JP3217072B2 - Aqueous lubricant with sulfur as coordinating atom and its use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION 【Technical field】

The present invention forms a lubricating film on at least one of the surface of the metal material and the molding surface of the metal mold to form a lubricating film on the metal surface, thereby reducing friction between the material and the mold and enabling high-quality plastic working. It relates to a water-based lubricant. The invention also relates to methods of using the water-based lubricant and chemicals particularly suitable for the manufacture of the water-based lubricant.

[Background Art]

When plastic processing such as forging, extrusion, drawing, rolling, and pressing is performed on a metal material, a lubricant film is formed on the surface of the metal material and / or the molding surface of the metal mold to reduce friction between the material and the mold. However, it is necessary to prevent the occurrence of galling, seizure and the like. Most commonly, a metal is immersed in a zinc phosphate solution to form a zinc phosphate or iron phosphate conversion film on the surface (hereinafter referred to as a phosphate film), which is then immersed in sodium soap or the like to form a metal. A soap layer forms on the surface. According to this method, a high-quality surface protective film is obtained, and heavy processing (processing in which the material surface has a large elongation) can be performed. However, in order to implement this method, various types of equipment are required, since a washing process such as water washing, hot water washing, and acid washing may be required. Further, each of the above processes takes a long time and the lead time becomes longer. Usually, it takes 30 minutes or more to complete a series of processes. Further, it is necessary to perform a surface treatment at a time on the entire amount of the metal to be plastically processed in the post-processing within the processing time, which is not suitable for the production of a small number of products. In order to overcome these problems, utilization of processing oil is being studied. For example, JP-A-7-118682 discloses a process in which a zinc or molybdenum salt such as zinc dithiophosphate or molybdenum dithiocarbamate imparted with a higher alkyl group to impart lipophilicity is dispersed in a mineral oil. Oil has been proposed. Although many of the problems described above can be solved by this processing oil, since oil is the main component, problems such as contamination of the peripheral machines due to oil adhesion and generation of oil mist occur. That is, deterioration of the working environment is inevitable. In addition, many problems remain, such as the necessity of degreasing the material surface after plastic working.

DISCLOSURE OF THE INVENTION

The present invention solves the above-mentioned problem, and forms a lubricating film on the surface by applying a water-based lubricant containing no oil. If this can be done, the problem of deteriorating the working environment or not requiring a degreasing treatment later since oil is not used is solved. In addition, the problem that large-scale equipment is required and a large amount of material must be processed at one time can be solved because coating is sufficient. The invention described in claim 1 relates to a chemical substance particularly suitable for producing a water-based lubricant. This chemical is a mixed ligand metal chelate compound in which a multidentate or polydentate chelate ligand having at least one of the coordinating atoms as sulfur forms one of zinc, manganese, iron, molybdenum, tin and antimony. While partially filling and coordinating a plurality of coordination sites of one or more metals, hydroxide ions, condensed phosphoric acid,
It is characterized in that a polycarboxylic acid type polymer activator and / or a polyoxycarboxylic acid are coordinated. In the mixed ligand metal chelate compound, a chelate ligand having sulfur as a coordinating atom is firmly coordinated with a metal, and a hydroxide ion, condensed phosphoric acid, a polycarboxylic acid type polymer activator and / or The polyoxycarboxylic acid coordinates weakly to the metal via the oxygen anion. The aqueous lubricant described in claim 2 is obtained by suspending or dispersing the mixed ligand metal chelate compound in water. When the mixed ligand metal chelate compound is suspended or dispersed in water and used as an aqueous lubricant, a very good lubricating film is formed. In the water-based lubricant according to claim 3, a soluble condensed phosphate, a soluble polycarboxylic acid type polymer activator and / or a soluble polyoxycarboxylate are added to the water-based lubricant. When these auxiliary agents are added, the performance of the lubricating film is improved. The soluble condensed phosphate, together with the surfactant present in the system, enhances the dispersibility of the metal chelate compound as hydrophobic fine particles. Soluble polycarboxylic acid type polymer activators and soluble polyoxycarboxylates increase the adhesion of the lubricating film to the metal surface. If an aqueous lubricant to which this auxiliary agent is added is used, severe heavy working becomes possible. The invention of claim 4 relates to a method for forming a lubricating film on a phosphoric acid film using an aqueous solution when a phosphoric acid film is previously formed on a metal surface. In this method, a metal material previously coated with a phosphoric acid film is immersed in an aqueous solution of a polydentate or a plurality of chelate ligands in which at least one of the coordination atoms is sulfur, and the chelate ligand and the phosphorous By reacting with zinc ions and / or iron ions in the acid film, a crystalline mixed ligand metal chelate compound is formed on the phosphoric acid film. According to this method, the lubricating effect of the phosphoric acid film and the lubricating effect of the metal chelate compound in which sulfur is coordinated to zinc ions and / or iron ions are used. The invention according to claim 5 also relates to a method for forming a lubricating film on a phosphoric acid film. In this method, a metal material previously coated with a phosphoric acid film is immersed in the water-based lubricant according to claim 2 or 3. And reacting a ligand which is not a chelating ligand having sulfur as a coordinating atom with zinc ions and / or iron ions in the phosphoric acid film to form a crystalline dinuclear metal chelate compound on the phosphoric acid film Generate According to this method, both the lubricating effect of the phosphoric acid film and the lubricating effect of the metal chelate compound obtained by chelating a metal with sulfur as a coordinating atom are used. The invention according to claim 6 relates to a method for using a water-based lubricant,
Prior to plastic working of the metal material, at least one of the surface of the metal material and the molding surface of the metal mold is coated with the aqueous lubricant according to claims 2 or 3 to form a lubricating film on the surface, The metal material can be plastically processed in a state where a lubricating film is formed on the surface. In this case, it is preferable that the aqueous lubricant is dried after the application, and plastic processing is performed after the drying.

BEST MODE FOR CARRYING OUT THE INVENTION

First, an embodiment of a metal chelate compound in which at least one of the coordinating atoms is sulfur and one or more metals of zinc, manganese, iron, molybdenum, tin, and antimony are chelated will be described. Chemical formulas 1 to 28 shown below exemplify this kind of metal chelate compound, and the chelate ligands (excluding M in the formula) shown in chemical formulas 1 to 28 are used in an aqueous solution or a water / organic solvent ( (Alcohols, ketones and dioxane) react with the above-mentioned metal ions in a mixed solvent to form a water-insoluble crystalline precipitate. The coordination structures of these crystalline precipitates are shown in Chemical Formulas 1 to 28. The resulting crystalline precipitate is a metal chelate compound. A crystalline lubricant of the metal chelate compound is refined, and one, two, or three or more different metal chelate compounds among them are suspended or dispersed in water to be an aqueous lubricant. In the chemical formula, M is divalent zinc, divalent or trivalent manganese, divalent or trivalent iron, trivalent or trivalent molybdenum, divalent [(MoOS) ₂ ] ²⁺ , divalent [ Mo ₂ S ₄ ] ²⁺ , 2
Or tetravalent tin, trivalent or pentavalent antimony or 2
It shows monovalent MoO or monovalent MoOS. In chemical formulas 1 to 12, 15, 16, 18, 19 and 28, n
Varies according to the type of M. For example, n = 1 or 2 when M is zinc, tin or antimony, n = 1, 2 or 3 when M is manganese or iron, and n = 1 or 2 when M is molybdenum. For example, in the case of zinc, n =
In 1, the chelating ligand having sulfur as a coordinating atom is coordinated only in two of the four coordination sites of zinc. In this case, the remaining two coordination sites are those other than the chelating ligand having sulfur as a coordinating atom, such as hydroxide ion, condensed phosphoric acid, polycarboxylic acid type polymer activator and / or polyoxygen. A carboxylic acid or the like coordinates. In general, in the chemical formula shown below, when the number of coordination sites of metal M cannot be filled with a chelating ligand having sulfur as a coordinating atom, a chelating ligand having sulfur as a coordinating atom A non-sulfur-containing ligand such as a hydroxide ion, condensed phosphoric acid, a polycarboxylic acid type polymer activator and / or a polyoxycarboxylic acid is coordinated to a non-coordinated metal coordination site. Means that

[Chemical formula 1] Here, R ₁ and R ₂ may be equal. In this case, R ₁ (=
R _{2) is, H, CH 3, C 2} H 5, n-C ₃ H _7, iso-C ₃ H _7, n-C ₄ H _9, iso C ₄ H _9, tert C ₄ H ₉ or C ₆ H ₅ It is. R ₁
And R ₂ may be different, and when R ₁ is H, R ₂ is CH ₃ , C ₂ H
₅ , normal C ₃ H ₇ , iso C ₃ H ₇ , normal C ₄ H ₉ , iso C
₄ H _9, a third C ₄ H ₉ or C ₄ H _9. When R ₁ is CH ₃ or C ₂ H ₅ , R ₂ is C ₆ H ₅ .

[Chemical formula 2] Here, R is H, CH ₃ , or C ₂ H ₅ .

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5] Here, R is ortho NO ₂ , para NO ₂ , meta OCH ₃ , meta CH ₃ or meta C ₂ H ₅ .

[Chemical formula 6] Where R is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ , or iso C ₃ H ₇
It is.

[Chemical formula 7] Here, R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[Chemical formula 8] Here, when m = 1 and 1 (ell) = 0, R _{1 to} R ₃ , R _{6 to} R ₈ are H, R ₁ is CH ₃ and R _{2 to} R ₃ , R _{6 to} R ₈ are H, R ₁ is C ₂ H ₅ and R _{2 to} R ₃ , R _{6 to} R ₈ are H, R ₁ is normal C ₃ H ₅ or isoC ₃ H ₅ , R _{2 to} R ₃ , R ₆
R ₈ is H, R ₁ is normal C ₄ H ₉ , iso C ₄ H ₉ , or tertiary C ₄ H ₉ ,
R _{2 to} R ₃ , R _{6 to} R ₈ are H, R ₂ and R ₃ are CH ₃ , R ₁ , R _{6 to} R ₈ are H, R ₂ and R ₆ are CH ₃ , R ₁ , R _3, R ₇ to R ₈ are H, R ₂ and R ₃ and R ₆ and R ₇ is CH _3, R ₁ and R ₈ is H, R ₁ and R ₈ is CH _3, R ₂ ~ R ₃ , R ₆ -R ₇ are H, R ₁ and R ₈ are C ₂ H ₅ , R ₂ -R ₃ , R ₆ -R ₇ are H, R ₁ and R ₈ are normal C ₃ H ₅ or Iso-C ₃ H ₅ and R ₂
R ₃ , R ₆ , R ₇ are H, R ₁ and R ₈ are normal C ₄ H ₉ , isoC ₄ H ₉ or tertiary C ₄ H ₉ , and R ₂ -R ₃ , R ₆ -R ₇ are H, or R ₂ and R ₆ are C ₆ H ₅ , and R ₁ , R ₃ , _{7 to} R ₈ are H. When m = 1 and 1 (ell) = 1, R _{1 to} R ₈ are H or R ₄ and R ₅ are CH ₃ , and R _{1 to} R ₃ and R ₆ to ₇ are H. When m = 1 and 1 (ell) = 2 to 7, R _{1 to} R ₈ are H. When m = 2 to 9 and 1 (ell) = 0, R _{1 to} R ₈ are H or R ₂ is CH ₃ , and R ₁ , R ₃ , R _{6 to} R ₈ are H. When m = 2-9 and 1 (ell) = 1, R ₁ -R ₈ are H.

[Chemical formula 9]

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12] Here, R is a linear or branched alkyl group having 1 to 12 carbon atoms.

[Chemical formula 13] Here, R is H, 1 (L) = 2 to 3, m = 1 or R is an alkyl group having 1 to 12 carbon atoms, and 1 = 2 to 3
Where m = 2-3.

[Chemical formula 14] Here, R _{1 to} R ₃ are H, m = 1, R ₁ is an alkyl group having 1 to 12 carbon atoms, and R _{2 to} R ₃ are H
And m = 2 or R _{1 to} R ₂ are H, R ₃ is NH ₂ and m = 2.

[Chemical formula 15]

[Chemical formula 16] Here, R is H, l = 1-6, n = 2-3 or R is COOH, l = 1-6, n = 2-3.

[Chemical formula 17] Wherein, R ₁ and R ₂ in H, l = 2~12, R ₁ is H, R ₂ is _{CH 3, l = 2~12, R} 1 is C ₂ H ₄ S ^- a, R ₂ in H, l = 2 to 12 or R ₁ is C ₂ H ₄ S ^- a, R ₂ is CH _3, a l = 2 to 12.

[Chemical formula 18] Here, R ₁ and R ₂ are H, l = 1 to 2, m = 1 to 6,
n = 2 to 3, or R ₁ is C ₂ H ₄ S ^- a, R ₂ is H, with m = 1~6, n =
It is one.

[Chemical formula 19]

[Chemical formula 20] Here, 1 is 0, 1, 2, or 3, and R ₁ and R ₂ are H, CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or isoC ₃ H
₇ , R ₁ is H, R ₂ is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or isoC
₃ H ₇ or R ₁ is C ₂ H ₅ and R ₂ is C ₆ H ₅ . X is a monodentate anionic ligand, where n = 2 to 3.

[Chemical formula 21] Here, 1 is 0, 1, 2, or 3, X is an anionic monodentate ligand, and n is 2-3.

[Chemical formula 22] Here, R is H, l = 1 to 4 or R is an alkyl group having 1 to 3 carbon atoms, and l = 1 to 4
It is. X is an anionic monodentate ligand, where n = 2 to 3.

[Chemical formula 23] Here, X is an anionic monodentate ligand and n = 2 to 3.

[Chemical formula 24] Here, R is H, CH ₃ , OCH ₃ , OH or C ₆ H ₅ . X is a monodentate anionic ligand, where n = 2 to 3.

[Chemical formula 25] Here, R is H, CH ₃ , OCH ₃ , or OH. X is a monodentate anionic ligand, where n = 2 to 3.

[Chemical formula 26]

[Chemical formula 27] Here, m = 1 to 12, X is an anionic monodentate ligand, and n =
2-3.

[Chemical formula 28] Here, R is an alkyl group (C = 1 to 12). As evident in Formulas 1-28, these metal chelates have at least one of the coordinating atoms sulfur.
It chelates one or more of zinc, manganese, iron, molybdenum, tin and antimony. The metal chelate compound is a hydrophobic fine particle, but is dispersed in water with an anionic or nonionic surfactant at pH 8.0 to 13.0, and is stably dispersed in water. Alternatively, when the metal chelate compound is pulverized, it can be suspended so as not to precipitate for a considerably long time without using a surfactant or the like, and physically suspended by applying vibration without stirring. It can be turbid. For this reason, an aqueous lubricant that does not require any oils or organic solvents can be realized. When this suspension or dispersion is applied to at least one of the surface of the metal material and the molding surface of the metal mold, a lubricating film is formed on the applied surface. The lubricating film adapts well to the surface and does not easily peel off from the surface during the plastic working of the metal material. It also has good lubricity and effectively prevents the material and mold from seizing. Further, this lubricant has an advantage that it adheres well to the surface of the metal to be applied as long as no oil is present on the surface of the metal, and has a feature that a preparation step such as degreasing and cleaning is required. Furthermore, the lubricant does not require any special management, is recyclable, and usually only needs to replenish its consumption. Also, when performing electron beam welding after plastic working,
Does not require rigorous cleaning. Various methods can be used for the application method.For example, when applying to the surface of the material, an arbitrary method such as immersing the material in a lubricant, applying with a brush, or spraying is used. Can be. When applying to the molding surface of the mold, a method such as painting with a brush or spraying can be adopted. Furthermore, the lubricant may be naturally dried by leaving the material or mold on which the lubricant is applied, or may be forcibly dried if necessary. In the case of forced drying, an arbitrary method such as a method of applying hot air, a method of preheating a material or a mold, and a method of drying by high frequency heating can be employed. In addition, the degree of drying can be adjusted as needed, and can be completely dried or semi-dried. The degree of drying can be arbitrarily adjusted depending on the drying temperature and drying time. Instead of adjusting the metal chelate compound in advance and adding it to water, the metal chelate compound may be generated in a liquid. That is, one or more chelating agents in which at least one of the coordinating atoms is sulfur, zinc, manganese,
A lubricant to which a salt, oxide or hydroxide of one or more of iron, molybdenum, tin and antimony and an anionic or nonionic surfactant are added may be used.
This lubricant can be used in exactly the same way. In the case of the metal chelate compounds represented by Chemical Formulas 1 to 28, a chelate ligand having sulfur as a coordinating atom may be coordinated in all of a plurality of metal coordination sites. Instead, a chelating ligand having sulfur as a coordinating atom is coordinated only in some of the metal coordination sites, and a ligand not having sulfur as a coordinating atom is coordinating in the remaining coordination sites. You may rank. As examples of ligands that do not have sulfur as a coordinating atom, hydroxide ions, condensed phosphoric acid, polycarboxylic acid type polymer activators and / or polyoxycarboxylic acids are suitable. Chemical formulas 1 to 28 also show those in which a chelate ligand having sulfur as a coordinating atom represented by the chemical formula is coordinated only in a part of a plurality of metal coordination sites. When the phosphoric acid film is applied to the metal surface, the chemical formula 1
When the metal is immersed in an aqueous solution of the chelating ligands (excluding M in the formula) shown in -28, the chelate having sulfur as a coordinating atom to zinc ions or iron ions present in the phosphate film The ligand coordinates to form a crystalline mixed-ligand metal chelate compound on the phosphoric acid film, which provides a lubricating effect. When a phosphoric acid film is provided on the metal surface, a chelating ligand having sulfur as a coordinating atom is coordinated in a part of a plurality of coordination sites of the metal, and the other coordination sites are in other coordination sites. When the metal is immersed in an aqueous solution of a metal chelate compound to which a ligand is coordinated, a crystalline dinuclear chelate compound is formed on the phosphoric acid film, which also provides a lubricating effect. When the lubricating film contains two or more metal chelate compounds, the respective lubricating actions are obtained in synergy, and very good results are obtained. The lubricants described above are mainly iron, especially steel,
Also, it forms a lubricating film by firmly adhering to the surface of an iron alloy, but can also be used for non-ferrous metals such as aluminum. Various additives such as a pH adjuster, a viscosity adjuster, a preservative, and an antifoaming agent can be added to the lubricant. In particular, soluble condensed phosphate, fatty acid sodium salt,
It is preferable to add a fatty acid potassium salt, a soluble polycarboxylic acid type polymer activator and / or a soluble polyoxycarboxylic acid salt. These enhance the dispersibility of the metal chelate compound in water and increase the adhesion of the lubricating film to the metal surface. Next, an experimental example will be described.

First Experimental Example 150 g of bis- (N, N-diethyldithiocarbamato) zinc was added to 20 g of sodium stearate previously dissolved in 1000 ml of warm water, and gently stirred to obtain an aqueous lubricant. The following can be pointed out as the same type of aqueous lubricant as in the first experimental example. The metal chelate compound is not limited to bi- (N, N-diethyldithiocarbamato) zinc, and various compounds exemplified in Chemical Formulas 1 to 28, for example, N, N
-Dibutyldithiocarbamatooxymolybdenum sulfide or the like. Although sodium stearate is used in this experimental example as an anionic or nonionic surfactant, other well-known anionic or nonionic surfactants,
For example, by adjusting the pH to 8.0 to 13.0 also with a fatty acid sodium salt and / or a fatty acid potassium salt, the metal chelate compound can be well dispersed in water.
Approximately the same water-based lubricant can be obtained by pulverizing a metal chelate compound, adding it to water, stirring and suspending it.

[Second Experimental Example] Sodium N, N-diethyldithiocarbamate trihydrate 7
A 50 g / 200 ml aqueous solution of zinc sulfate heptahydrate is added to an 8 g / 300 ml aqueous solution while stirring to prepare a suspension of bis- (N, N-diethyldithiocarbamato) zinc. Separately, a warm liquid (500 ml) containing 20 g of sodium stearate, 20 g of tri-condensed sodium phosphate and 20 g of a polycarboxylic acid type polymer activator is added with N,
A suspension in which 100 g of N-dibutyldithiocarbamatooxymolybdenum sulfide is dispersed is prepared. Both suspensions were stirred and mixed to obtain an aqueous lubricant. The following can be pointed out as the same type of aqueous lubricant as in the second experimental example. In addition to the aqueous solution of sodium N, N-diethyldithiocarbamate trihydrate, the aqueous solution of zinc sulfate which produces a metal chelate compound can be replaced with another water-soluble zinc salt or zinc hydroxide. It can also be replaced by water-soluble salts of manganese, iron, molybdenum, tin, and antimony. The second experimental example is significantly different from the first experimental example in that a metal chelate compound of two or more kinds of metals is used. In the above-described example, zinc and molybdenum are used. Any combination of two or more of zinc, manganese, iron, molybdenum, tin, and antimony can be used. As the chelating ligand to be used, any one of those shown in Chemical Formulas 1 to 28 can be adopted. Although sodium tri-condensed phosphate may not be necessary, the addition thereof improves the dispersibility of the metal chelate compound. Although the polycarboxylic acid type activator may not be used, the addition of the polycarboxylic acid type activator improves the adhesion of the lubricating film to the metal. A soluble polyoxycarboxylic acid salt may be added in place of the polycarboxylic acid type polymer activator.

[Third Experimental Example] First, N, N- was added to a 57.8 g / 300 ml aqueous solution of zinc sulfate heptahydrate.
A solution prepared by dissolving 45.3 g of sodium diethyldithiocarbamate trihydrate and 8.5 g of sodium hydroxide in 200 ml of water was gradually added with stirring to obtain mono- (N, N-diethyldithiocarbamato) -hydroxyaqua. Prepare the zinc suspension. Mono- (N, N-diethyldithiocarbamato) -hydroxoaquazinc has a structure in which a chelating ligand having sulfur as a coordinating atom is strongly coordinated in a part of a plurality of zinc coordination sites, and the remaining ligand is coordinated. Sodium hydroxide ion is weakly coordinated at the position. Mono- (N, N-diethyldithiocarbamite) -hydroxyoxoaquazinc can be dispersed in water with a sodium salt of a fatty acid such as sodium stearate and / or a potassium salt of the fatty acid. The following lubricants can be exemplified as the same kind as in this experimental example. The chelating ligand having sulfur as a coordinating atom, which partially chelates a plurality of metal coordination sites, can be replaced by any ligand shown in Chemical Formulas 1 to 28. The sodium hydroxide ion coordinating to the remaining coordination sites can be replaced by any hydroxide ion except sulfur. Similarly to the experimental example, a soluble condensed phosphate, a soluble polycarboxylic acid type polymer activator, and / or a soluble polyoxycarboxylate may be added as necessary.

[Fourth experimental example] First, 18 g / 100 ml of sodium tri-condensed phosphate was gradually added to an aqueous solution of 57.8 g / 300 ml of zinc sulfate heptahydrate while stirring to suspend the crystalline precipitate of tri-condensed zinc phosphate. Adjust the liquid. To this, 45.3 g / 200 ml of sodium N, N-diethyldithiocarbamate trihydrate was gradually added with stirring to obtain a crystalline precipitate of mono- (N, N-diethyldithiocarbamato) -triposphatozinc (hereinafter referred to as G). Is obtained. Separately, 20 g of sodium stearate, 5 condensed phosphoric acid
A solution (hereinafter, referred to as H) is prepared by dispersing 100 g of N, N-dibutyldithiocarbamatooxymolybdenum sulfide in a solution of 10 g of sodium and 12 g of a polycarboxylic acid type activator in 500 ml of warm water. A yellow dispersion obtained by stirring and mixing G and H is used as a lubricant. Mono- (N, N-diethyldithiocarbamato) -triposphatozinc is a compound in which a chelating ligand having sulfur as a ligand is strongly coordinated in a part of a plurality of zinc coordination sites, and the remaining coordination sites are coordinated. Pentasodium 3-condensed phosphate is weakly coordinated via an oxygen anion. Those which weakly coordinate to the remaining coordination sites via an oxygen anion are not limited to condensed phosphoric acid such as pentasodium tricondensed phosphate, but may be used for polycarboxylic acid type polymer activators and / or polyoxycarboxylic acids. Can be replaced. The fourth experimental example is significantly different from the third experimental example in that a metal chelate compound of two or more metals is used.
In the above example, zinc and molybdenum are used. Instead, any two or more of zinc, manganese, iron, molybdenum, tin, and antimony can be used in combination. In two or more metal chelate compounds, a chelate ligand having both sulfur as a coordinating atom may be coordinated at a part of a plurality of coordination sites of the metal. In the metal chelate compound, a chelate ligand having sulfur as a coordinating atom may be coordinated in all of a plurality of coordination sites of the metal. As the chelating ligand to be used, any one of those shown in Chemical Formulas 1 to 28 can be adopted.

Fifth Experimental Example A metal material previously coated with a phosphoric acid film was immersed in a warm solution (pH 10) of 5% -N, N-diethyldithiocarbamate sodium trihydrate to form on the phosphoric acid film. The crystalline mixed ligand zinc chelate compound is used as a lubricant. If the pH is adjusted in the range of 6.5 to 13.5, sodium N, N-diethyldithiocarbamate (a ligand having sulfur as a coordinating atom) coordinates with zinc ions or iron ions in the phosphate film. A crystalline mixed ligand zinc or iron chelate compound is formed on the phosphoric acid film, and this becomes a lubricating film. The chelating ligand may be any of those shown in Formulas 1-28.

[Sixth Experimental Example] A mixed aqueous solution (150 ml) of 31 g of sodium N, N-diethyldithiocarbamate trihydrate and 5.9 g of sodium hydroxide was gradually poured into 40 g / 200 ml of zinc sulfate heptahydrate while stirring. To obtain a suspension of mono- (N, N-diethyldithiocarbamato) hydroxoaquazinc (hereinafter referred to as I) (pH
11.5-12.0). A metal material pre-coated with phosphoric acid is coated with a 40-50 mm I
When immersed in and stirred for 30 to 60 seconds, a crystalline binuclear zinc chelate is obtained on the phosphoric acid film. This is used as a lubricating film. Also, by immersing a metal material previously coated with a phosphoric acid film in the lubricant obtained in Experimental Examples 1 to 4, a crystalline dinuclear zinc chelate can be obtained on the phosphoric acid film. The chelating ligand may be any of the chemical formulas 1 to 28. In particular, the chelating ligand having a sulfur ligand coordinates a part of the metal coordination site and the remaining coordination sites It is preferable that a ligand containing no sulfur is coordinated. In this case, the chelating ligand containing sulfur coordinates to the metal, and the ligand not containing sulfur coordinates with zinc ions or iron ions in the phosphoric acid film, and a crystalline dinuclear metal chito compound is obtained. The lubricant prepared in each of the first to sixth examples was applied to the inner surface of a hole of a test-drilled billet (in the case of a reduction of area of 12%, using a cylindrical member having an inner diameter of 15 mm, an outer diameter of 29.9 mm, and a length of 50 mm). It was applied and dried by blowing hot air at 150 ° C. for 60 seconds. The time required for this treatment was approximately 2 minutes. For comparison, a phosphoric acid film was formed on the same billet, and a metal soap film was formed thereon (Comparative Example 1). The time required for this treatment was 30 minutes or more. Further, for comparison, the same billet was prepared by applying a processing oil (to which a lubricating aid was added) (Comparative Example 2). The time required for this process was approximately 30 seconds. A ball passing test was performed for each billet. In this test, the load required for forcibly passing an iron ball having a diameter larger than the diameter of the billet through the hole of the billet to plastically deform the billet is measured, and lubrication is performed based on the surface properties of the inner diameter of the billet. To evaluate performance,
It shows that the lower the load, the better the lubrication and the smoother the plastic working. The results (maximum load) are shown in the table below. The surface reduction rate in the table indicates the rate of change in the diameter of the hole in the billet before and after the deformation, and the larger the number, the higher the degree of deformation, that is, the higher the work. Further, it can be understood that the better the lubrication is, the shorter the length of the surface property does not occur or even if it occurs. In the table, NG indicates that the iron ball and the billet were seized and good surface properties could not be obtained. Although not all experimental examples of the present invention enable heavy machining, light machining is possible in all experimental examples, and good lubrication performance is better than when oil is used in all experimental examples. It was confirmed that it could be obtained. In addition, heavy working becomes possible by appropriately selecting from the lubricants of the present invention. In the case of this example, the same results as in Comparative Example 1 can be obtained only by forming a lubricating film by coating, and it is confirmed that this can be sufficiently put into practical use. The processing time is about 2
It takes only minutes and can be treated in a very short time. In particular, Comparative Example 2
The difference in performance is remarkable as compared with Comparative Example 2, and it is confirmed that even when processing cannot be performed in Comparative Example 2, processing can be performed according to this example.

【The invention's effect】

According to the lubricant liquid of the present invention, the same operation as that of a troublesome and troublesome operation of forming a phosphoric acid film and forming a metal soap film thereon by a simple operation of application is realized. A strong lubricating film can be formed. In the present invention, since no oil is used, there is no problem of deteriorating the working environment or requiring a degreasing treatment later. In addition, the problem that large-scale equipment is required and that a large amount must be processed at a time can be solved because coating is sufficient. For this reason, a device for forming a lubricating film is placed in a narrow space adjacent to the plastic working device for the material, and the lubricating film is formed following the cycle of the plastic working device and extra stock is required between both processes Or a short lead time can be realized.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07F 15/02 C07F 15/02 C10M 135/18 C10M 135/18 139/00 139/00 Z 173/00 173/00 // C10N 40:20 C10N 40:20 Z 40:24 40:24 Z 80:00 80:00 (72) Inventor Masahiko Takeuchi 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Tomio Ikesue 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Inventor Tokutoshi Kashimura 1 Toyota Town Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Inventor Fumio Kawahara 7 Kakimotocho, Toyota City, Aichi Prefecture Inside Mec International Co., Ltd. (72) Inventor Mitsuru Banno 7-16-1, Kakimoto-cho, Toyota City, Aichi Prefecture Inside Mec International Co., Ltd. (56) References JP 58-63794 (JP, A) JP-A-57-167397 (JP, A) JP-A-53-32274 (JP, A) JP-A-56-34796 (JP, A) JP-A-7-118283 (JP, A) A) JP-A-50-62207 (JP, A) JP-A-62-272692 (JP, A) JP-A-3-246272 (JP, A) JP-A-61-291159 (JP, A) JP-A-2 -305897 (JP, A) JP 38-8117 (JP, B1) JP 47-45487 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 3/06 C07F 7/22 C07F 9/90 C07F 11/00 C07F 13/00 C07F 15/02 C10M 135/18 C10M 139/00 C10M 173/00 C10N 40:20 C10N 40:24 C10N 80:00

Claims (7)

(57) [Claims] 1. A multidentate or multidentate chelating ligand in which at least one of the coordinating atoms is sulfur is zinc, manganese, iron,
Molybdenum, tin, and antimony partially or partially fill multiple coordination sites of one or more metals, and the remaining coordination sites include hydroxide ions, condensed phosphoric acid, and polycarboxylic acid type polymers. A mixed ligand metal chelate compound in which an activator and / or a polyoxycarboxylic acid is coordinated. 2. An aqueous lubricant in which the mixed-ligand metal chelate compound according to claim 1 is suspended or dispersed in water. 3. An aqueous lubricant obtained by adding a soluble condensed phosphate, a soluble polycarboxylic acid type polymer activator and / or a soluble polyoxydicarboxylate to the aqueous lubricant according to claim 2. 4. A metal material which has been previously coated with a phosphoric acid film is immersed in an aqueous solution of a multidentate chelate ligand having at least one of coordination atoms as sulfur, and A method of producing a crystalline mixed ligand metal chelate compound on the phosphoric acid film by reacting with zinc ions and / or iron ions in the phosphoric acid film. 5. A metal material, which has been previously coated with a phosphoric acid film, is immersed in the aqueous lubricant according to claim 2 or 3, and the ligand is not a chelating ligand having sulfur as a coordinating atom. A method in which a crystalline dinuclear metal chelate compound is formed on the phosphoric acid film by reacting with zinc ions and / or iron ions in the acid film. 6. An aqueous lubricant according to claim 2 is applied to at least one of the surface of the metal material and the molding surface of the metal mold prior to plastic working of the metal material to lubricate the surface. 4. The method of using water-based lubrication according to claim 2, wherein a film is formed, and the metal material can be plastically worked in a state where a lubricating film is formed on the surface. 7. The method according to claim 6, further comprising a step of drying after coating.