KR100268118B1 - Aqueous lubricant containing metal chelate having sulfur as ligand and method of using same - Google Patents

Abstract

A water-based lubricant that does not contain oil is realized by only applying to a metal surface to form a lubricating film necessary for heavy processing of the metal.

This aqueous lubricant is a suspension or dispersion of a metal chelate compound in water with a surfactant or the like. The metal chelate compound used here is one in which a double or multidentate chelating ligand with one or more sulfur members is assigned to the coordination position of one or more metals among zinc, manganese, iron, molybdenum, tin and antimony.

When applied to a metal surface, this water-based lubricant forms a firm lubricating film on the metal surface. Since this lubricating film uses sulfur as the exhaust gas, when it is extreme pressure, it decompose | disassembles by a dry beam reaction and produces | generates a sulfur radical. These sulfur radicals are rich in reactivity and react quickly with the metal surface to produce metal sulfides with a lubricating effect. This sulfur radical reacts with the metal ions produced by the decomposition of the metal chelate compound, which also produces a metal sulfide having a lubricating effect. In this way, this water-based lubricant produces good lubrication.

Description

Sulfur-based water-based lubricant and method of use {AQUEOUS LUBRICANT CONTAINING METAL CHELATE HAVING SULFUR AS LIGAND AND METHOD OF USING SAME}

The present invention relates to an aqueous lubricant that is applied to at least one of the metal material surface and the metal mold surface to form a lubricating film on the metal surface, and to reduce the friction between the material and the mold to enable high quality plastic working. . The present invention also relates to a method of using the water based lubricant and a chemical substance particularly suitable for producing the water based lubricant.

When the metal material is subjected to plastic working such as forging, extrusion, drawing, rolling, pressing, etc., a lubrication film is formed on the surface of the metal material and / or the metal molding to reduce the friction between the material and the mold, drugging, baking, etc. need to be prevented.

Most commonly, the metal is immersed in a zinc phosphate solution to form a zinc phosphate to iron phosphate chemical coating (hereinafter referred to as a phosphate coating), which is then immersed in sodium soap or the like to form a metal soap layer on the surface. . According to this method, a high quality surface protective film is obtained, and it can become heavy processing (processing whose material surface has a large elongation rate) is attained. However, in order to perform this method, washing | cleaning processes, such as water washing, hot water washing and pickling, may be required, and various apparatuses are required. Moreover, each of these processes takes a long time, leading to a long lead time. Usually 30 minutes or more are required to complete a series of processes. In addition, it is necessary to surface-treat the whole amount of the amount of metal which is plastically processed in a later step within the treatment time at one time, and is not suitable for the production of small quantities of various kinds.

In order to overcome these problems, use of processed oil is examined. For example, Japanese Unexamined Patent Application Publication No. 7-118682 discloses a salt containing zinc to molybdenum, such as zinc dithiophosphate or molybdenum dithiocarbamate, to which lipophilic is imparted by introducing a higher alkyl group into mineral oil. Process oil is proposed. According to this processed oil, most of the above problems are solved. However, since the oil is mainly composed of oil, oils adhere to the surrounding machines, resulting in problems such as oil mist and oil mist. That is, deterioration of the working environment is inevitable. In addition, many problems remain such as degreasing treatment of the surface of the raw material after plastic working.

This invention solves the said subject and makes a lubricating film form on the surface by apply | coating the water-based lubricant which does not contain an oil. If this is possible, the problem of worsening the working environment or requiring degreasing later, since no oil is used, is solved. In addition, the problem of requiring large scale equipment or having to process a large amount of raw materials at one time is solved as it can be applied.

The invention described in claim 1 relates to an aqueous lubricant itself, which is a suspension or dispersion of a metal chelate compound in water. The metal chelate compound used here is one in which a double or multidentate chelating ligand with one or more sulfur as a sulfur is assigned to a ligand of one or more metals among zinc, manganese, iron, molybdenum, tin and antimony. Suspension here means that the metal chelate compound is distributed in water by continuing stirring etc., for example. In addition, dispersion means that the metal chelate compound is distributed in water in the state which does not cause precipitation by surfactant etc. In order to disperse a metal chelate compound in water, an anionic or nonionic surfactant is suitably used.

Although there are plural ligands in the metal, the chelator ligand may be coordinated to all of the plural ligands, but the chelator ligand is coordinated only to a part of plural ligands, and the remaining ligands are coordinated with other than the chelator ligand. do. This lubricant may be prepared by dispersing a previously prepared metal chelate compound in water, or may be prepared by adding a chelate ligand to an aqueous solution in which a metal salt is dissolved. The kind of metal is one or more kinds of arbitrary kinds, and when the number of kinds increases, the conditions which can be processed and the kind of metal which can be processed are expanded.

This water based lubricant is applied to the metal material surface and / or the metal mold surface to form a firm lubricating film on the metal surface. Since the lubricating film uses sulfur as the exhaust gas, when it is extreme pressure, it is decomposed by a drybo reaction to generate sulfur radicals. These sulfur radicals are rich in reactivity and react quickly with the metal surface to produce hardened metals with a lubricating effect. This sulfur radical is decomposed by the metal chelate compound

It reacts with the produced | generated metal ion (zinc, manganese, iron, molybdenum, tin, antimony), and this also produces | generates metal sulfide which has a lubricating effect. In this way, this water-based lubricant produces good lubrication.

The invention described in claim 2 relates to a chemical which is particularly suitable for the production of water-based lubricants. This chemical is a coordinator metal chelate compound, in which a double or multidentate chelating ligand with one or more sulfurs in the ligands partially supports a plurality of coordination positions of one or more metals of zinc, manganese, iron, molybdenum, tin, and antimony. At the same time, the rest of the coordinator was coordinated with Hwang as the commissioner. That is, a chelate ligand having sulfur as its coordinator is characterized in that it is coordinating to some coordinating seats without filling all the coordinating seats of the metal.

This mixed ligand metal chelate compound, when suspended or dispersed in water and used as an aqueous lubricant, produces a very good lubricating film.

The chemical substance is coordinated with a chelate ligand having sulfur as a coordinating member of a plurality of coordinating positions of the metal, and coordinating hydroxide ions, condensed phosphoric acid, polycarboxylic acid type active agent and / or polycarboxylic acid to the remaining coordinating position. It is characterized by that.

In this mixed ligand metal chelate compound, a chelate ligand having sulfur as its coordinator is strongly coordinated with the metal, and hydroxide ions, condensed phosphoric acid, polycarboxylic acid-type high-molecular active agent and / or polycarboxylic acid are formed through the oxygen anion ion. Weakly in coordination

do.

This mixed ligand metal chelate compound, when suspended or dispersed in water and used as an aqueous lubricant, forms a very good lubricating film.

The water-based lubricant according to claim 4 is added to the above-mentioned water-based lubricant, a soluble condensed phosphate, a soluble polycarboxylic acid type polymer active agent and / or a soluble polyoxycarboxylate.

If these adjuvants are added, the performance of a lubricating film will improve. Soluble condensed phosphate, together with the surfactant present in the system, enhances the dispersibility of the metal chelate compound, which is hydrophobic fine particles. A soluble polycarboxylic acid type high molecular weight active agent and a soluble polyoxy carboxylate raise the adhesive force to the metal surface of a lubricating film. The use of the water-based lubricant to which this auxiliary agent is added makes difficult heavy processing possible.

The invention of claim 5 relates to a method of forming a lubricating film on the phosphate film by using an aqueous solution when the phosphate film is previously formed on the metal surface. In this method, a metal material to which a phosphate coating has been previously applied is immersed in an aqueous solution of a multi- or double-chelating chelate ligand having one or more of its constituents as sulfur, and zinc ions and / or iron ions in the chelating ligand and the phosphate coating. To form a crystalline mixed ligand metal chelate compound on the phosphate film.

According to this method, the lubrication effect by a phosphate coating, and the lubrication effect by the metal chelate compound which chelated sulfur to zinc ion and / or iron ion as a ship member are used together.

The invention of claim 6 also relates to a method for producing a lubricating film on a phosphate coating, wherein in this method, a metallic material subjected to phosphate coating in advance is immersed in an aqueous lubricant according to claims 3 or 4, and coordinated with sulfur. A crystalline binuclear metal chelate compound is produced on the phosphate film by reacting with a ligand of an atomic chelating ligand and zinc ions and / or iron ions in the phosphate film.

According to this method, the lubrication effect by a phosphate coating and the lubrication effect by the metal chelate compound which chelated sulfur to the metal as a backbone are used together.

The invention of claim 7 relates to the invention of a method of using an aqueous lubricant, which is described in claims 1, 3 or 4 on at least one of the surface of the metal material and the metal mold surface prior to plastic working of the metal material. It is possible to apply an aqueous lubricant to form a lubricating film on the surface thereof, and to plastically process the metal material in a state where the lubricating film is formed on the surface.

The present invention is clearly understood by referring to the following description.

First, an embodiment of a metal chelate compound in which one or more metals of zinc, manganese, iron, molybdenum, tin, and antimony is chelated with at least one of the bachelors as sulfur is described. Formulas 1 to 28 shown below exemplify such metal chelate compounds, and chelate ligands (except M in formulas) shown in formulas 1 to 28 are in aqueous solution or water and organic solvents (alcohols, ketones and dioxane). Reaction with the above metal ions in the mixed solvent causes insoluble crystalline precipitation in water. The coordination structure of these crystalline precipitates is shown in the formulas (1) to (28). The crystalline precipitate generated here is a metal chelate compound. A microcrystalline crystalline precipitate of the metal chelate compound and suspended, dispersed or dispersed in one, two or three or more of these different metal chelate compounds in water form an aqueous lubricant.

In the formula, M is divalent zinc, divalent or trivalent manganese, divalent or trivalent iron, trivalent or tetravalent molybdenum, divalent [(MoOS) ₂ ] ²⁺ , divalent [Mo ₂ S ₄ ] ²⁺ , Di or tetravalent tin, tri or pentavalent antimony or divalent MoO or monovalent MoOS is shown.

In the formulas (1) to (12), (15), (16), (18), (19), and (28), n changes depending on the kind 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, at n = 1, only two of the four coordinating positions of zinc are coordinated with the chelate ligand with sulfur as the coordinator. In this case, the remaining two coordination positions are coordinated with a substance other than a chelating ligand having sulfur as a coordinating member, for example, hydroxide ions, condensed phosphoric acid, polycarboxylic acid type polymer active agent and / or polyoxycarboxylic acid. In general, in the chemical formula shown below, when the number of the coordination positions of the metal M cannot be completely purchased by the chelate ligand having sulfur as the ligand, the hydroxide is added to the coordination position of the metal which is not coordinated with the chelate ligand having sulfur as the ligand. It means that a ligand having no sulfur, such as an ion, a condensed phosphoric acid, a polycarboxylic acid type active agent, and / or a polyoxycarboxylic acid, is coordinated.

Here, R1 and R2 are the same or, 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 , third C ₄ H ₉ or C ₆ H ₅ . 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 , 3 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 .

Here, R is H, CH ₃ , or C ₂ H ₅ .

Wherein R is ortho NO ₂ , para NO ₂ , meta OCH ₃ , meta CH ₃ or meta C ₂ H ₅ .

Wherein R is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ , or iso C ₃ H ₇ .

R is a hydrogen atom or a C1-C12 alkyl group here.

Where m = 1 and l = 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 iso C ₃ H ₅ , and R ₂ to R ₃ , R ₆ to R ₈ are H,

R ₁ is normal C ₄ H ₉ , iso C ₄ H ₉ , or 3 C ₄ H ₉ , and R ₂ to R ₃ , R ₆ to R ₈ are H,

R ₂ and R ₃ are CH ₃ , and R ₁ , R ₆ to R ₈ are H,

R ₂ and R ₆ are CH ₃ , and R ₁ , R ₃ , R ₇ to R ₈ are H,

R ₂ , R ₃ , R ₆ and R ₇ are CH ₃ , and R ₁ and R ₈ are H,

R ₁ and R ₈ are CH ₃ , and R ₂ to R ₃ , R ₆ to R ₇ are H,

R ₁ and R ₈ are C ₂ H ₅ , and R ₂ to R ₃ , R ₆ to R ₇ are H,

R ₁ and R ₈ are normal C ₃ H ₅ or iso C ₃ H ₅ , and R ₂ to R ₃ , R ₆ , R ₇ are H,

R ₁ and R ₈ are normal C ₄ H ₉ , iso C ₄ H ₉ or 3 C ₄ H ₉ , and R ₂ to R ₃ , R ₆ to R ₇ are H, or

R ₂ and R ₆ are C ₆ H ₅ , and R ₁ , R ₃ , and R ₇ to R ₈ are H.

when m = 1 and l = 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 R ₇ are H.

when m = 1 and l = 2-7,

R ₁ to R ₈ are H.

when m = 2 to 9 and l = 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 to 9 and l = 1,

R ₁ to R ₈ are H.

R is a C1-C12 linear or branched alkyl group here.

R is H, 1 = 2-3, m = 1 or R is a C1-C12 alkyl group, l = 2-3, and m = 2-3.

Wherein R ₁ to R ₃ are H, m = 1, R ₁ is an alkyl group having 1 to 12 carbon atoms, R ₂ to R ₃ are H, m = 2 or R ₁ to R ₂ are H, and R ₃ is NH ₂ and m = 2.

R is H, L = 1-6, n = 2-3, or R is COOH, L = 1-6, n = 2-3.

Wherein R ₁ and R ₂ are H, and L = 2 to 12,

R ₁ is H, R ₂ is CH ₃ , L = 2-12,

R ₁ is C ₂ H ₄ S ⁻ , R ₂ is H, ℓ = 2-12 or,

R ₁ is C ₂ H ₄ S ⁻ , R ₂ is CH ₃ , and L = 2 to 12.

And where R ₁ and R ₂ are H, and ℓ = 1 ~ 2, and m = 1 ~ 6, n = 2 ~ 3 , or R ₁ is C ₂ H ₄ S ^- and, R ₂ is H, m = 1-6 and n = 1.

Where l is 0, 1, 2 or 3,

R ₁ and R ₂ are H, CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or iso C ₃ H ₇ ,

R ₁ is H, R ₂ is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or iso C ₃ H ₇ ,

Or R ₁ is C ₂ H ₅ and R ₂ is C ₆ H ₅ .

Moreover, X is a negative ion single ligand, and n = 2-3.

Where l is 0, 1, 2 or 3,

X is a negative ion single ligand, and n = 2-3.

Here, R is H, and L = 1-4 or

R is a C1-C3 alkyl group and L = 1-4.

X is a negative ion single ligand, and n = 2-3.

Here, X is a negative ion single ligand, and n = 2-3.

Wherein R is H, CH ₃ , OCH ₃ , OH or C ₆ H ₅ .

Moreover, X is an anion single-stage ligand, n = 2-3.

Wherein R is H, CH ₃ , OCH ₃ , or OH.

In addition, X is an anion single-position ligand, n = 2-3.

Here m is 1-12, X is a negative ion single-location ligand, and n = 2-3.

R is an alkyl group (C = 1-12) here.

As apparent from the formulas (1) to (28), at least one of these metal chelate compounds is sulfur, and chelates with one or more metals among zinc, manganese, iron, molybdenum, tin, and antimony. Although this metal chelate compound is hydrophobic microparticles | fine-particles, in pH 8.0-13.0, it disperses in water with an anion or a nonionic surfactant, and it disperse | distributes stably in water continuously. Alternatively, when the metal chelate compound is micronized, it can be suspended so as not to settle for a very long time without using a surfactant or the like, or can be physically suspended by adding agitation or vibration. For this reason, an aqueous lubricant which requires no oil or organic solvent at all can be realized.

When the suspension or dispersion is applied to at least one of the metal material surface and the metal mold surface, a lubricating film is formed on the coated surface. This lubricating film is well matched 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 being baked. Moreover, this lubricant has the advantage that it adheres well to the surface if there is no oil in the metal surface to apply | coat, and it has the characteristic that the preparation process, such as degreasing and washing | cleaning, is unnecessary. In addition, this lubricant can be recycled without requiring any special management, and the normal management only needs to supplement the consumption. Moreover, even when electron beam welding is performed after plastic working, severe washing | cleaning is not needed.

Various methods can be used for the method of coating, for example, when apply | coating to the surface of a raw material, arbitrary methods, such as immersing a raw material in a lubrication, apply | coating with a brush, or spraying, can be employ | adopted. Moreover, when apply | coating to the shaping | molding surface of a mold, the method of apply | coating with a brush, spraying, etc. can be employ | adopted.

The lubricant may be naturally dried by leaving the material or mold coated with the lubricant, or may be forcedly dried as necessary. In the case of forced drying, any method may be employed, such as a method of applying hot air, a method of filtering the material or mold, or a method of drying by heating at high frequency. The degree of drying can also be adjusted as needed and can be fully or semi-dry. The degree of drying can be arbitrarily adjusted by drying temperature or drying time.

Alternatively, the metal chelate compound may be generated in the liquid instead of being adjusted in advance and added to the water. That is, at least one chelating agent comprising at least one of the constituents as sulfur, salts, oxides or hydroxides of at least one metal in zinc, manganese, iron, molybdenum, tin, antimony, and anionic or nonionic surfactants. You may use the added lubricant. This lubricant can be used in exactly the same way.

In the case of the metal chelate compounds represented by the formulas (1) to (28), a chelate ligand having sulfur as a ligand may be coordinated to all of the plurality of coordination positions of the metal. Alternatively, a chelate ligand with sulfur as the coordinator may be coordinated only to a partial coordinating part of the metal, and a ligand without sulfur as a coordinator may be coordinating with the remaining coordinator. As the heat of the ligand which does not use sulfur as a ligand, hydroxide ions, condensed phosphoric acid, polycarboxylic acid type polymer active agents and / or polycarboxylic acids are suitable. Formula 1-28 also shows that the chelate ligand which makes sulfur represented by a chemical formula only in a part of the some coordination position of a metal is coordinated.

In the case where the phosphate coating is applied to the metal surface, when the metal is immersed in an aqueous solution of the chelate ligand (except M in the formula) shown in Chemical Formulas 1 to 28, sulfur is converted into a zinc ion to iron ion present in the phosphate coating. The chelate ligand is coordinated to produce a crystalline mixed ligand metal chelate compound on the phosphate film, which causes lubrication.

In the case where a phosphate coating is applied to the metal surface, a chelate ligand having sulfur as a coordinating member coordinates a part of a plurality of coordinating positions of the metal, and in an aqueous solution of a metal chelate compound in which a ligand other than the coordinating ligand is coordinated at the remaining coordinating position. When the metal is immersed, a crystalline binuclear chelate compound is produced on the phosphate film, which also brings a lubricating action.

If a lubricating film contains two or more types of metal chelate compounds, each lubrication action will rise up and a very favorable result will be obtained.

Although the lubricant described above is mainly firmly attached to the surface of iron, particularly steel and iron alloy, to form a lubricating film, it can also be used for nonferrous metals such as aluminum.

Various additives, for example, a pH adjuster, a viscosity adjuster, a preservative, an antifoaming agent, etc. can be added. In particular, it is preferable to add soluble condensate phosphate, fatty acid sodium salt, fatty acid potassium salt, soluble polycarboxylic acid type polymer active agent and / or soluble polycarboxylate. They increase the dispersibility of the metal chelate compound in water, or increase the adhesion of the lubricating film to the metal surface.

Next, an experimental example is demonstrated.

Experimental Example 1

150 g of bis- (N, N-diethyldithiocarbamart) zinc was added in the thing which dissolve | melted 20 g of sodium stearate in 1000 ml of warm water previously, it was stirred quietly, and it was set as the water-based lubricant.

The following can be pointed out as an aqueous lubricant similar to this Experimental Example 1. The metal chelate compound is not limited to bis- (N, N-diethyldithiocarbamat) zinc, and various ones exemplified in the formulas (1) to (28), for example, N, N-dibutyldithiocar It may be replaced with bamatoxy molybdenum sulfide and the like. Although sodium stearate is used in this experimental example as an anionic or nonionic surfactant, other well-known anionic or nonionic surfactants such as sodium salts of fatty acids and / or potassium salts of fatty acids are well known. Also by adjusting to pH 8.0-13.0, a metal chelate compound can be disperse | distributed to water well. Even when the metal chelate compound is finely powdered, added to water, suspended and suspended, an almost equivalent aqueous lubricant is obtained.

Experimental Example 2

To a 78 g / 300 mL aqueous solution of sodium N, N-diethyldithiocarbamate 3 whisker, 50 g / 200 mL aqueous solution of zinc sulfate 7 was added while stirring, and bis- (N, N-diethyldithiocar Bamart) Adjust the suspension of zinc. Separately, 100 g of N, N-dibutyldithiocarbamartoxymolybdenum sulfide was dispersed in a warm solution (500 ml) containing 20 g of sodium stearate, 20 g of tricondensed sodium phosphate, and 20 g of a polycarboxylic acid type active agent. Adjust the suspension. Both suspensions were stirred and mixed to obtain an aqueous lubricant.

The following can be pointed out as an aqueous lubricant similar to this Experimental Example 2.

In addition to the aqueous N, N-diethyldithiocarbamate 3 whisker solution, the zinc sulfate aqueous solution, which produces a metal chelate compound, may be replaced with another water-soluble zinc salt or zinc hydroxide. Moreover, it can substitute with the water-soluble salt of manganese, iron, molybdenum, tin, and antimony. The point that Experimental Example 2 differs greatly from Experimental Example 1 is that a metal chelate compound of two or more kinds of metals is used, and zinc and molybdenum are used in the above examples. Any two or more of zinc, manganese, iron, molybdenum, tin, and antimony may be used in combination. The chelate ligand to be used may employ any of those shown in the formulas (1) to (28).

Although tri-condensed sodium phosphate does not need to be added, the addition improves the dispersibility of a metal chelate compound. Although the polycarboxylic acid type activator may not be required, the addition improves the adhesion of the lubricating film to the metal. Soluble polyoxycarboxylate may be added in place of the polycarboxylic acid type active agent.

Experimental Example 3

First, a solution in which 45.3 g of N, N-diethyldithiocarbamate 3 beard and 8.5 g of sodium hydroxide was dissolved in 200 ml of water in a 57.8 g / 300 ml aqueous solution of zinc sulfate 7 was gradually injected while stirring, The suspension of mono- (N, N-diethyldithiocarbamat) -hydroxyaquazinc is adjusted.

Mono- (N, N-diethyldithiocarbamat) -hydroxyaqua zinc strongly coordinates a chelating ligand with sulfur as a coordinating member to a part of a plurality of coordinating positions of zinc, and sodium hydroxide to the remaining coordinating groups. Ions are weakly coordinated. Mono- (N, N-diethyldithiocarbamat) -hydroxyaqua zinc can be disperse | distributed to water by the sodium salt of fatty acids, such as sodium suarate, and / or the potassium salt of a fatty acid.

The following lubricants can be exemplified by the same kind as in this experimental example. The chelate ligand having sulfur as a chelate as part of a plurality of coordination positions of the metal as a ligand can be substituted with any ligand shown in Formulas (1) to (28). The sodium hydroxide ions coordinated with the balance coordinates can be substituted with any hydroxide ions except sulfur.

In the same manner as in the above experimental example, soluble condensed phosphate, soluble polycarboxylic acid type polymer active agent and / or soluble polycarboxylate may be added as necessary.

Experimental Example 4

First, in a 57.8 g / 300 mL aqueous solution of zinc sulfate 7 whisker, 18 g / 100 mL of tri-condensed sodium phosphate is slowly injected while stirring to adjust the suspension of tri-condensed zinc phosphate crystalline precipitate. In this case, when 45.3 g / 200 ml of N, N-diethyldithiocarbamate 3 whiskers are slowly injected while stirring, the crystallinity of mono- (N, N-diethylthiocarbamat) -triphosphite zinc is increased. Precipitation (hereinafter referred to as G) is obtained.

Separately, 100 g of N, N-dibutyldithiocarbamartoxymolybdenum sulfide was dispersed in a solution obtained by dissolving 20 g of sodium stearate, 10 g of tricondensate phosphate 5 g and 12 g of a polycarboxylic acid-type activator in 500 ml of warm water. Prepare the solution (hereinafter referred to as H). A yellow dispersion system obtained by stirring and mixing G and H is used as a lubricant.

Mono- (N, N-diethyldithiocarbamat) -triphosphite zinc strongly coordinates a chelate ligand with sulfur as a ligand to a part of a plurality of coordination positions of zinc, and condenses three to the remaining coordination positions. Sodium phosphate is weakly coordinated through oxygen ions. The weak coordination of the remaining coordination groups through oxygen anion ions is not limited to condensed phosphoric acid such as trisodium condensate phosphate, and can be replaced with a polycarboxylic acid-type polymerizable active agent and / or polyoxycarboxylic acid.

The point that Experimental Example 4 differs greatly from Experimental Example 3 is to use a metal chelate compound of two or more kinds of metals, in which zinc and molybdenum are used. Instead, any two or more kinds of zinc, manganese, iron, molybdenum, tin, and antimony may be used in combination. In two or more kinds of metal chelate compounds, both of the chelate ligands having sulfur as the coordinating member may be coordinated with a part of the plurality of coordination positions of the metal, but as described above, in one metal chelate compound, All may be coordinated with a chelate ligand with sulfur as the commissioner. The chelate ligand to be used may employ any of those shown in the formulas (1) to (28).

Experimental Example 5

5% -N, N-diethyldithiocarbamate 3 In a warm solution of beard (pH 10), a crystalline mixed ligand zinc chelate compound produced by immersing a metal material subjected to phosphate coating on a phosphate coating was produced. Use lubricant.

When the pH is adjusted in the range of 6.5 to 13.5, sodium N, N-diethyldithiocarbamate (a ligand having sulfur as a ligand) coordinates with zinc ions to iron ions in the phosphate coating to form crystallinity on the phosphate coating. A mixed ligand zinc to iron chelate compound is produced, which becomes a lubricating film. The chelate ligand may be any of those shown in formulas (1) to (28).

Experimental Example 6

In 40 g / 200 ml of zinc sulfate 7 beard, a mixed aqueous solution (150 ml) of 31 g of N, N-diethyldithiocarbamate 3 beard and 5.9 g of sodium hydroxide was slowly injected with stirring to mono- (N, N -A suspension of diethyldithiocarbamat) hydroxyaquazinc (hereinafter referred to as I) is obtained (pH 11.5 to 12.0).

The crystalline binuclear zinc chelate is obtained on a phosphate film by immersing the metal material which performed the phosphate film previously in 40-50 degree I, and stirring I for 30 to 60 second. This is called a cab.

Moreover, crystalline binuclear zinc chelate is obtained on a phosphate film also by immersing the metal material which previously performed the phosphate film in the lubricant obtained by Experimental Examples 1-4. The chelate ligands may be any of those shown in the formulas (1) to (28), and in particular, it is preferable that the chelate ligands having sulfur as ligands coordinate with a part of the metal coordination loci and the ligands containing no sulfur in the remaining coordination loci are coordinated. Do. In this case, the sulfur-containing chelate ligand coordinates with the metal, and the sulfur-free ligand coordinates with zinc ions to iron ions in the phosphate film, thereby obtaining a crystalline binuclear metal chelate compound.

The lubricant prepared in the first to sixth examples was applied to the inner surface of the hole of the billet (for a reduction rate of 12%: using a cylindrical member having a bore diameter of 15 mm, an outer diameter of 29.9 mm, and a length of 50 mm) having a hole for testing, and 150. 60 degreeC hot air was made to dry for 60 second. The time required for this treatment was roughly 2 minutes.

For comparison, a phosphate film was formed on the same billet and a film of metal soap was prepared thereon (Comparative Example 1). The time required for this treatment was 30 minutes or more.

In addition, the thing which apply | coated the process oil (lubrication aid addition completion) was applied to the same billet for comparison (comparative example 2). The time required for this treatment was roughly 30 seconds.

Each billet was tested for ball penetration. This test measures the load required when forcibly deforming a billet through a billet hole by a steel ball having a diameter larger than that of the billet's hole, and also the lubrication performance from the surface properties of the billet's inner diameter. The lower the load, the better the lubrication and the smoother plastic working. The result (maximum load) is shown in the following table | surface. The reduction rate in a table | surface shows the rate of change of the diameter of the hole of the billet before and after deformation, and the larger the number is, the higher the degree of deformation, that is, the more processed. Moreover, it turns out that lubrication is performed well, so that the baking of a surface property does not generate | occur | produce or if the length is short.

Numbers in the table represent loads (unit (t))

Reduction rate 6% 8% 10% 12% Processing time Experimental Example 1 19.625 NG NG NG 2 mins Experimental Example 2 11.676 15.858 20.721 NG 2 mins Experimental Example 3 13.930 16.710 NG NG 2 mins Experimental Example 4 9.265 9.876 11.934 15.992 2 mins Experimental Example 5 10.176 13.945 17.116 20.174 2 mins Experimental Example 6 8.096 9.371 10.767 15.130 2 mins Comparative Example 1 8.383 10.128 14.068 18.060 30 minutes Comparative Example 2 21.391 NG NG NG 30 sec

In the table, NG indicates that the iron balls and the billets were baked so that a good surface property could not be obtained. In all the experimental examples of the present invention, heavy processing was not possible, but light processing was possible in all the experimental examples, and it was confirmed that good lubrication performance was obtained as compared with the case of using oil in all the experimental examples. Moreover, by selecting suitably from the lubricant of this invention, heavy processing also becomes possible.

Only the thing of this Example was apply | coated and a lubricating film was formed, and the grade equivalent to the comparative example 1 was obtained, and it was confirmed that it can be fully utilized. In addition, the treatment time is roughly 2 minutes, and can be treated in a very short time. In particular, when compared with the comparative example 2, the performance difference is remarkable, and even if it cannot process in the comparative example 2, it was confirmed that it can process according to this Example.

According to the lubricating liquid of the present invention, it is possible to form a firm lubricating film that realizes the same performance as in the case of a troublesome and difficult operation of forming a phosphate film and forming a film of metal soap thereon by a simple operation of coating. Since the oil is not used in the present invention, it does not deteriorate the working environment or cause a problem of requiring degreasing later. In addition, since the coating is required, the problem of requiring a large-scale facility or treating a large amount at once is also solved. For this reason, a device for forming a lubricating film is placed in a narrow space adjacent to the plastic processing device of the raw material, and a lubricating film is formed following the cycle of the plastic processing device, so that no extra inventory is required between the two processing. It becomes possible to realize a short lead time.

Claims (7)

At least one of the members of the goblet is represented by the following formulas 1 to 28 (wherein M is excluded, n is 1 or 2 when the metal is zinc, tin or antimony, 1, 2 when the metal is manganese or iron, or 3, a chelate ligand of 1 or 2 if the metal is molybdenum and at least one chelate ligand selected from chelate ligands having substantially the same structure and properties as those of zinc, manganese, iron, molybdenum, tin An aqueous lubricant in which a metal chelate compound coordinated to the coordination seat of at least one metal in antimony is suspended or dispersed in water: [Formula 1] Here, R1 and R2 are the same or, 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 , third C ₄ H ₉ or C ₆ H ₅ . 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 , 3 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 . [Formula 2] Here, R is H, CH ₃ , or C ₂ H ₅ . [Formula 3] [Formula 4] [Formula 5] Wherein R is ortho NO ₂ , para NO ₂ , meta OCH ₃ , meta CH ₃ or meta C ₂ H ₅ . [Formula 6] Wherein R is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ , or iso C ₃ H ₇ . [Formula 7] R is a hydrogen atom or a C1-C12 alkyl group here. [Formula 8] Where m = 1 and l = 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 iso C ₃ H ₅ , and R ₂ to R ₃ , R ₆ to R ₈ are H, R ₁ is normal C ₄ H ₉ , iso C ₄ H ₉ , or 3 C ₄ H ₉ , and R ₂ to R ₃ , R ₆ to R ₈ are H, R ₂ and R ₃ are CH ₃ , and R ₁ , R ₆ to R ₈ are H, R ₂ and R ₆ are CH ₃ , and R ₁ , R ₃ , R ₇ to R ₈ are H, R ₂ , R ₃ , R ₆ and R ₇ are CH ₃ , and R ₁ and R ₈ are H, R ₁ and R ₈ are CH ₃ , and R ₂ to R ₃ , R ₆ to R ₇ are H, R ₁ and R ₈ are C ₂ H ₅ , and R ₂ to R ₃ , R ₆ to R ₇ are H, R ₁ and R ₈ are normal C ₃ H ₅ or iso C ₃ H ₅ , and R ₂ to R ₃ , R ₆ , R ₇ are H, R ₁ and R ₈ are normal C ₄ H ₉ , iso C ₄ H ₉ or 3 C ₄ H ₉ , and R ₂ to R ₃ , R ₆ to R ₇ are H, or R ₂ and R ₆ are C ₆ H ₅ , and R ₁ , R ₃ , and R ₇ to R ₈ are H. when m = 1 and l = 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 R ₇ are H. when m = 1 and l = 2-7, R ₁ to R ₈ are H. when m = 2 to 9 and l = 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 to 9 and l = 1, R ₁ to R ₈ are H. [Formula 9] [Formula 10] [Formula 11] [Formula 12] R is a C1-C12 linear or branched alkyl group here. [Formula 13] R is H, 1 = 2-3, m = 1 or R is a C1-C12 alkyl group, l = 2-3, and m = 2-3. [Formula 14] Wherein R ₁ to R ₃ are H, m = 1, R ₁ is an alkyl group having 1 to 12 carbon atoms, R ₂ to R ₃ are H, m = 2 or R ₁ to R ₂ are H, and R ₃ is NH ₂ and m = 2. [Formula 15] [Formula 16] R is H, L = 1-6, n = 2-3, or R is COOH, L = 1-6, n = 2-3. [Formula 17] Wherein R ₁ and R ₂ are H, and L = 2 to 12, R ₁ is H, R ₂ is CH ₃ , L = 2-12, R ₁ is C ₂ H ₄ S ⁻ , R ₂ is H, ℓ = 2-12 or, R ₁ is C ₂ H ₄ S ⁻ , R ₂ is CH ₃ , and L = 2 to 12. [Formula 18] And where R ₁ and R ₂ are H, and ℓ = 1 ~ 2, and m = 1 ~ 6, n = 2 ~ 3 , or R ₁ is C ₂ H ₄ S ^- and, R ₂ is H, m = 1-6 and n = 1. [Formula 19] [Formula 20] Where l is 0, 1, 2 or 3, R ₁ and R ₂ are H, CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or iso C ₃ H ₇ , R ₁ is H, R ₂ is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or iso C ₃ H ₇ , Or R ₁ is C ₂ H ₅ and R ₂ is C ₆ H ₅ . Moreover, X is a negative ion single ligand, and n = 2-3. [Formula 21] Where l is 0, 1, 2 or 3, X is a negative ion single ligand, and n = 2-3. [Formula 22] Here, R is H, and L = 1-4 or R is a C1-C3 alkyl group and L = 1-4. X is a negative ion single ligand, and n = 2-3. [Formula 23] Here, X is a negative ion single ligand, and n = 2-3. [Formula 24] Wherein R is H, CH ₃ , OCH ₃ , OH or C ₆ H ₅ . Moreover, X is an anion single-stage ligand, n = 2-3. [Formula 25] Wherein R is H, CH ₃ , OCH ₃ , or OH. In addition, X is an anion single-position ligand, n = 2-3. [Formula 26] [Formula 27] Here m is 1-12, X is a negative ion single-location ligand, and n = 2-3. [Formula 28] R is an alkyl group (C = 1-12) here. One or more of the members of the bailout is sulfur, and the following Chemical Formulas 1 to 28 (wherein M is excluded, n is 1 or 2 when the metal is zinc, tin or antimony, 1, 2 or 3 when the metal is manganese or iron) , A chelate ligand of 1 or 2 if the metal is molybdenum and at least one chelate ligand selected from chelate ligands whose structure and properties are substantially equivalent to those of zinc, manganese, iron, molybdenum, tin or One partially selected from the group consisting of hydroxide ions, condensed phosphoric acid, polycarboxylic acid type active agent and polyoxycarboxylic acid while partially filling and coordinating a plurality of coordinating positions of at least one metal in antimony Mixed ligand metal chelate compound coordinated by the above ligand. [Formula 1] Here, R1 and R2 are the same or, 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 , third C ₄ H ₉ or C ₆ H ₅ . 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 , 3 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 . [Formula 2] Here, R is H, CH ₃ , or C ₂ H ₅ . [Formula 3] [Formula 4] [Formula 5] Wherein R is ortho NO ₂ , para NO ₂ , meta OCH ₃ , meta CH ₃ or meta C ₂ H ₅ . [Formula 6] Wherein R is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ , or iso C ₃ H ₇ . [Formula 7] R is a hydrogen atom or a C1-C12 alkyl group here. [Formula 8] Where m = 1 and l = 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 iso C ₃ H ₅ , and R ₂ to R ₃ , R ₆ to R ₈ are H, R ₁ is normal C ₄ H ₉ , iso C ₄ H ₉ , or 3 C ₄ H ₉ , and R ₂ to R ₃ , R ₆ to R ₈ are H, R ₂ and R ₃ are CH ₃ , and R ₁ , R ₆ to R ₈ are H, R ₂ and R ₆ are CH ₃ , and R ₁ , R ₃ , R ₇ to R ₈ are H, R ₂ , R ₃ , R ₆ and R ₇ are CH ₃ , and R ₁ and R ₈ are H, R ₁ and R ₈ are CH ₃ , and R ₂ to R ₃ , R ₆ to R ₇ are H, R ₁ and R ₈ are C ₂ H ₅ , and R ₂ to R ₃ , R ₆ to R ₇ are H, R ₁ and R ₈ are normal C ₃ H ₅ or iso C ₃ H ₅ , and R ₂ to R ₃ , R ₆ , R ₇ are H, R ₁ and R ₈ are normal C ₄ H ₉ , iso C ₄ H ₉ or 3 C ₄ H ₉ , and R ₂ to R ₃ , R ₆ to R ₇ are H, or R ₂ and R ₆ are C ₆ H ₅ , and R ₁ , R ₃ , and R ₇ to R ₈ are H. when m = 1 and l = 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 R ₇ are H. when m = 1 and l = 2-7, R ₁ to R ₈ are H. when m = 2 to 9 and l = 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 to 9 and l = 1, R ₁ to R ₈ are H. [Formula 9] [Formula 10] [Formula 11] [Formula 12] R is a C1-C12 linear or branched alkyl group here. [Formula 13] R is H, 1 = 2-3, m = 1 or R is a C1-C12 alkyl group, l = 2-3, and m = 2-3. [Formula 14] Wherein R ₁ to R ₃ are H, m = 1, R ₁ is an alkyl group having 1 to 12 carbon atoms, R ₂ to R ₃ are H, m = 2 or R ₁ to R ₂ are H, and R ₃ is NH ₂ and m = 2. [Formula 15] [Formula 16] R is H, L = 1-6, n = 2-3, or R is COOH, L = 1-6, n = 2-3. [Formula 17] Wherein R ₁ and R ₂ are H, and L = 2 to 12, R ₁ is H, R ₂ is CH ₃ , L = 2-12, R ₁ is C ₂ H ₄ S ⁻ , R ₂ is H, ℓ = 2-12 or, R ₁ is C ₂ H ₄ S ⁻ , R ₂ is CH ₃ , and L = 2 to 12. [Formula 18] And where R ₁ and R ₂ are H, and ℓ = 1 ~ 2, and m = 1 ~ 6, n = 2 ~ 3 , or R ₁ is C ₂ H ₄ S ^- and, R ₂ is H, m = 1-6 and n = 1. [Formula 19] [Formula 20] Where l is 0, 1, 2 or 3, R ₁ and R ₂ are H, CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or iso C ₃ H ₇ , R ₁ is H, R ₂ is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or iso C ₃ H ₇ , Or R ₁ is C ₂ H ₅ and R ₂ is C ₆ H ₅ . Moreover, X is a negative ion single ligand, and n = 2-3. [Formula 21] Where l is 0, 1, 2 or 3, X is a negative ion single ligand, and n = 2-3. [Formula 22] Here, R is H, and L = 1-4 or R is a C1-C3 alkyl group and L = 1-4. X is a negative ion single ligand, and n = 2-3. [Formula 23] Here, X is a negative ion single ligand, and n = 2-3. [Formula 24] Wherein R is H, CH ₃ , OCH ₃ , OH or C ₆ H ₅ . Moreover, X is an anion single-stage ligand, n = 2-3. [Formula 25] Wherein R is H, CH ₃ , OCH ₃ , or OH. In addition, X is an anion single-position ligand, n = 2-3. [Formula 26] [Formula 27] Here m is 1-12, X is a negative ion single-location ligand, and n = 2-3. [Formula 28] R is an alkyl group (C = 1-12) here. An aqueous lubricant in which the mixed ligand metal chelate compound according to claim 2 is suspended or dispersed in water. An aqueous lubricant to which the at least one selected from the group consisting of soluble condensed phosphate, soluble polycarboxylic acid type active agent and soluble polyoxycarboxylate is added to the aqueous lubricant according to claim 1. A metal material subjected to a phosphate coating containing zinc ions, iron ions, or both is sulfur as one or more members of the exhaustor, and the following Chemical Formulas 1 to 28 (wherein M is excluded and n is a metal ion is a zinc ion) Immersed in an aqueous solution of at least one multidentate or double chelating ligand selected from chelating ligands of 1 or 2, and 1, 2, or 3 of iron ions) and chelating ligands of substantially equivalent structure and properties to them. And reacting the chelating ligand with zinc ions, iron ions, or both in the phosphate coating to produce a crystalline mixed ligand metal chelate compound on the phosphate coating. [Formula 1] Here, R1 and R2 are the same or, 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 , third C ₄ H ₉ or C ₆ H ₅ . 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 , 3 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 . [Formula 2] Here, R is H, CH ₃ , or C ₂ H ₅ . [Formula 3] [Formula 4] [Formula 5] Wherein R is ortho NO ₂ , para NO ₂ , meta OCH ₃ , meta CH ₃ or meta C ₂ H ₅ . [Formula 6] Wherein R is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ , or iso C ₃ H ₇ . [Formula 7] R is a hydrogen atom or a C1-C12 alkyl group here. [Formula 8] Where m = 1 and l = 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 iso C ₃ H ₅ , and R ₂ to R ₃ , R ₆ to R ₈ are H, R ₁ is normal C ₄ H ₉ , iso C ₄ H ₉ , or 3 C ₄ H ₉ , and R ₂ to R ₃ , R ₆ to R ₈ are H, R ₂ and R ₃ are CH ₃ , and R ₁ , R ₆ to R ₈ are H, R ₂ and R ₆ are CH ₃ , and R ₁ , R ₃ , R ₇ to R ₈ are H, R ₂ , R ₃ , R ₆ and R ₇ are CH ₃ , and R ₁ and R ₈ are H, R ₁ and R ₈ are CH ₃ , and R ₂ to R ₃ , R ₆ to R ₇ are H, R ₁ and R ₈ are C ₂ H ₅ , and R ₂ to R ₃ , R ₆ to R ₇ are H, R ₁ and R ₈ are normal C ₃ H ₅ or iso C ₃ H ₅ , and R ₂ to R ₃ , R ₆ , R ₇ are H, R ₁ and R ₈ are normal C ₄ H ₉ , iso C ₄ H ₉ or 3 C ₄ H ₉ , and R ₂ to R ₃ , R ₆ to R ₇ are H, or R ₂ and R ₆ are C ₆ H ₅ , and R ₁ , R ₃ , and R ₇ to R ₈ are H. when m = 1 and l = 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 R ₇ are H. when m = 1 and l = 2-7, R ₁ to R ₈ are H. when m = 2 to 9 and l = 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 to 9 and l = 1, R ₁ to R ₈ are H. [Formula 9] [Formula 10] [Formula 11] [Formula 12] R is a C1-C12 linear or branched alkyl group here. [Formula 13] R is H, 1 = 2-3, m = 1 or R is a C1-C12 alkyl group, l = 2-3, and m = 2-3. [Formula 14] Wherein R ₁ to R ₃ are H, m = 1, R ₁ is an alkyl group having 1 to 12 carbon atoms, R ₂ to R ₃ are H, m = 2 or R ₁ to R ₂ are H, and R ₃ is NH ₂ and m = 2. [Formula 15] [Formula 16] R is H, L = 1-6, n = 2-3, or R is COOH, L = 1-6, n = 2-3. [Formula 17] Wherein R ₁ and R ₂ are H, and L = 2 to 12, R ₁ is H, R ₂ is CH ₃ , L = 2-12, R ₁ is C ₂ H ₄ S ⁻ , R ₂ is H, ℓ = 2-12 or, R ₁ is C ₂ H ₄ S ⁻ , R ₂ is CH ₃ , and L = 2 to 12. [Formula 18] And where R ₁ and R ₂ are H, and ℓ = 1 ~ 2, and m = 1 ~ 6, n = 2 ~ 3 , or R ₁ is C ₂ H ₄ S ^- and, R ₂ is H, m = 1-6 and n = 1. [Formula 19] [Formula 20] Where l is 0, 1, 2 or 3, R ₁ and R ₂ are H, CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or iso C ₃ H ₇ , R ₁ is H, R ₂ is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ or iso C ₃ H ₇ , Or R ₁ is C ₂ H ₅ and R ₂ is C ₆ H ₅ . Moreover, X is a negative ion single ligand, and n = 2-3. [Formula 21] Where l is 0, 1, 2 or 3, X is a negative ion single ligand, and n = 2-3. [Formula 22] Here, R is H, and L = 1-4 or R is a C1-C3 alkyl group and L = 1-4. X is a negative ion single ligand, and n = 2-3. [Formula 23] Here, X is a negative ion single ligand, and n = 2-3. [Formula 24] Wherein R is H, CH ₃ , OCH ₃ , OH or C ₆ H ₅ . Moreover, X is an anion single-stage ligand, n = 2-3. [Formula 25] Wherein R is H, CH ₃ , OCH ₃ , or OH. In addition, X is an anion single-position ligand, n = 2-3. [Formula 26] [Formula 27] Here m is 1-12, X is a negative ion single-location ligand, and n = 2-3. [Formula 28] R is an alkyl group (C = 1-12) here. A method of producing a crystalline binuclear metal chelate compound on a phosphate coating, characterized by immersing a metal material subjected to phosphate coating containing zinc ions, iron ions or both in an aqueous lubricant according to claim 3. Prior to the plastic working of the metal material, the water-based lubricant according to claim 1 is applied to at least one direction between the surface of the metal material and the metal-shaped molding surface to form a lubricating film on the surface thereof, in a state where a lubricating film is formed on the surface. A method of using the water-based lubricant according to claim 1, which makes it possible to plastically process the metal material.