of shot blast, sand blast, alkaline degreasing, and acid cleaning, Is brought into contact with the above-mentioned lubricant for processing a metal material and then dried. It is preferable that the metal material heated to 60 to 100 ° C. is brought into contact with the metal material processing lubricant.
以下、 更に、 詳しく 説明する。  The details will be described below.
[リ ン酸塩 （ A ) ] ' 本発明の金属材料用塑性加工用水系潤滑剤に使用される リ ン 酸塩 （ A) は、 加工時の追従性および滑剤のキャ リ ア性を付与す る為のものである。 この為、 リ ン酸塩 （A) は、 溶液中では均一 に分散あるいは溶解し、 且つ、 乾燥時に強固な皮膜を形成する性 質を持つこ とが大事である。 このよ うな性質を持つリ ン酸塩と し て、 Z n， F e , M n， N i ， C o , C a , M g及び A l の群の 中か ら選ばれる二価も し く は三価の金属の少な く と も一種を含 有する リ ン酸塩 （ A ) が挙げられる。 これらは単独で用いても良 いし、 二種以上組み合わせて用いても良い。 以下に具体例を挙げ る。  [Phosphate (A)] 'The phosphate (A) used in the water-based lubricant for plastic working of metal materials of the present invention imparts followability during working and carrier properties of the lubricant. It is for doing. For this reason, it is important that the phosphate (A) has the property of being uniformly dispersed or dissolved in a solution and of forming a strong film when dried. As a phosphate having such properties, a divalent material selected from the group consisting of Zn, Fe, Mn, Ni, Co, Ca, Mg, and Al may be used. Is a phosphate (A) containing at least one trivalent metal. These may be used alone or in combination of two or more. Specific examples are given below.
Zn3(PO4)2,Zn2Fe(PO4)2,Zn2Ni(P04)2,Ni3(P04)2,Zn2Mn(P04)2, Mn3(P04)2iMn2Fe(P04)2,Ca3(PO4)2)Zn2Ca(P04)2,FeP04jAlP04, Co3(P04)2 Mg3(P04)2 Zn 3 (PO 4) 2, Zn 2 Fe (PO 4) 2, Zn 2 Ni (P0 4) 2, Ni 3 (P0 4) 2, Zn 2 Mn (P0 4) 2, Mn 3 (P0 4) 2i Mn 2 Fe (P0 4) 2 , Ca 3 (PO 4) 2) Zn 2 Ca (P0 4) 2, FeP0 4j AlP0 4, Co 3 (P0 4) 2 Mg 3 (P0 4) 2
リ ン酸塩 （A) の粒径は算術平均粒子径で 3 以下である こ とが好ましい。 これは処理液の分散安定性が粒子径が大きいと劣 化する為である。  The particle size of the phosphate (A) is preferably an arithmetic mean particle size of 3 or less. This is because the dispersion stability of the treatment liquid is deteriorated when the particle diameter is large.
[分散剤 （ B )]  [Dispersant (B)]
本発明者らは、 後述する分散剤の何れかを含有した本発明の金 属材料加工用潤滑剤が塗布されて設けられた皮膜は、 優れた追従 性、 キャ リ ア性、 接着性を呈する こ とを見出した。 The inventors of the present invention have prepared the gold of the present invention containing any of the dispersants described below. It has been found that a film provided by applying a lubricant for processing a metal material exhibits excellent conformability, carrier properties, and adhesiveness.
本発明の分散剤 （ B ) は、 リ ン酸塩粒子の分散安定性を高め、 且つ、 リ ン酸塩を金属材料表面へ定着させる働きを有している。  The dispersant (B) of the present invention has a function of improving the dispersion stability of the phosphate particles and fixing the phosphate to the surface of the metal material.
即ち、 分散剤 （ B ) は、 リ ン酸塩粒子表面に吸着し、 その電荷 による反発力および立体障害作用 によって表面処理剤中での リ ン酸塩同士の衝突を妨げ、 凝集沈降を防止する。  In other words, the dispersant (B) is adsorbed on the surface of the phosphate particles, and the repulsion and steric hindrance of the charge prevent the phosphates from colliding with each other in the surface treatment agent, thereby preventing aggregation and sedimentation. .
又、 分散剤 （ B ) は、 その構造上、 金属表面への吸着能力を有 している。 この為、 リ ン酸塩の金属表面への定着が可能となる。 よって、 本発明の金属材料加工用潤滑剤を被処理金属表面に塗布 乾燥するだけで優れた皮膜が得られる。  Further, the dispersant (B) has an adsorption ability to a metal surface due to its structure. For this reason, it becomes possible to fix the phosphate on the metal surface. Therefore, an excellent film can be obtained only by applying and drying the lubricant for processing a metal material of the present invention on the surface of the metal to be treated.
本発明の分散剤 （ B ) と して、 正リ ン酸、 ポリ リ ン酸、 有機ホ スホン酸化合物、 及びその誘導体の群の中から選ばれる少なく と も一種が好ま し く用いられる。  As the dispersant (B) of the present invention, at least one selected from the group consisting of orthophosphoric acid, polyphosphoric acid, organic phosphonic acid compounds, and derivatives thereof is preferably used.
正リ ン酸はオルソ リ ン酸である。 ポリ リ ン酸としては、 ピロ リ ン酸、 ト リ リ ン酸、 ト リ メタ リ ン酸、 テ ト ラメタ リ ン酸、 へキサ メタ リ ン酸も し く はそのアル力 リ 金属塩及びア ンモニゥム塩を 使用できる。 有機ホスホン酸化合物と しては、 アミ ノ ト リ メチレ ンホスホン酸、 1 ー ヒ ドロキシェチリ デンー 1 , 1 ージホスホン 酸、 エチレンジアミ ンテ ト ラメチレンホスホン酸、 ジエチレン ト リ アミ ンペンタメチレンホスホン酸、 又はそのアルカ リ 金属塩を 使用できる。 正リ ン酸、 ポリ リ ン酸または有機ホスホン酸化合物 の 1 種類を使用 しても何種類かを組み合わせて使用しても良い。  Orthophosphoric acid is orthophosphoric acid. Examples of polyphosphoric acid include pyrrolic acid, triphosphoric acid, trimethacrylic acid, tetramethylphosphoric acid, hexametaphosphoric acid, and metal salts thereof and alcohols thereof. Monmonium salt can be used. Examples of the organic phosphonic acid compound include aminotrimethylenephosphonic acid, 1-hydroxyxethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and alkali alcohols thereof. Metal salts can be used. One type of orthophosphoric acid, polyphosphoric acid or organic phosphonic acid compound may be used, or a combination of several types may be used.
上記以外の分散剤 （ B ) と して、 不飽和カルボン酸及び Z又は エステルを用いて得られた重合体の群の中か ら選ばれる少な く とも一種を用いても良い。 更に詳しく述べる と、 下記の一般式 （ I ) で表されるアク リル 酸 （又はメタク リ ル酸） エステルの単量体及び a， /3不飽和カル ボン酸の単量体の群の中か ら選ばれる少なく と も一種以上の単 量体を用いて構成された重合体、 又は前記単量体と共重合可能な 単量体 （ 5 0重量％以下） とを用いて構成された共重合体が好ま しく 用いられる。 As the dispersant (B) other than the above, at least one selected from the group of polymers obtained using unsaturated carboxylic acids and Z or esters may be used. More specifically, the group of monomers of acrylic acid (or methacrylic acid) ester represented by the following general formula (I) and a // 3 unsaturated carboxylic acid monomer A polymer composed of at least one monomer selected from the group consisting of at least one monomer, or a copolymer composed of a monomer (50% by weight or less) copolymerizable with the monomer. Coalescing is preferably used.
一般式 （ I ) 卢1 General formula (I) 卢1
XI 9 C  XI 9 C
COOR2 COOR 2
(式中、 R 1は Hまたは C H 3、 R 2は H、 炭素数が 1 〜 5 のアルキル基または炭素数が 1 〜 5 のヒ ド ロキシアルキル基） 上記一般式 （ I ) で表される単量体と して、 アク リル酸メチル アク リル酸ェチル、 アク リル酸プロ ピル、 アク リ ル酸プチル、 ァ ク リ ル酸ペンチル、 メタク リル酸メチル、 メタク リル酸ェチル、 メタク リル酸プロ ピル、 メタク リル酸プチル、 メタク リ ル酸ペン チル、 アク リル酸ヒ ド ロキシメチル、 アク リル酸ヒ ドロキシェチ ル、 アク リル酸ヒ ドロキシプロピル、 アク リル酸ヒ ドロキシプチ ル、 ァク リル酸ヒ ドロキシペンチル、 メタク リ ル酸ヒ ド ロキシメ チル、 メタク リル酸ヒ ドロキシェチル、 メタク リ ル酸ヒ ド ロキシ プロ ピル、 メ夕ク リル酸ヒ ドロキシブチル、 メタク リル酸ヒ ドロ キシペンチル等が挙げられる。 (Wherein, R 1 is H or CH 3 , R 2 is H, an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms) represented by the above general formula (I) Monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, methyl methacrylate, ethyl methacrylate, and propyl methacrylate. , Butyl methacrylate, pentyl methacrylate, hydroxymethyl acrylate, hydroxyxyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate Hydroxymethyl methacrylate, Hydroxyshetyl methacrylate, Hydroxypropyl methacrylate, Hydroxybutyl methacrylate, Hydroxybutyl methacrylate Doxypentyl and the like.
, |3不飽和カルボン酸の単量体としては、 アク リル酸、 メタ アク リル酸、 マレイ ン酸等が挙げられる。 上記単量体と共重合可能な単量体としては、 酢酸ビニル、 スチ レン、 塩化ビエル、 ビニルスルホン酸等が挙げられる。 , | 3 Unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, and maleic acid. Examples of the monomer copolymerizable with the above monomer include vinyl acetate, styrene, biel chloride, vinyl sulfonic acid, and the like.
前記単量体のう ち 1 種類の単量体を重合して得 られた重合体 を使用 しても、 前記単量体の何種類かを組み合わせて重合して得 られた共重合体を使用 しても良い。  Even when a polymer obtained by polymerizing one kind of the monomers is used, a copolymer obtained by polymerizing a combination of several kinds of the monomers is used. You may.
上記以外の分散剤 （ B ) と して、 単糖類、 多糖類及びその誘導 体の群の中から選ばれる少なく とも一種を用いても良い。  As the dispersant (B) other than the above, at least one selected from the group consisting of monosaccharides, polysaccharides and derivatives thereof may be used.
本発明に用いられる単糖類、 多糖類、 及びその誘導体の基本構 成糖類と しては、 例えばフルク ト一ス、 夕ガ トース、 プシコース スルポース、 エリ ト ロース、 ト レオース、 リ ポース、 ァラビノー ス、 キシロース、 リ キソース、 ァロース、 アル ト ロース、 ダルコ ース、 マンノース、 グロース、 イ ド一ス、 ガラク ト一ス及びタロ ース等が挙げられる。 単糖類を用いる場合は、 前記基本構成糖類 そのものを使用できる。 多糖類を用いる場合は、 前記基本構成糖 '類のホモ多糖もしく はヘテロ多糖を使用できる。 それらの誘導体 と しては、 基本構成糖類の水酸基を N 02 、 C H 3 、 C 2 H 4 O H、 C H 2 C H (O H)C H 3 、 C H 2 C O O H等の置換基でエーテル化 して得られる単糖類や、 前記置換基で置換された単糖類を構造に 含むホモ多糖やへテロ多糖を使用できる。 数種類の単糖類、 多糖 類、 及びその誘導体を組み合わせて使用しても構わない。 糖類の 分類を行う際に、 加水分解の度合いによって、 単糖類、 小糖類、 及び多糖類と分類される場合がある。 しかし、 本発明では、 加水 分解によ り二個以上の単糖類を生ずるものを多糖類、 それ自身が それ以上加水分解されない糖類を単糖類と した。 The basic constituent saccharides of the monosaccharides, polysaccharides and derivatives thereof used in the present invention include, for example, fructos, evening gatose, psicose sulfose, erythrose, threose, reportose, arabinose, and the like. Xylose, lyxose, arose, altrose, darcose, mannose, growth, ide, galactose and talose. When a monosaccharide is used, the basic constituent saccharide itself can be used. When a polysaccharide is used, a homopolysaccharide or a heteropolysaccharide of the basic constituent saccharides can be used. Is a derivative thereof, obtained by etherifying the basic configuration saccharide hydroxyl groups at N 0 2, CH 3, C 2 H 4 OH, CH 2 CH (OH) CH 3, CH 2 COOH , etc. substituents A monosaccharide, a homopolysaccharide or a heteropolysaccharide containing a monosaccharide substituted with the substituent in the structure can be used. Several types of monosaccharides, polysaccharides, and derivatives thereof may be used in combination. When classifying saccharides, they may be classified as monosaccharides, small saccharides, and polysaccharides depending on the degree of hydrolysis. However, in the present invention, polysaccharides that generate two or more monosaccharides by hydrolysis are referred to as polysaccharides, and saccharides that themselves are not further hydrolyzed are referred to as monosaccharides.
本発明の用途は、 生体化学反応とは無関係である。 従って、 基 本構成糖類の立体配置および旋光性によって効果が左右され無 い。 よって、 D -単糖、 L -単糖と旋光性 （十， 一） の如何なる組み 合わせでも使用できる。 又、 単糖類、 多糖類、 及びその誘導体の 水溶性を高める為、 前記単糖類、 多糖類、 及びその誘導体のアル カ リ金属塩またはアンモニゥム塩を使用しても良い。 更に、 前記 構造で水溶化が困難な場合は、 予め、 水と相溶性を有する有機溶 剤に溶解した後に使用 しても良い。 The use of the present invention is independent of biochemical reactions. Therefore, the effect depends on the steric configuration and optical rotation of the basic constituent saccharides. No. Therefore, any combination of D-monosaccharide, L-monosaccharide and optical rotation (10,1) can be used. Further, in order to increase the water solubility of the monosaccharide, the polysaccharide, and the derivative thereof, an alkali metal salt or an ammonium salt of the monosaccharide, the polysaccharide, and the derivative thereof may be used. Further, when it is difficult to make water soluble with the above-mentioned structure, it may be used after previously dissolving it in an organic solvent compatible with water.
上記以外の分散剤 （ B ) と して、 酢酸ビニル系重合体の群の中 か ら選ばれる少なく と も一種を用いても良い。  As the dispersant (B) other than the above, at least one selected from the group of vinyl acetate polymers may be used.
酢酸ビニル系重合体としては、 酢酸ビニルの重合体、 酢酸ビニ ルと共重合可能な単量体と酢酸ビニルとの共重合体、 及びその誘 導体などの水性高分子化合物が挙げられる。  Examples of the vinyl acetate-based polymer include an aqueous polymer compound such as a vinyl acetate polymer, a copolymer of vinyl acetate and a monomer copolymerizable with vinyl acetate, and a derivative thereof.
具体的には、 酢酸ビエル重合体のケン化物であるポリ ビニルァ ルコール、 更にポリ ビエルアルコールをァク リ ロニ ト リルによる シァ ノ エチル化して得られる シァ ノ エチル化ポ リ ビニルアルコ ール、 ポリ ビニルアルコールをホルマリ ンによるァセタール化し て得られるホルマール化ポ リ ビニルアルコール、 ポ リ ビニルアル コールを尿素による ウ レタ ン化して得られる ウ レタ ン化ポ リ ビ ニルアルコール、 及びポリ ビニルアルコールに力ルポキシル基、 スルホン基、 アミ ド基等を導入した水性高分子化合物などが挙げ られる。  Specifically, polyvinyl alcohol, which is a saponified product of biel acetate, and cyanoethylated poly (vinyl alcohol) and polyvinyl alcohol, which are obtained by cyanoethylating polyvinyl alcohol with acrylonitrile Of formalized polyvinyl alcohol obtained by acetalizing with formalin, urethanized polyvinyl alcohol obtained by urethanizing polyvinyl alcohol with urea, and urepoxyl group and sulfone of polyvinyl alcohol And an aqueous polymer compound into which a amide group or the like is introduced.
本発明における酢酸ビニルと共重合可能な単量体と しては、 ァ ク リル酸、 ク ロ ト ン酸、 無水マレイ ン酸、 エチレン等が挙げられ る。 前記酢酸ビニルの重合体、 若し く は酢酸ビニルと共重合可能 な単量体と酢酸ビエルとの共重合体、 又はその誘導体は、 水性で あれば、 本発明における効果を十分に発揮できる。 従って、 その 重合度や官能基の導入率に劾果は左右され無い。 又、 前記単量体 も し く は共重合体の 1 種類を使用 しても何種類かを組み合わせ て使用 しても差し支えはない。 Examples of the monomer copolymerizable with vinyl acetate in the present invention include acrylic acid, crotonic acid, maleic anhydride, and ethylene. If the vinyl acetate polymer, or a copolymer of vinyl acetate and a monomer copolymerizable with vinyl acetate and biel acetate, or a derivative thereof is aqueous, the effects of the present invention can be sufficiently exerted. Therefore, impeachment does not depend on the degree of polymerization or the rate of introduction of functional groups. In addition, the monomer It is permissible to use one type of copolymer or a combination of several types.
上記以外の分散剤 （ B ) と して、 ウレタン系重合体の群の中か ら選ばれる少なく とも一種を用いても良い。  As the dispersant (B) other than the above, at least one selected from the group of urethane polymers may be used.
ウ レタ ン系重合体と しては、 ウレタ ン樹脂、 ウレタ ンと共重合 可能な単量体とウレタ ンとの共重合体、 及びその誘導体などの水 性高分子化合物が挙げられる。  Examples of the urethane-based polymer include a urethane resin, a copolymer of urethane and a monomer copolymerizable with urethane, and a water-soluble polymer compound such as a derivative thereof.
[滑剤 （ C ) ]  [Lubricant (C)]
本発明者らは、 滑剤 （ C ) がリ ン酸塩 （ A ) 及び分散剤 （ B ) と共に存在すると、 塑性加工時の摩擦係数が低減し、 良好な潤滑 性が発揮される ことを見出した。  The present inventors have found that, when the lubricant (C) is present together with the phosphate (A) and the dispersant (B), the friction coefficient during plastic working is reduced, and good lubricity is exhibited. .
このよ うな特長を奏する本発明の滑剤 （ C ) は、 ワッ クス、 及 び脂肪酸の金属塩の群の中か ら選ばれる少な く と も一種の滑剤 である。  The lubricant (C) of the present invention having such features is at least one kind of lubricant selected from the group consisting of waxes and metal salts of fatty acids.
ワ ッ クス と しては合成ワ ッ クスが好ましい。 ワックスは、 塑性 加工時に発生する熱によ り融解し、 皮膜の滑り性を良く する。 こ の為、 加工初期に効果を発揮するよ う に、 融点が 7 0 〜 1 5 0 °C で、 更に水溶液中で安定で、 かつ、 皮膜強度を低下させないもの が望ま しい、 具体的には、 例えばマイ ク ロク リ スタ リ ンワ ックス ポリ エチレンワッ クス、 ポリ プロ ピレンワッ クス、 カリレナウノ ヮ ッ クス等を挙げる こ とが出来る。 これらの成分は、 水デイ スパー ジ ョ ンゃ水ェマルジ ョ ンの形態で他成分と混合 して含有させる のが良い。  As the wax, a synthetic wax is preferable. Wax is melted by the heat generated during plastic working, improving the lubricity of the film. For this reason, it is desirable that the material has a melting point of 70 to 150 ° C, is stable in an aqueous solution, and does not reduce the film strength so that the effect is exerted at the initial stage of processing. Examples thereof include microcrystalline wax, polyethylene wax, polypropylene wax, and karenenaunox. These components are preferably mixed with other components in the form of a water dispersion / water emulsion.
脂肪酸の金属塩は如何なる ものでも良い。 但し、 炭素数 1 2 〜 2 6 の脂肪酸と、 亜鉛、 カルシウム、 ノ リ ウム、 アルミニウム、 マグネシウム、 及びリ チウムから成る群から選ばれた少なく と も 一種の金属とを反応させて得られた脂肪酸の金属塩が好ま しい。 中でも、 ステアリ ン酸カルシウム、 ステア リ ン酸亜鉛、 ステア リ ン酸バリ ウム、 ステア リ ン酸マグネシウム、 ステアリ ン酸リチウ ムが好ま しい。 Any metal salt of a fatty acid may be used. However, a fatty acid having 12 to 26 carbon atoms and at least one selected from the group consisting of zinc, calcium, nordium, aluminum, magnesium, and lithium. Metal salts of fatty acids obtained by reacting with a kind of metal are preferred. Of these, calcium stearate, zinc stearate, barium stearate, magnesium stearate, and lithium stearate are preferred.
本発明の脂肪酸金属塩は、 本発明の水系潤滑剤に分散した形で 存在している。 分散して存在させる為、 必要に応じて、 公知の界 面活性剤を用いる。  The fatty acid metal salt of the present invention exists in a form dispersed in the aqueous lubricant of the present invention. A known surfactant is used, if necessary, to disperse and exist.
滑剤を分散させる為、 界面活性剤が必要な場合には、 非イオン 性界面活性剤、 陰イオン性界面活性剤、 両性界面活性剤、 陽ィ ォ ン性界面活性剤の何れを用いても良い。 これらの界面活性剤は単 独または 2種以上組み合わせて使用しても良い。 これらの界面活 性剤は特に限定される ものでは無い。 尚、 非イオン界面活性剤と しては、 例えばポリ オキシエチレンアルキルエーテル、 ポリ オキ シアルキレン (エチレンおよび/またはプロ ピレン） アルキルフ ェニルエーテル、 ポリ エチレングリ コール (も し く はエチレンォ キシ ド） と高級脂肪酸 （例えば炭素数 1 2 〜 1 8 ) とか ら構成さ れるポリ ォキシエチレンアルキルエステル、 ソルビタンとポリ エ チレングリ コールと高級脂肪酸 （例えば炭素数 1 2 ~ 1 8 ) とか ら構成されるポ リ オキシエチ レンソルビ夕 ンアルキルエステル 等が挙げられる。 陰イオン性界面活性剤としては、 例えば脂肪酸 塩、 硫酸エステル塩、 スルホン酸塩、 リ ン酸エステル塩、 ジチォ リ ン酸エステル塩等が挙げられる。 両性界面活性剤としては、 例 えばアミ ノ酸型およびべタイ ン型のカルボン酸塩、 硫酸エステル 塩、 スルホン酸塩、 リ ン酸エステル塩等が挙げられる。 陽イオン 性界面活性剤としては、 例えば脂肪酸アミ ン塩、 第四級アンモニ ゥム塩等が挙げられる。 本発明においては、 皮膜の強度や密着性を調整する 目的で、 硫 酸塩、 ケィ酸塩、 ホウ酸塩、 モリ ブデン酸塩、 及びタングステン 酸塩か らなる群か ら選ばれる少なく と も一種である無機塩 （ D ) が用い られる。 これら無機塩の例と しては、 硫酸ナ ト リ ウム、 硫 酸カ リ ウム、 ゲイ酸カ リ ウム、 ホウ酸ナ ト リ ウム （四ホウ酸ナ ト リ ウム）、 ホウ酸カ リ ウム （四ホウ酸カ リ ウム等）、 ホウ酸アンモ ニゥム （四ホウ酸アンモニゥム等）、 モリ ブデン酸アンモニゥム、 モリ ブデン酸ナ ト リ ウム、 タ ングステン酸ナ ト リ ウム等が挙げら れる。 これらは単独で用いても良いし、 2種以上組み合わせても 良い。 When a surfactant is required to disperse the lubricant, any of a nonionic surfactant, an anionic surfactant, an amphoteric surfactant, and a cationic surfactant may be used. . These surfactants may be used alone or in combination of two or more. These surfactants are not particularly limited. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyalkylene (ethylene and / or propylene) alkyl phenyl ether, and polyethylene glycol (or ethylene oxide). Polyoxyethylene alkyl esters composed of fatty acids (for example, having 12 to 18 carbon atoms), and polyoxyethylenes composed of sorbitan, polyethylene glycol, and higher fatty acids (for example, having 12 to 18 carbon atoms). And rensorbin alkyl esters. Examples of the anionic surfactant include a fatty acid salt, a sulfate, a sulfonate, a phosphate, a dithiophosphate, and the like. Examples of the amphoteric surfactant include amino acid type and betaine type carboxylate, sulfate, sulfonate, phosphate and the like. Examples of the cationic surfactant include a fatty acid amine salt and a quaternary ammonium salt. In the present invention, at least one selected from the group consisting of sulfates, silicates, borates, molybdates, and tungstates for the purpose of adjusting the strength and adhesion of the film. The inorganic salt (D) is used. Examples of these inorganic salts include sodium sulfate, potassium sulfate, potassium gayate, sodium borate (sodium tetraborate), and sodium borate ( Examples thereof include ammonium tetraborate, ammonium borate (ammonium tetraborate, etc.), ammonium molybdate, sodium molybdate, sodium tungstate, and the like. These may be used alone or in combination of two or more.
又、 皮膜形成を補助する 目的で、 必要に応じて、 公知の粘度向 上剤が用い られる。 例えば、 平滑性を向上させ、 皮膜ムラを抑制 する場合に、 粘度向上剤は有効である。 粘度向上剤の一例として スメ クタイ ト系の粘度鉱物 （モンモリ ロナイ ト、 ソーコナイ ト、 パイデライ ト、 ヘク トライ ト等） が挙げられる。 この配合量や種 類などは特に限定され無い。  In addition, a known viscosity improver is used as needed for the purpose of assisting film formation. For example, a viscosity improver is effective for improving smoothness and suppressing film unevenness. Examples of viscosity improvers include smectite-based viscosity minerals (montmorillonite, sauconite, paiderite, hectrite, etc.). There are no particular restrictions on the amount or type of the composition.
本発明の潤滑剤において、 リ ン酸塩 （ A )、 分散剤 （ B )、 滑剤 ( C ) の固形分重量比率のう ち、 （ B ) / ( A ) は 0 . 0 1 〜 5 . 0 の範囲が好ましい。 よ り好ま しく は、 0 . 1 〜 2 の範囲である この比が 0 . 0 1 未満では、 分散安定性が劣る。 5 を超えても安 定性に悪影響はないが、 コス トが高く なる。  In the lubricant of the present invention, (B) / (A) is 0.01 to 5.0 of the solid content weight ratio of the phosphate (A), the dispersant (B), and the lubricant (C). Is preferable. More preferably, the ratio is in the range of 0.1 to 2 If the ratio is less than 0.01, the dispersion stability is poor. Exceeding 5 does not adversely affect stability, but increases costs.
本発明の潤滑剤において、 （ C ) / ( A ) は 0 ' · 1 〜 5 の範囲 が好ましい。 よ り好ましく は、 0 . 5 〜 2 . 5 の範囲である。 0 1 未満では、 滑り性が劣る。 5 を超える と、 塑性加工時にカスの 発生が多く なり、 金型づま り の原因となる。  In the lubricant of the present invention, (C) / (A) is preferably in the range of 0 ′ · 1 to 5. More preferably, it is in the range of 0.5 to 2.5. If it is less than 0, the sliding property is poor. If it exceeds 5, more scum will be generated during plastic working, which may cause mold stagnation.
本発明において、 無機塩を添加する場合、 リ ン酸塩 （ A )、 無 機塩 （ D ) の固形分重量比率 （ D ) / ( A ) が 0 . 0 1 〜 ： L 0 の 範囲が好ましい。 よ り好ましい範囲は 0 . 1 〜 4である。 無機塩 は密着性を向上させる 目的で添加する。 この重量比が 0 . 0 1 未 満では、 その効果が充分発揮され難い。 重量比が 1 0 を超えても 性能上問題はないが、 処理液の安定性に問題を生じる場合がある , 尚、 加工が厳しい強加工の場合には'、 本発明の金属材料用塑性 加工用水系潤滑剤中に更に油や固体潤滑剤等を潤滑補助剤と し て添加する。 In the present invention, when an inorganic salt is added, phosphate (A), The weight ratio of solid content (D) / (A) of the salt (D) is preferably in the range of 0.01 to L 0. A more preferred range is from 0.1 to 4. The inorganic salt is added for the purpose of improving the adhesion. If the weight ratio is less than 0.01, the effect is difficult to sufficiently exert. Even if the weight ratio exceeds 10, there is no problem in performance, but there may be a problem in the stability of the processing solution.In case of severe processing, the plastic working for the metal material of the present invention Oil and solid lubricants are further added to the water-based lubricant as lubrication aids.
本発明の塑性加工用水系潤滑剤は、 鉄もしく は鋼、 ステンレス . 銅も しく は銅合金、 アルミニウムも しく はアルミニウム合金、 チ タンも し く はチタン合金等の金属材料に適用される。 金属材料の 形状としては、 棒材ゃブロック材等の素材だけでなく、 鍛造後の 形状物 （ギヤやシャ フ ト等） の加工も考えられ、 特に限定されな い。  The water-based lubricant for plastic working of the present invention is applied to metal materials such as iron or steel, stainless steel, copper or copper alloy, aluminum or aluminum alloy, titanium or titanium alloy. The shape of the metal material is not particularly limited, because not only materials such as a bar material and a block material but also a forged shape (gear, shaft, etc.) can be processed.
本発明の皮膜処理方法は、 清浄化した金属材料を前記潤滑剤に 接触させ、 次いで乾燥させる方法である。 これによ り、 金属材料 表面に潤滑皮膜が形成される。 こ の潤滑皮膜は未反応型のもので ある。 金属表面に形成させる潤滑皮膜の付着量は、 その後の加工 の程度によ り 適宜コ ン ト ロールされるが、 0 . 5 〜 4 0 g Z m 2 の範囲である。 よ り好まし く は 2 〜 2 0 g / m 2 の範囲である。 この付着量が 0 . 5 g / m 2未満の場合は、 潤滑性が不充分とな る傾向がある。 付着量が 4 0 g / m 2 を超える と、 潤滑性は問題 ないが、 金型へのカス詰ま り等が生じ易い。 尚、 付着量は処理前 後の金属材料の重量差および表面積よ り計算できる。 The coating treatment method of the present invention is a method in which a cleaned metal material is brought into contact with the lubricant and then dried. As a result, a lubricating film is formed on the surface of the metal material. This lubricating film is of the unreacted type. Adhesion amount of the lubricant film to be formed on the metal surface, but is then appropriate Control This setup rolls Ri by the degree of work, in the range of 0. 5 ~ 4 0 g Z m 2. More preferably, it is in the range of 2 to 20 g / m 2 . If the amount is less than 0.5 g / m 2 , lubricity tends to be insufficient. If the amount of adhesion exceeds 40 g / m 2 , there is no problem in lubrication, but clogging of the mold easily occurs. The amount of adhesion can be calculated from the weight difference and the surface area of the metal material before and after the treatment.
前述の付着量になるよう にコ ン ト ロールする為には、 水系潤滑 剤の固形分重量 （濃度） を適宜調節する。 実際には、 高濃度の潤 滑剤を希釈し、 その処理液にて使用する場合が多い。 希釈調整す る水は、 特に限定されないが、 脱イオン水や蒸留水が好ましい。 In order to control the amount to be the above-mentioned amount, the weight (concentration) of the solid content of the aqueous lubricant is appropriately adjusted. In fact, high concentrations of Lubricants are often diluted and used in their processing solutions. The water for dilution adjustment is not particularly limited, but deionized water or distilled water is preferable.
金属材料の潤滑皮膜処理に際して、 ショ ッ トブラス ト、 サン ド ブラス ト、 アルカ リ脱脂および酸洗浄から成る群から選ばれる少 なく とも一種の手法によって、 金属材料の清浄化をするのが好ま しい。 こ こで、 清浄化とは、 焼鈍等によ り成長した酸化スケール や各種の汚れ （油など） を除去する こ とを目的と したものである 特に、 近年、 環境問題よ り、 廃水処理負荷の低減が望まれてい る。 この場合、 金属材料表面をショ ッ トブラス ト によ り清浄にし 次いで、 本発明の潤滑剤および処理方法を用いる，こ とによ り、 廃 水ゼロに近づく こ とが出来る。  Preferably, the metal material is cleaned by at least one method selected from the group consisting of shot blasting, sand blasting, alkaline degreasing and acid cleaning when treating the lubricating coating on the metal material. Here, the purpose of cleaning is to remove oxide scales and various stains (oil, etc.) grown by annealing or the like. It is hoped that this will be reduced. In this case, the surface of the metal material is cleaned with a shot blast, and then the lubricant and the treatment method of the present invention are used, whereby zero wastewater can be approached.
本発明の水系潤滑剤を金属材料と接触させる方法は特に限定 されるものでは無い。 例えば、 浸漬法、 フロ一コー ト法、 スプレ 一法などを用いる こ とが出来る。 塗布は表面が本発明の水系潤滑 剤に覆われれば良い。 塗布時間に制限は無い。 塗布後は乾燥する 乾燥は常温放置でも良い、 6 0 〜 1 5 0 °< で 1 〜 3 0分行っても 良い。  The method for bringing the aqueous lubricant of the present invention into contact with a metal material is not particularly limited. For example, an immersion method, a flow coat method, a spray method, or the like can be used. The coating may be performed as long as the surface is covered with the aqueous lubricant of the present invention. There is no limitation on the application time. Dry after application. Drying may be performed at room temperature, or may be performed at 60 to 150 ° <1 to 30 minutes.
乾燥性を高める為には、 金属材料を 6 0 〜 1 0 0 °Cに加温し、 これを水系潤滑剤と接触させる こ とが好ま しい。 尚、 5 0 〜 9 0 °cに加温した水系潤滑剤に金属材料を接触させても良い。 これ らによ り、 乾燥性が大幅に向上し、 乾燥が常温で可能になる場合 もあ り、 熱エネルギーのロスを少なく 出来る。  In order to enhance the drying property, it is preferable to heat the metal material to 60 to 100 ° C and bring it into contact with an aqueous lubricant. The metal material may be brought into contact with an aqueous lubricant heated to 50 to 90 ° C. As a result, the drying property is greatly improved, and drying can be performed at room temperature in some cases, thereby reducing heat energy loss.
以下、 具体的な実施例を挙げて説明する。  Hereinafter, a specific example will be described.
[実施例]  [Example]
<素材 > <Material>
• 後方せん孔試験片 後方せん孔試験に供した材料は、 市販の S 4 5 C球状化焼鈍材 である。 試験片の形状は、 直径 3 0 mm、 高さが 1 6〜 4 0 mm まで 2 mm単位で変えたものである。 • Posterior drilling specimen The material subjected to the posterior drilling test was a commercially available S45C spheroidized annealed material. The shape of the test piece was changed from 30 mm in diameter and 16 to 40 mm in 2 mm increments.
• スパイ ク試験片  • Spike specimens
試験に供した材料は、 市販の S 4 5 C球状化焼鈍材である。 試 験片の形状は、 直径 2 5 mm、 高さが 3 0 mmである。  The material tested was a commercially available S45C spheroidized annealed material. The shape of the test specimen is 25 mm in diameter and 30 mm in height.
<処理工程 > <Treatment process>
工程 A Process A
① 脱脂 ： 日本パーカライジング社製の脱脂剤フ ァイ ンク リ ーナ 一 4 3 6 0 (登録商標） 濃度 2 0 g / L に 6 0 °Cで 1 0 分間浸漬 (1) Degreasing: Immersion for 10 minutes at 60 ° C in a concentration of 20 g / L of Degreasing agent Fine Cleaner (manufactured by Nippon Parkerizing Co., Ltd.)
② 水洗 ： 水道水に室温で 3 0 秒間浸漬 ② Rinse: Immerse in tap water at room temperature for 30 seconds
③ 表面処理 ： 本発明の処理剤に 6 0 °Cで 1 0秒間浸漬  ③ Surface treatment: Immerse in the treatment agent of the present invention at 60 ° C for 10 seconds.
④ 乾燥 ： 8 0 で 3分間  ④ Drying: 80 minutes for 3 minutes
工程 B Process B
①ショ ッ トブラス ト ： 直径が 0 . 5 mmのショ ッ ト球によ り 5 分(1) Shot blast: 5 minutes using a shot ball with a diameter of 0.5 mm
②水洗 ： 水道水に 9 0 °Cで 9 0秒間浸漬 ②Washing: Immerse in tap water at 90 ° C for 90 seconds
③表面処理 ： 本発明の処理剤に 7 0 °Cで 5秒間浸漬  (3) Surface treatment: Immerse in the treatment agent of the present invention at 70 ° C for 5 seconds.
④乾燥 ： 常温 （送風） で 3 分間  ④Drying: 3 minutes at normal temperature (blast)
<評価 > <Evaluation>
· 後方せん孔試験 （第 1 図〜第 3 図を参照）  · Posterior drill test (see Fig. 1 to Fig. 3)
第 1 図の円筒型試験材 1 を、 第 2 図の 2 0 0 t ク ランクプレス のダイ 2 とパンチ 3 とによって成形加工し、 第 3 図のカ ッ プ状成 型品を作成する。 成形においては、 1 0 mm を残し、 減面率 5 0 % の加工である。 尚、 ダイ 2 は S K D 1 1 、 パンチ 3 は H A P 4 0 ラン ド径 2 1 . 2 1 πιιηΦで、 加工速度は 3 0 ス ト ローク Z分で ある。 内面にキズが入っていない試験片のカ ップ内高さを、 良好穿孔 深さ （mm) とする。 穿孔深さは深いほど良い。 従来技術で得ら れる良好穿孔深さ 5 6 mmを一つの目安と して判断する。 The cylindrical test material 1 shown in Fig. 1 is formed by a die 2 and a punch 3 of the 200 t crank press shown in Fig. 2 to produce a cup-shaped molded product shown in Fig. 3. In forming, it is a process of 50% reduction in area, leaving 10 mm. The die 2 has SKD 11, the punch 3 has HAP 40 land diameter 21.2 1 πιιηΦ, and the processing speed is 30 strokes Z. The height in the cup of the test piece with no scratches on the inner surface shall be the good drilling depth (mm). The deeper the hole, the better. The good drilling depth of 56 mm obtained with the conventional technology is used as a guide.
• スパイ ク試験 （第 4 図及び第 5 図を参照）  • Spike test (see Figures 4 and 5)
スパイ ク試験は、 特開平 5 — 7 9 6 9号に準じた。 即ち、 第 4 図に示す如く 、 円柱状の供試片 5 をロー ト状の内面形状を有する ダイ 6 に乗せ、 プラテン 7 によ り荷重を掛け、 供試片 5 をダイ 6 内に押し込んで成形する。  The spike test was performed according to Japanese Patent Application Laid-Open No. 5-7969. That is, as shown in FIG. 4, a columnar specimen 5 is placed on a die 6 having a funnel-shaped inner surface, a load is applied by a platen 7, and the specimen 5 is pushed into the die 6. Molding.
これによ り、 ダイ形状に従うスパイ ク を形成し、 スパイ ク高さ (mm) で潤滑性を評価した。 従って、 高さが高い方が潤滑性に 優れる との評価であ り、 高い方が良い。 従来技術で得られる高さ 1 3 . 0 mmを一つの目安と して判断する。  As a result, spikes were formed according to the die shape, and lubricity was evaluated based on the spike height (mm). Therefore, it is evaluated that the higher the height, the better the lubricity, and the higher, the better. Use the height of 13.0 mm obtained with the conventional technology as a guide.
〔本発明の表面処理剤の作成に関して〕  [Regarding Preparation of Surface Treatment Agent of the Present Invention]
実施例に使用 したリ ン酸塩 （ A) は、 以下の.よう にして作成さ れた。  The phosphate (A) used in the examples was prepared as follows.
5 0 °Cに加温した 0 . 5 m o 1 L の硫酸鉄 （ I I ) 溶液 1 L に、 l m o 1 Z Lの硫酸亜鉛溶液 1 0 O mL、 及び l m o 1 Z Lの リ ン酸一水素ナ ト リ ウム溶液 1 0 O m L を交互に加え、 沈澱を生 成させた。 沈澱を含む水溶液を 9 0 °Cで 1 時間加温して沈澱粒子 を熟成させた。 この後、 傾斜洗浄を 1 0 回繰り返した。 濾過して 得られた沈澱物を乾燥し、 X線回折で分析した。 その結果、 沈澱 物は、 一部第三リ ン酸鉄を含むフォスフオ フイ ラィ ト [Zn2 Fe(PO 4)2 ·4Η20]であった。 5 0 °Cに加温した 0 . 1 m 0 1 Z Lの硝酸カルシウム溶液 1 L に l m o 1 / Lの硝酸亜鉛溶液 2 0 O mL を加え、 更に l m o 1 / L の リ ン酸一水素ナ ト リ ウム溶液 2 0 0 mL を加え、 沈澱を生 成させた。 沈澱を含む水溶液を 9 0 °Cで 1 時間加温して沈澱粒子 を熟成させた。 この後、 傾斜洗浄を 1 0 回繰り返した。 濾過して 得られた沈澱物を乾燥し、 X線回折で分析した。 その結果、 沈澱 物は、 ショ ルタイ ト [Zn2 Ca(P04 )2 ·2Η20]であった。 ホパイ ト （Ζη3 (Ρ04)2 ·4Η20) は試薬を使用した。 実施例 1 〜 3 に使用 した分散剤 （ Β ) の正リ ン酸、 ポリ リ ン酸 有機ホスホン酸化合物は、 試薬及び市販品 （例えば日本モンサン ト工業 （株） 製等） の中から、 その構造をも とに選定した。 処理 液の ρ Ηは本発明の効果に影響を与えない。 伹し、 正リ ン酸、 ポ リ リ ン酸または有機ホスホン酸化合物水溶液の ρ Ηが著し く 低 い場合は、 リ ン酸塩の溶解を防止する為、 予め、 水酸化ナ ト リ ウ ムで水溶液の Ρ Ηを中性に調整した。 実施例 4 の分散剤 （ Β ) は、 一般式 （ I ) の式中 R 1が Η R が C 2 Η 4の単量体を用いた。 実施例 5 の分散剤 （ Β ) は、 ひ ， ι8 不飽和カルボン酸 （ァク リ ル酸） を用い、 過硫酸アンモニゥムを触媒と して重合した重合体 (共重合体） を用いた。 水溶性に難点のある単量体については市 販の界面活性剤を使用 して乳化した後に重合した。 重合体 （共重 合体） の ρ Ηが著し く低い場合は、 リ ン酸塩の溶解を防止する為 予め、 水酸化ナ ト リ ウムで重合体 （共重合体） 溶液の ρ Ηを中性 に調整した。 実施例 6〜 9 で使用 した分散剤 （ B ) の単糖類、 多糖類、 及び その誘導体は、 市販品、 例えばダイセル化学工業株式会社、 第一 工業製薬株式会社、 旭化成工業株式会社製、 大日本製薬株式会社 等の中か ら、 その基本構成糖の種類、 重合度、 置換基、 置換度を もとに選定した。 尚、 置換基については化学式 （ I I ) に基本構 成糖の一つであるグルコースを例示した。 To 1 L of 0.5 mo 1 L iron (II) sulfate solution heated to 50 ° C, add 10 OmL of lmo 1 ZL of zinc sulfate solution, and lmo 1 ZL of monohydrogen phosphate The solution was alternately added with 10 OmL of Pt solution to produce a precipitate. The aqueous solution containing the precipitate was heated at 90 ° C. for 1 hour to mature the precipitated particles. Thereafter, the inclined cleaning was repeated 10 times. The precipitate obtained by filtration was dried and analyzed by X-ray diffraction. As a result, the precipitate was Fosufuo Hui Rai that contains the part third Li down iron [Zn 2 Fe (PO 4) 2 · 4Η 2 0]. To 0.1 m 0 1 ZL of calcium nitrate solution heated to 50 ° C, add lmo 1 / L zinc nitrate solution 20 O mL to 1 L of calcium nitrate solution, and further add lmo 1 A 200 L / L solution of sodium hydrogen phosphate was added to produce a precipitate. The aqueous solution containing the precipitate was heated at 90 ° C. for 1 hour to mature the precipitated particles. Thereafter, the inclined cleaning was repeated 10 times. The precipitate obtained by filtration was dried and analyzed by X-ray diffraction. As a result, the precipitate was sucrose Rutai preparative [Zn 2 Ca (P0 4) 2 · 2Η 2 0]. Hopai Doo (Ζη 3 (Ρ0 4) 2 · 4Η 2 0) was used reagents. The orthophosphoric acid and polyphosphoric acid organic phosphonic acid compound of the dispersant (II) used in Examples 1 to 3 were selected from reagents and commercial products (for example, manufactured by Nippon Monsanto Industry Co., Ltd.). The structure was selected based on the structure. The ρ の of the processing solution does not affect the effect of the present invention. However, if the ρ 正 of the aqueous solution of orthophosphoric acid, polyphosphoric acid or organic phosphonic acid compound is remarkably low, sodium hydroxide is added in advance to prevent dissolution of phosphate. The pH of the aqueous solution was adjusted to neutral with a system. Dispersant Example 4 (beta) is wherein R 1 in the general formula (I) is Eta R was used monomers C 2 Eta 4. As the dispersant (Β) of Example 5, a polymer (copolymer) polymerized using i8 unsaturated carboxylic acid (acrylic acid) and ammonium persulfate as a catalyst was used. For monomers having difficulty in water solubility, polymerization was carried out after emulsification using a commercially available surfactant. If the ρ の of the polymer (copolymer) is extremely low, the ρ の of the polymer (copolymer) solution must be adjusted with sodium hydroxide in advance to prevent dissolution of phosphate. It was adjusted to sex. Monosaccharides, polysaccharides and derivatives thereof of the dispersant (B) used in Examples 6 to 9 are commercially available products, for example, Daicel Chemical Industries, Daiichi Kogyo Pharmaceutical Co., Ltd., Asahi Kasei Kogyo Co., Ltd. Pharmaceuticals Co., Ltd. and others were selected based on the type, degree of polymerization, substituents, and degree of substitution of the basic constituent sugars. The substituent is exemplified by glucose which is one of the basic constituent sugars in the chemical formula (II).
化学式 （ I I )  Chemical formula (II)
Figure imgf000025_0001
Figure imgf000025_0001
グルコースの場合は R 3， R 4, R 5の 3 力所の水酸基をエーテル 化する こ とが出来る。 本実施例では、 置換基の種類および置換度 (置換基による基本構成糖 1単位あた り の水酸基の置換数） を変 え、 その効果を調査した。 水溶性が低い単糖類、 多糖類、 及びそ の誘導体についてはナ ト リ ゥム塩を使用 した。 実施例 6 〜 7 は、 置換基 CH2COOH、 NO2、 置換度 8 以上、 重合度 3 0 0 0 以上のものを用いた。 実施例 8 は、 置換基 CH2COOH、 置換度 0 . 7 、 重合度 1 0 0 以上のものを用いた。 実施例 1 0 ， 1 1 に用いた分散剤 （ B ) の酢酸ビニルの重合体 またはその誘導体としては、 実施例 1 0 に関しては市販のポリ ビ ニルアルコールを用いた。 実施例 1 1 に関しては、 市販の酢酸ビ ニルとエチレンの共重合体を用いた。 In the case of glucose, the hydroxyl groups at three sites, R 3 , R 4 , and R 5 , can be etherified. In this example, the type and degree of substitution (the number of substitutions of hydroxyl groups per unit of the basic constituent sugar by the substituent) were changed, and the effect was investigated. For low water-soluble monosaccharides, polysaccharides, and their derivatives, sodium salts were used. In Examples 6 and 7, the substituents CH 2 COOH, NO 2 , the degree of substitution of 8 or more, and the degree of polymerization of 300 or more were used. In Example 8, one having a substituent of CH 2 COOH, a degree of substitution of 0.7, and a degree of polymerization of 100 or more was used. As the vinyl acetate polymer or the derivative of the dispersant (B) used in Examples 10 and 11, a commercially available polyvinyl alcohol was used in Example 10. In Example 11, a commercially available copolymer of vinyl acetate and ethylene was used.
[実施例 1 ]  [Example 1]
フ ォス フ オ フ イ ライ ト （リ ン酸塩 （ A )) 1 0 0 gに対し、 ト リボリ リ ン酸 1 0 w t %の希釈溶液 （分散剤 （ B ) ) を 1 k g添 加した。 この後、 直径 0 . 5 m mのジルコニァビーズを用いたポ ールミルで約 1 時間粉碎した。 粉砕後、 液中の微粒子の算術平均 粒子径を レーザー回折 Z散乱式粒度分布測定装置 （ L A— 9 2 0 ： (株） 堀場製作所） で測定した。 算術平均粒子径は 0 . 5 mであった。  To 100 g of phosphophyllite (phosphate (A)), 1 kg of a dilute solution (dispersant (B)) of 10 wt% of triribolinic acid was added. . Thereafter, the mixture was ground for about 1 hour with a pole mill using 0.5 mm diameter zirconia beads. After pulverization, the arithmetic average particle diameter of the fine particles in the liquid was measured with a laser diffraction Z-scattering particle size distribution analyzer (LA-920: HORIBA, Ltd.). The arithmetic mean particle size was 0.5 m.
この溶液とマイ ク ロ ク リ スタ リ ンワ ッ ク スの分散溶液 （滑剤 ( C )) とを用いて調整し、 表面処理剤 1 を作成した。 この処理 剤 1 の （ B ) / ( A ) は 1 . 0 、 （ C ) / ( A ) は 1 . 0 である。  The surface treatment agent 1 was prepared by using this solution and a dispersion solution of microcrystalline wash (lubricant (C)). (B) / (A) of this treating agent 1 is 1.0, and (C) / (A) is 1.0.
そして、 この処理剤を用い、 工程 Aにて、 皮膜付着量が 8 gノ m 2になるよう に処理を行った。 Then, using this treating agent, a treatment was carried out in step A so that the amount of coating film became 8 g nom 2 .
[実施例 2 ]  [Example 2]
フ ォス フ オ フイ ライ ト （リ ン酸塩 （ A )) 5 0 g に対し、 へキ サメ夕 リ ン酸 1 0 w t %希釈溶液 （分散剤 （ B ) ) を 1 k g添加 した。 この後、 直径 0 . 5 m mのジルコ二アビ一ズを用いたポー ルミルで約 1 時間粉砕した。 粉砕後、 液中の微粒子の算術平均粒 子径を L A— 9 2 0 で測定した。 算術平均粒子径は 0 . 5 mで あった。 50 g of phosphophyllite (phosphate (A)) 1 kg of a 10 wt% shark phosphate solution (dispersant (B)) was added. This was followed by grinding for about 1 hour with a pole mill using 0.5 mm diameter zirconia beads. After pulverization, the arithmetic average particle diameter of the fine particles in the liquid was measured with LA-920. The arithmetic mean particle size was 0.5 m.
この溶液とステア リ ン酸カルシウムの分散溶液 （滑剤 （ C ) ) とを用いて調整し、 表面処理剤 2 を作成した。 この処理剤 2 の ( B ) / (A) は 2 . 0 、 ( C ) / ( A ) は 4. 0 である。  The surface treatment agent 2 was prepared by using this solution and a dispersion solution of calcium stearate (lubricant (C)). (B) / (A) of this treating agent 2 is 2.0, and (C) / (A) is 4.0.
そして、 この処理剤を用い、 工程 Aにて、 皮膜付着量が 1 0 g / m 2になるよう に処理を行った。 Then, in this step A, a treatment was carried out in step A so that the amount of the coating film became 10 g / m 2 .
[実施例 3 ]  [Example 3]
ホパイ ト （リ ン酸塩 （ A )) 1 0 0 g に対し、 アミ ノ ト リ メチ レンホスホン酸 1 0 w t %希釈溶液 （分散剤 （ B )) を l k g添 加した。 この後、 直径 0 . 5 m mのジルコニァビーズを用いたポ ールミルで約 1 時間粉砕した。 粉砕後、 溶液中の微粒子の算術平 均粒子径を L A— 9 2 0で測定した。 算術平均粒子径は 1 . マ 11 mであった。  To 100 g of Hopite (phosphate (A)), lkg of a 10 wt% aminotrimethylenephosphonic acid diluted solution (dispersant (B)) was added. Thereafter, the mixture was ground for about 1 hour by a pole mill using 0.5 mm diameter zirconia beads. After pulverization, the arithmetic average particle diameter of the fine particles in the solution was measured by LA-920. The arithmetic mean particle size was 1.11 m.
この溶液とポリ エチレンワ ッ クスの分散溶液 （滑剤 （ C )) と を用いて調整し、 表面処理剤 3 を作成した。 この処理剤 3 の （ B ) / ( A ) は 1 · 0 、 ( C ) / ( A ) は 0 . 5 である。  The surface treatment agent 3 was prepared by using this solution and a dispersion solution of polyethylene wax (lubricant (C)). (B) / (A) of this treating agent 3 is 1.0, and (C) / (A) is 0.5.
この処理剤を用い、 工程 Aにて、 皮膜付着量が 1 0 g / m 2 に なるよう に処理を行った。 Using this treating agent, a treatment was performed in step A so that the amount of coating film became 10 g / m 2 .
[実施例 4 ]  [Example 4]
フォスフオ フイ ライ ト （リ ン酸塩 （ A )) 2 0 g に対し、 単量 体 （化学式 （ I ) の式中 R 1が H、 R 2が C 2 H 4 ) から作成した重 合体 1 0 wt %希釈溶液 （分散剤 （ B ) ) を 1 k g添加した。 この 後、 直径 0 . 5 m mのジルコニァビーズを用いたポールミルで約 1 時間粉砕した。 粉碎後、 水道水で懸濁液中のフォスフオフイ ラ イ ト濃度が 1 % となるよう に調整した。 溶液中の微粒子の算術平 均粒子径を L A— 9 2 0 で測定した。 算術平均粒子径は 0 . 5 a mであった。 For 20 g of phosphophyllite (phosphate (A)), a polymer prepared from a monomer (R 1 is H and R 2 is C 2 H 4 ) in the formula of chemical formula (I) is 10 1 kg of a wt% diluted solution (dispersant (B)) was added. this Thereafter, the mixture was ground for about 1 hour with a pole mill using 0.5 mm-diameter zirconia beads. After pulverization, the suspension was adjusted with tap water so that the concentration of phosphoric acid in the suspension was 1%. The arithmetic average particle size of the fine particles in the solution was measured with LA-920. The arithmetic mean particle size was 0.5 am.
この溶液とステア リ ン酸カルシウムの分散溶液およびマイ ク 口ク リ スタ リ ンワ ッ クスの分散溶液 （滑剤 （ C ) ) とを用いて調 整し、 表面処理剤 4 を作成した。 尚、 ステアリ ン酸カルシウムと マイ ク ロク リスタ リ ンワッ クスとの重量比は 1 ： 1 とした。 この 処理剤 4 の （ B ) / ( A ) は 5 . 0 、 ( C ) / ( A ) は 2 . 5 で ある。  The surface treatment agent 4 was prepared by adjusting this solution, a dispersion solution of calcium stearate, and a dispersion solution of crystal mouth wax (lubricant (C)). The weight ratio of calcium stearate to microcrystalline detergent was 1: 1. (B) / (A) of this treating agent 4 is 5.0, and (C) / (A) is 2.5.
この処理剤を用い、 工程 Aにて、 皮膜付着量が 1 0 g / m 2 に なるよう に処理を行った。 Using this treating agent, a treatment was performed in step A so that the amount of coating film became 10 g / m 2 .
[実施例 5 ]  [Example 5]
ショルタイ ト （リ ン酸塩 （ A ) ) 1 0 0 g に対し、 α， ）3不飽 和カルボン酸単量体 （アク リル酸） を用いて構成した重合体 1 0 w t %希釈溶液 （分散剤 （ B ) ) を 1 k g添加した。 この後、 直 径 0 . 5 m mのジルコニァビーズを用いたボールミルで約 1 時間 粉碎した。 溶液中の微粒子の算術平均粒子径を L A— 9 2 0 で測 定した。 算術平均粒子径は 0 . 5 / mであった。  100 wt% of a polymer composed of α,) 3 unsaturated carboxylic acid monomer (acrylic acid) per 100 g of cholesterol (phosphate (A)) (dispersion 1 kg of the agent (B)) was added. Thereafter, the mixture was ground for about 1 hour with a ball mill using zirconia beads having a diameter of 0.5 mm. The arithmetic average particle size of the fine particles in the solution was measured by LA-920. The arithmetic mean particle size was 0.5 / m.
この溶液とステア リ ン酸カルシウムの分散溶液およびバラフ イ ンワックスの分散溶液 （滑剤 （ C ) ) とを用いて調整した。 尚、 ステア リ ン酸カルシウム とマイ ク ロク リ ス夕 リ ンワッ クス との 重量比は 1 ： 2 と した。  An adjustment was made using this solution, a dispersion of calcium stearate, and a dispersion of paraffin wax (lubricant (C)). In addition, the weight ratio of calcium stearate to microcrystalline sugar was set to 1: 2.
更に、 前記溶液に四ほう酸ナ ト リ ウム （無機塩 （ D ) ) を添加 し、 表面処理剤 5 を作成した。 この処理剤 5 の （ B ) Z ( A ) は 1 . 0 、 ( C ) / ( A) は 1 . 5 、 ( D ) / ( A ) は 0 . 5 である この処理剤を用い、 工程 Aにて、 皮膜付着量が 1 5 g m 2 に なるよう に処理を行った。 Further, sodium tetraborate (inorganic salt (D)) was added to the solution to prepare a surface treating agent 5. (B) Z (A) of this treating agent 5 is 1.0, (C) / (A) is 1.5, and (D) / (A) is 0.5. Using this treatment agent, the amount of coating film becomes 15 gm 2 in process A. Processing was performed as follows.
[実施例 6 ]  [Example 6]
フ ォスフオ フイ ライ ト （リ ン酸塩 （ A )) 5 0 g に対し、 ダル コース誘導体を予めィ ソ プロ ピルアルコ ール及び水で 1 0 w t % に希釈溶解した溶液 （分散剤 （ B ) ) を 1 k g添加した。 こ の後、 直径 0 . 5 m mのジルコニァビーズを用いたポールミルで 約 1 時間粉碎した。 粉砕後、 溶液中の微粒子の算術平均粒子径を L A— 9 2 0 で測定した。 算術平均粒子径は 0 . 5 mであった こ の溶液とマイ ク ロ ク リ スタ リ ンワ ッ クスの分散溶液 （滑剤 ( C )) とを用いて調整し、 表面処理剤 6 を作成した。 この処理 剤 6 の （ B ) / ( A ) は 2 . 0 、 ( C ) / ( A ) は 1 . 0 である。  A solution prepared by diluting 50 g of phosphophyllite (phosphate (A)) with 10 wt% of a DACOS derivative in advance with isopropyl alcohol and water (dispersant (B)) Was added in an amount of 1 kg. Thereafter, the mixture was ground for about 1 hour with a pole mill using 0.5 mm diameter zirconia beads. After pulverization, the arithmetic average particle diameter of the fine particles in the solution was measured by LA-920. The surface treatment agent 6 was prepared by adjusting the arithmetic mean particle size of the solution having a diameter of 0.5 m and a dispersion solution of microcrystalline detergent (lubricant (C)). (B) / (A) of this treating agent 6 is 2.0, and (C) / (A) is 1.0.
この処理剤を用い、 工程 B にて、 皮膜付着量が 1 5 g / m 2 に なるよう に処理を行った。 Using this treating agent, a treatment was performed in step B so that the amount of coating film became 15 g / m 2 .
[実施例 7 ]  [Example 7]
フ ォスフオ フイ ライ ト （リ ン酸塩 （ A )) 2 0 g に対し、 ダル コース誘導体を予め水で 1 0 w t %に希釈溶解した溶液 （分散剤 ( B ) ) を 1 k g添力 Qした。 この後、 直径 0 . 5 m mのジルコ二 ァビーズを用いたポールミルで約 1 時間粉枠した。 粉碎後、 溶液 中の微粒子の平均粒径を L A— 9 2 0 で測定した。 算術平均粒子 径は 0 . 5 x mであった。  To 20 g of phosphophyllite (phosphate (A)), 1 kg of a solution (dispersant (B)) prepared by diluting and dissolving a DACOS derivative in water with 10 wt% in advance was added. . Thereafter, the powder was ground for about 1 hour by a pole mill using zirconia beads having a diameter of 0.5 mm. After pulverization, the average particle size of the fine particles in the solution was measured using LA-920. The arithmetic mean particle size was 0.5 x m.
この溶液とステア リ ン酸カルシウムの分散溶液 （滑剤 （ C ) ) とを用いて調整し、 表面処理剤 7 を作成した。 この処理剤 7 の ( B ) / ( A ) は 5 . 0 、 ( C ) / ( A ) は 3 . 0 である。  Using this solution and a dispersion solution of calcium stearate (lubricant (C)), a surface treatment agent 7 was prepared. (B) / (A) of this treating agent 7 is 5.0, and (C) / (A) is 3.0.
この処理剤を用い、 工程 B にて、 皮膜付着量が 2 0 g Z m 2 に なるよう に処理を行った。 Using this treatment agent, in step B, the coating weight was reduced to 20 g Z m 2 The treatment was performed as follows.
[実施例 8 ]  [Example 8]
フォスフオフイ ライ ト （リ ン酸塩 （ A ) ) 2 0 g に対し、 ダル コース誘導体を予め水で 1 w t % に希釈溶解した溶液 （分散剤 ( B ) ) を l k g添加した。 この後、 直径 0 . 5 m mのジルコ二 アビ一ズを用いたボールミルで約 1 時間粉砕した。 粉砕後、 溶液 中の微粒子の算術平均粒子径を L A — 9 2 0 で測定した。 算術平 均粒子径は 0 . 5 mであった。  To 20 g of phosphophyllite (phosphate (A)), lkg of a solution (dispersant (B)) in which a darkose derivative was previously diluted to 1 wt% with water and dissolved was added. Thereafter, the mixture was ground for about 1 hour with a ball mill using 0.5 mm diameter zirconia beads. After pulverization, the arithmetic mean particle size of the fine particles in the solution was measured using LA-920. The arithmetic mean particle size was 0.5 m.
この溶液とポリ エチレンワッ クスの分散溶液 （滑剤 （ C ) ) と を用いて調整し、 表面処理剤 8 を作成した。 この処理剤 8 の （ B ) / ( A ) は 5 . 0 、 ( C ) / ( A ) は 0 . 5 である。  The surface treatment agent 8 was prepared by using this solution and a dispersion solution of polyethylene wax (lubricant (C)). (B) / (A) of this treating agent 8 is 5.0, and (C) / (A) is 0.5.
この処理剤を用い、 工程 B にて、 皮膜付着量が 1 0 g Z m 2 に なるよう に処理を行った。 Using this treating agent, a treatment was performed in step B so that the amount of coating film became 10 g Zm 2 .
[実施例 9 ]  [Example 9]
ホパイ ト （リ ン酸塩 （ A ) ) 2 0 g に対し、 グルコースを予め 水で 1 0 w t %に希釈溶解した溶液 （分散剤 （ B ) ) を 1 k g添 加した。 この後、 直径 0 . 5 m mのジルコニァビーズを用いたポ ールミルで約 1 時間粉碎した。 粉碎後、 溶液中の微粒子の算術平 均粒子径を L A — 9 2 0 で測定した。 算術平均粒子径は 0 . 6 β mであった。  To 20 g of Hopite (phosphate (A)), 1 kg of a solution (dispersant (B)) prepared by diluting glucose in water to 10 wt% in advance was added. Thereafter, the mixture was ground for about 1 hour with a pole mill using 0.5 mm diameter zirconia beads. After pulverization, the arithmetic mean particle size of the fine particles in the solution was measured using LA-920. The arithmetic mean particle size was 0.6 β m.
この溶液とステア リ ン酸亜鉛の分散溶液およびマイ ク ロ ク リ ス夕 リ ンワ ッ クスの分散溶液 （滑剤 （ C )) とを用いて調整し、 表面処理剤 9 を作成した。 尚、 ステアリ ン酸亜鉛とマイ ク ロク リ スタ リ ンワ ッ クス との重量比は 1 ： 1 と した。 こ の処理剤 9 の ( B ) / ( A ) は 5 . 0 、 ( C ) / ( A ) は 2 . 5 である。  The surface treatment agent 9 was prepared by using this solution, a dispersion solution of zinc stearate, and a dispersion solution of micro-crosslinking solution (lubricant (C)). The weight ratio of zinc stearate to microcrystalline wax was 1: 1. (B) / (A) of this treating agent 9 is 5.0, and (C) / (A) is 2.5.
この処理剤を用い、 工程 B にて、 皮膜付着量が 2 0 g Z m 2 に なるよ う に処理を行った。 Using this treatment agent, in step B, the coating weight was reduced to 20 g Z m 2 Processing was performed as follows.
[実施例 1 0 ]  [Example 10]
フォス フオ フイ ライ ト （ リ ン酸塩 （ A )) 1 0 0 g に対し、 ポ リ ビニルアルコールを 1 0 w t % に希釈溶解した溶液 （分散剤 ( B ) ) を l k g添加した。 この後、 直径 0 . 5 mmのジルコ二 ァビーズを用いたポールミルで約 1 時間粉砕した。 粉砕後、 溶液 中の微粒子の算術平均粒子径を L A— 9 2 0で測定した。 算術平 均粒子径は 0 . 5 mであった。  To 100 g of phosphophyllite (phosphate (A)), lkg of a solution (dispersant (B)) obtained by diluting and dissolving polyvinyl alcohol in 10 wt% was added. Thereafter, the mixture was ground for about 1 hour with a pole mill using zirconia beads having a diameter of 0.5 mm. After pulverization, the arithmetic average particle diameter of the fine particles in the solution was measured by LA-920. The arithmetic mean particle size was 0.5 m.
この溶液とステア リ ン酸ナ ト リ ゥムの分散溶液およびパ ラフ イ ンワ ッ クスの分散溶液 （滑剤 （ C ) ) とを用いて調整した。 尚、 ス テア リ ン酸ナ ト リ ウム とパ ラ フィ ン ワ ッ ク ス と の重量比は 1 ： 2 と した。  Preparation was performed using this solution, a dispersion of sodium stearate and a dispersion of paraffin wax (lubricant (C)). The weight ratio between sodium stearate and paraffin wax was set to 1: 2.
更に、 前記溶液に四ほう酸ナ ト リ ウム （無機塩 （ D ) ) を添加 し、 表面処理剤 1 0 を作成した。 こ の処理剤 1 0 の （ B ) / ( A ) は 1 . 0 、 ( C ) / ( A ) は 1 . 5 . ( D ) / ( A) は 5 . 0 であ る。  Further, sodium tetraborate (inorganic salt (D)) was added to the solution to prepare a surface treating agent 10. (B) / (A) of this treating agent 10 is 1.0, (C) / (A) is 1.5. (D) / (A) is 5.0.
この処理剤を用い、 工程 B にて， 皮膜付着量が 5 g / m 2 にな るよう に処理を行った。 Using this treatment agent, treatment was performed in step B so that the amount of coating film became 5 g / m 2 .
[実施例 1 1 ]  [Example 11]
ショ ルタイ ト （リ ン酸塩 （ A ) ) 0 0 g に対し、 酢酸ビニル とエチレンとの共重合体を予め水で 1 O w t % に希釈溶解した 溶液 （分散剤 （ B ) ) を 1 k g添加した。 この後、 直径 1 0 m m のジルコニァビーズを用いたポールミルで約 1 時間粉砕した。 粉 砕後、 溶液中の微粒子の算術平均粒子径を L A— 9 2 0 で測定し た。 算術平均粒子径は 0 . 5 mであった。  1 kg of a solution (dispersant (B)) prepared by diluting and dissolving a copolymer of vinyl acetate and ethylene in water at a concentration of 1 O wt% with respect to 100 g of cholesterol (phosphate (A)) Was added. Thereafter, the mixture was ground for about 1 hour by a pole mill using zirconia beads having a diameter of 10 mm. After pulverization, the arithmetic mean particle size of the fine particles in the solution was measured by LA-920. The arithmetic mean particle size was 0.5 m.
この溶液とマイ ク ロク リ スタ リ ンワ ッ クスの分散溶液 （滑剤 ( C )) とを用いて調整した。 Dispersion solution of this solution and Microcrystalline Linwax (lubricant (C)).
更に、 前記溶液にケィ酸カ リ ウム （無機塩 （ D ) ) を添加し、 表面処理剤 1 1 を作成した。 この処理剤 1 1 の （ B ) / ( A ) は 1 . 0 、 ( C ) / ( A ) は 1 . 0 、 （ D ) / ( A) は 2 . 0 である この処理剤を用い、 工程 B にて、 皮膜付着量が 1 5 g Z m 2 に なるよう に処理を行った。 Further, potassium silicate (inorganic salt (D)) was added to the solution to prepare a surface treatment agent 11. (B) / (A) of this treating agent 11 is 1.0, (C) / (A) is 1.0, and (D) / (A) is 2.0. In B, the treatment was performed so that the coating amount became 15 g Zm 2 .
[比較例 1 ]  [Comparative Example 1]
フ ォスフオ フ イ ライ ト （リ ン酸塩 （ A )) 1 0 0 g に対し、 ト リボ リ リ ン酸 1 0 w t %の希釈溶液 （分散剤 （ B ) ) を 1 k g添 加した。 この後、 直径 0 . 5 mmのジルコ二アビ一ズを用いたポ ールミルで約 1 時間粉砕した。 粉砕後、 液中の微粒子の算術平均 粒子径を L A— 9 2 0 で測定した。 算術平均粒子径は 0 . 5 m ' であった。  To 100 g of phosphophyllite (phosphate (A)), 1 kg of a dilute solution (dispersant (B)) of 10 wt% of triribolinic acid was added. Thereafter, the mixture was ground for about 1 hour by a pole mill using 0.5 mm diameter zirconia beads. After pulverization, the arithmetic average particle diameter of the fine particles in the liquid was measured with LA-920. The arithmetic mean particle size was 0.5 m '.
この溶液を表面処理剤 1 2 とした。 この処理剤 1 2 の （ B ) / ( A ) は 1 . 0 である。  This solution was used as a surface treatment agent 12. (B) / (A) of this treating agent 12 is 1.0.
この処理剤を用い、 工程 Aにて、 皮膜付着量が 5 g Z m 2 にな るよう に処理を行った。 Using this treating agent, a treatment was performed in step A so that the amount of coating film became 5 g Zm 2 .
[比較例 2 ]  [Comparative Example 2]
グルコース誘導体を予め水で 1 0 w t %に希釈溶解した溶液 (分散剤 （ B ) ) 1 k g にステアリ ン酸カルシウムの分散溶液 （滑 剤 （ C ) ) 及び水を用いて調整し、 表面処理剤 1 3 を作成した。 尚、 分散剤 （ B ) の濃度は 5 %、 滑剤 （ C ) の濃度も 5 % となる よう調整した。  A solution prepared by diluting and dissolving a glucose derivative to 10 wt% with water (dispersant (B)) in 1 kg using a calcium stearate dispersion solution (lubricant (C)) and water, and a surface treatment agent Created 1 3. The concentration of the dispersant (B) was adjusted to 5%, and the concentration of the lubricant (C) was adjusted to 5%.
この処理剤を用い、 工程 B にて、 皮膜付着量が 1 0 g / m 2 に なるよう に処理を行った。 Using this treating agent, a treatment was performed in step B so that the amount of coating film became 10 g / m 2 .
[比較例 3 ] 以下の処理工程にて処理を行った。 [Comparative Example 3] The processing was performed in the following processing steps.
<処理工程 > <Treatment process>
① 脱脂 ： 日本パーカライジング社製の脱脂剤ファイ ンク リーナ ① Degreasing: Fine Cleaner, a degreasing agent manufactured by Nippon Parkerizing Co., Ltd.
- 4 3 6 0 (登録商標） 濃度 2 0 g Z L に 6 0 °Cで 1 0分間浸漬 ② 水洗 ： 水道水に室温で 3 0秒間浸漬 -4 360 (registered trademark) concentration 20 g Immerse in ZL at 60 ° C for 10 minutes ② Rinse: Immerse in tap water at room temperature for 30 seconds
③ 化成処理 ： 日本パーカライジング社製のリ ン酸亜鉛化成処理 剤パルポン ド 1 8 1 X (登録商標） 濃度 9 0 g / Lに 8 0 °Cで 1 0分間浸漬  3) Chemical conversion treatment: Zinc phosphate chemical conversion treatment palpond manufactured by Nippon Parkerizing Co., Ltd. Immerse in 180 g / L at 90 g / L at 80 ° C for 10 minutes
④ 水洗 ： 水道水に室温で 3 0秒間浸漬  ④ Rinse: Immerse in tap water at room temperature for 30 seconds
⑤ 石鹼処理 ： 日本パーカライジング社製の反応石鹼潤滑剤パル ーブ 2 3 5 (登録商標） 濃度 7 0 g Z L に 8 0 °Cで 5分間浸漬 ⑥ 乾燥 ： 8 0 で 3分間 ⑤ Stone treatment: Reaction stone manufactured by Nippon Parkerizing Co., Ltd. 鹼 Lubricant tube 2 35 5 (registered trademark) concentration 70 g Dipped in ZL at 80 ° C for 5 minutes 乾燥 Drying: 80 minutes for 3 minutes
[比較例 4 ]  [Comparative Example 4]
以下に示す水系潤滑剤 1 4 (特開平 1 0 — 8 0 8 5号の発明に 準拠） を用い、 工程 Aにて、 皮膜付着量が 1 0 g / m 2 になるよ う処理した。 Using the following aqueous lubricant 14 (based on the invention of Japanese Patent Application Laid-Open No. 10-85085), in step A, treatment was performed so that the coating amount became 10 g / m 2 .
[水系潤滑剤 1 4 ]  [Water-based lubricant 1 4]
水溶性無機塩 ： 四ホウ酸ナ ト リ ウム 1 0 %  Water-soluble inorganic salt: sodium tetraborate 10%
固体潤滑剤 ： ステアリ ン酸カルシウム 1 0 %  Solid lubricant: Calcium stearate 10%
油成分 ： パーム油 0 . 5 %  Oil component: palm oil 0.5%
界面活性剤 ； ポ リ オキシエチレンアルキルアルコール 1 % 残分 ： 水  Surfactant: Polyoxyethylene alkyl alcohol 1% Residue: Water
[比較例 5 ]  [Comparative Example 5]
以下に示す水系潤滑剤 1 5 (特開 2 0 0 0 — 6 3 8 8 0 号の発 明に準拠） を用い、 工程 Aにて、 皮膜付着量が 1 0 g Z m 2 にな るよう処理した。 [水系潤滑剤 1 5 ] Using the aqueous lubricant 15 shown below (based on the invention of Japanese Patent Application Laid-Open No. 2000-0-6380), in the process A, the coating amount becomes 10 g Zm 2 in the process A. Processed. [Water-based lubricant 15]
水溶性無機塩 ： 四ほう酸ナ ト リ ウム 6 %  Water-soluble inorganic salt: sodium tetraborate 6%
合成樹脂 ： ウ レタ ン樹脂 3 %  Synthetic resin: Urethane resin 3%
脂肪酸の金属塩 ： ステア リ ン酸カルシウム 9 %  Fatty acid metal salt: Calcium stearate 9%
界面活性剤 ： ノ ニオン系界面活性剤 1 %  Surfactant: Nonionic surfactant 1%
残分 ： 水  Residue: water
固形分比 （水溶性無機塩/合成樹脂） = 2ノ 1  Solid content ratio (water-soluble inorganic salt / synthetic resin) = 2 1
固形分比 （ステア リ ン酸カルシウムノ合成樹脂） = 3 以上の試験結果を表一 1 に示す。  Table 1 shows the test results for solid content ratio (calcium stearate synthetic resin) = 3 or more.
1  1
処理工程数 処理 後方せん孔深さ スパイ ク高さ  Number of processing steps Processing Back drilling depth Spike height
(mm) 実施例 1 4 塗布型 6 0 1 3 . 1 実施例 2 4 6 0 1 3 . 2 実施例 3 4 塗布型 6 0 1 3 . 3 実施例 4 4 塗布型 6 0 1 3 . 1 実施例 5 4 塗布型 6 0 1 3 . 4 実施例 6 4 塗布型 6 0 1 3 . 4 実施例 7 4 塗布.型 6 0 1 3 . 2 実施例 8 4 塗布型 6 0 1 3 . 2 実施例 9 4 塗布型 6 0 1 3 . 4 実施例 1 0 4 塗布型 6 0 1 3 . 5 実施例 1 1 4 6 0 1 3 . 5 比較例 1 4 塗布型 3 6 焼き付き 比較例 2 4 塗布型 4 0 1 1 . 0 比較例 3 6 反応型/廃棄物多 5 6 1 3 . 0 比較例 4 4 塗布型 5 6 1 2 . 5 比較例 5 4 塗布型 5 6 1 2 . 6 この表— 1 から、 本発明の金属材料用塑性加工用水系潤滑剤を 用いた実施例 1 〜 1 1 は優れた潤滑性を発揮する こ とが判る。 又 処理工程数も多く ない。 (mm) Example 14 4 Coating type 60.13.1 Example 2 4 6 0 13.2 Example 3 4 Coating type 60.13.3 Example 4 4 Coating type 60.13.1 Example 5 4 coating type 6 0 1 3 4 Example 6 4 coating type 6 0 1 3 4 Example 7 4 coating type 6 0 1 3 2 Example 8 4 coating type 6 0 1 3 2 2 Example 9 4 Coating type 6 1 1 3 4 Example 1 0 4 Coating type 6 0 1 3 .5 Example 1 1 4 6 0 1 3 .5 Comparative example 1 4 Coating type 3 6 Burn-in Comparative example 2 4 Coating type 4 0 1 1. 0 Comparative Example 3 6 Reaction Type / Waste Waste 5 6 1 3 .0 Comparative Example 4 4 Coating Type 5 6 1 2 .5 Comparative Example 5 4 Coating Type 5 6 12.6. It can be seen that Examples 1 to 11 using the water-based lubricant for plastic working for materials exhibit excellent lubricity. Also, the number of processing steps is not large.
これに対して、 成分 （ C ) を含まない比較例 1 では潤滑性が劣 つていた。 特に、 スパイ クテス トでは焼付きを生じ、 成形する こ とが出来なかった。  On the other hand, Comparative Example 1 containing no component (C) had poor lubricity. In particular, the spike test caused seizure and could not be formed.
成分 （ A ) を含まない比較例 2 も潤滑性が劣っていた。  Comparative Example 2 containing no component (A) also had poor lubricity.
又、 リ ン酸塩皮膜と反応石鹼潤滑剤とを用いた比較例 3 は、 潤 滑性が比較的良いものの、 本発明のものよ り も多少劣る。 又、 廃 水処理や液管理が必要で、 簡便な設備では使用できない。 更に、 反応に伴う廃棄物を生じる為、 環境負荷が大きい。  Further, Comparative Example 3 using a phosphate film and a reaction stone / lubricant has relatively good lubricity, but is somewhat inferior to that of the present invention. In addition, wastewater treatment and liquid management are required, and it cannot be used with simple equipment. In addition, waste is generated due to the reaction, resulting in a large environmental burden.
又、 特開平 1 0 — 8 0 8 5号の発明に相当する比較例 4、 及び 特開 2 0 0 0 - 6 3 8 8 0 号の発明に相当する合成樹脂を主成 分とする比較例 5 は、 スパイ ク試験や後方せん孔試験にて潤滑性 が劣っている。 産業上の利用可能性  Further, Comparative Example 4 corresponding to the invention of JP-A-10-85085, and Comparative Example in which the main component is a synthetic resin corresponding to the invention of JP-A-2000-6380. 5 has poor lubricity in spike test and posterior drill test. Industrial applicability
金属材料を鍛造、 伸線、 伸管のような塑性加工を行う際、 潤滑 性が良い為に、 製造歩留ま りが高い。 しかも、 その際、 地球環境 保全が考慮される。 即ち、 廃棄物が少なく 、 かつ、 作業環境も良 好である。 更には、 化成処理が不要であるなど簡便な処理で行え る。  When performing plastic working such as forging, drawing, or drawing metal materials, the production yield is high due to good lubricity. In addition, at that time, global environmental preservation is considered. That is, the amount of waste is small and the working environment is good. Furthermore, it can be performed by a simple treatment such as no chemical conversion treatment is required.

Claims

請 求 の 範 囲 The scope of the claims
1 . Z n， F e , M n , N i ， C o , C a， M g及び A l の群 の中か ら選ばれる二価も し く は三価の金属の少な く と も一種を 含有する リ ン酸塩 （ A) と、 1. At least one divalent or trivalent metal selected from the group consisting of Zn, Fe, Mn, Ni, Co, Ca, Mg and Al. Containing phosphate (A),
分散剤 （ B ) と、  A dispersant (B),
ワックス、 及び脂肪酸の金属塩の群の中か ら選ばれる少なく と も一種の滑剤 （ C )  At least one lubricant selected from the group of waxes and metal salts of fatty acids (C)
とを含有する こ とを特徴とする金属材料加工用潤滑剤。 A lubricant for processing metal materials, comprising:
2 . リ ン酸塩 （A ) は平均粒径が 3 m以下の粒子である こ と を特徴とする請求項 1 記載の金属材料加工用潤滑剤。 2. The lubricant for processing metal materials according to claim 1, wherein the phosphate (A) is a particle having an average particle diameter of 3 m or less.
3 . 分散剤 （ B ) が、 正リ ン酸、 ポリ リ ン酸、 有機ホスホン酸 化合物、 及びその誘導体の群の中から選ばれる少なく とも一種で ある こ と を特徴とする請求項 1 又は請求項 2 記載の金属材料加 ェ用潤滑剤。 3. The method according to claim 1, wherein the dispersant (B) is at least one selected from the group consisting of orthophosphoric acid, polyphosphoric acid, organic phosphonic acid compounds, and derivatives thereof. Item 2. Lubricants for adding metal materials according to item 2.
4 . 分散剤 （ B ) が、 不飽和カルボン酸及びノ又はそのエステ ルを用いて得られた重合体の群の中か ら選ばれる少な く と も一 種である こ と を特徴とする請求項 1 又は請求項 2 記載の金属材 料加工用潤滑剤。 4. The method according to claim 1, wherein the dispersant (B) is at least one member selected from the group consisting of unsaturated carboxylic acids and polymers obtained by using the esters thereof. The lubricant for processing a metal material according to claim 1 or 2.
5 . 分散剤 （ B ) が、 単糖類、 多糖類、 及びその誘導体の群の 中か ら選ばれる少な く と も一種である こ と を特徴とする請求項5. The dispersant (B) is characterized in that it is at least one selected from the group consisting of monosaccharides, polysaccharides, and derivatives thereof.
1 又は請求項 2記載の金属材料加工用潤滑剤。 3. The lubricant for processing a metal material according to claim 1 or 2.
6 . 分散剤 （ B ) が、 酢酸ビエル系重合体の群の中から選ばれ る少な く と も一種である こ と を特徴とする請求項 1 又は請求項 2記載の金属材料加工用潤滑剤。 6. The lubricant for processing metal materials according to claim 1 or 2, wherein the dispersant (B) is at least one member selected from the group consisting of biel acetate polymers. .
7 . 分散剤 （ B ) が、 ウ レタン系重合体の群の中から選ばれる 少な く と も一種である こ と を特徴とする請求項 1 又は請求項 2 記載の金属材料加工用潤滑剤。 7. The lubricant according to claim 1, wherein the dispersant (B) is at least one member selected from the group consisting of urethane polymers.
8 . 滑剤 （ C ) が、 水に分散した合成ワッ クスである こ とを特 徴とする請求項 1 〜請求項 7 いずれかに記載の金属材料加工用 潤滑剤。 8. The lubricant for metal material processing according to any one of claims 1 to 7, wherein the lubricant (C) is a synthetic wax dispersed in water.
9 . 滑剤 （ C ) が、 Z n , C a， B a , A 1 , M g及び L i の 群の中から選ばれる少なく とも一種と、 炭素数 1 2 〜 2 6 の脂肪 酸との反応物である こ と を特徴とする請求項 1 〜請求項 7 いず れかに記載の金属材料加工用潤滑剤。 9. Reaction of the lubricant (C) with at least one selected from the group consisting of Zn, Ca, Ba, A1, Mg and Li with a fatty acid having 12 to 26 carbon atoms. The lubricant for processing metal materials according to any one of claims 1 to 7, wherein the lubricant is a material.
1 0 . リ ン酸塩 （ A )、 分散剤 （ B )、 滑剤 （ C ) の割合 （固形 分重量比率） が、 ( B ) / ( A ) = 0 . 0 1 〜 5 、 ( C ) / ( A )10. The ratio (solid content weight ratio) of phosphate (A), dispersant (B) and lubricant (C) is (B) / (A) = 0.01 to 5, (C) / (A)
= 0 . 1 〜 5 である こ とを特徴とする請求項 1 〜請求項 9 いずれ かに記載の金属材料加工用潤滑剤。 10. The lubricant for processing a metal material according to claim 1, wherein 0.1 to 5 is satisfied.
1 1 . 硫酸塩、 ケィ酸塩、 ホウ酸塩、 モリ ブデン酸塩、 及び夕 ングステン酸塩の群の中か ら選ばれる少な く と も一種の無機塩 ( D ) を更に含有する こ とを特徴とする請求項 1 〜請求項 1 0 い ずれかに記載の金属材料加工用潤滑剤。 11 1. It must further contain at least one inorganic salt (D) selected from the group consisting of sulfates, silicates, borates, molybdates, and ungustenoates. Claims 1 to 10 A lubricant for processing a metal material according to any one of the above.
1 2 . 無機塩 （ D ) の割合 （固形分重量比率） が、 （ D ) / ( A ) = 0 . 0 1 〜 1 0 である こ とを特徴とする請求項 1 1 に記載の金 属材料加工用潤滑剤。 12. The metal according to claim 11, wherein the ratio (solid content weight ratio) of the inorganic salt (D) is (D) / (A) = 0.01 to 10. Lubricant for material processing.
1 3 . 金属材料表面に、 請求項 1 〜請求項 1 2 いずれかに記載 の金属材料加工用潤滑剤が 0 . 5 〜 4 0 g / m 2 の厚さ設けられ てなる こ とを特徴とする表面処理金属材料。 1 3. The metal material surface, and wherein a call made provided the thickness of the metal material working lubricant according to any one claims 1 to 1 2 0. 5 ~ 4 0 g / m 2 Surface treated metal material.
1 4 . 請求項 1 〜請求項 1 2 いずれかに記載の金属材料加工用 潤滑剤に金属材料を接触させ、 次いで乾燥させる こ とを特徴とす る金属材料の潤滑皮膜形成方法。 14. A method for forming a lubricating film of a metal material, comprising bringing the metal material into contact with the lubricant for processing a metal material according to any one of claims 1 to 12, and then drying the metal material.
1 5 . ショ ッ トブラス ト、 サン ドブラス ト、 アルカ リ 脱脂、 及 び酸洗浄の群の中か ら選ばれる少なく と も一つの清浄化手段に よ り 金属材料の表面を清浄化した後、 この金属材料を請求項 1 〜 請求項 1 2 いずれかに記載の金属材料加工用潤滑剤に接触させ、 次いで乾燥させる こ と を特徴とする金属材料の潤滑皮膜形成方 法。 15 5. After cleaning the surface of the metal material by at least one cleaning means selected from the group consisting of shot blast, sand blast, alkaline degreasing, and acid cleaning, A method for forming a lubricating film of a metal material, comprising contacting the metal material with the lubricant for processing a metal material according to any one of claims 1 to 12, followed by drying.
1 6 . 6 0 〜 1 0 0 °Cに加温した金属材料を金属材料加工用潤 滑剤に接触させる こ と を特徴とする請求項 1 4 又は請求項 1 5 に記載の金属材料の潤滑皮膜形成方法。 The lubricating film of a metal material according to claim 14 or 15, wherein the metal material heated to 16.6 to 100 ° C is brought into contact with a lubricant for processing a metal material. Forming method.
1 7 . 金属材料表面に設けられる金属材料加工用潤滑剤の厚さ が 0 . 5 〜 4 0 g /m2 である こ とを特徴とする請求項 1 4〜請 求項 1 6 いずれかに記載の金属材料の潤滑皮膜形成方法。 1 7. Thickness of metal material processing lubricant provided on metal material surface There 0. 5 ~ 4 0 g / claim 1 4請Motomeko 1 6 lubrication film forming method of a metal material according to any one of m and 2. It features a call.
PCT/JP2002/003813 2001-04-19 2002-04-17 Lubricating agent for use in working of metal material, and method for treatment thereof WO2002086038A1 (en)

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