JP2001323294A - Aqueous lubricating agent having sulfur as coordinated atom and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize an aqueous lubricating agent not containing oil and capable of forming a lubricating oil necessary for a heavy processing of a metal by only applying it on the metal surface. SOLUTION: This aqueous lubricating agent is obtained by suspending or dispersing a metal chelate compound with a surfactant, or the like. The used metal chelate compound is obtained by coordinating plural or multiple site chelate ligands having sulfur, as at least one of the ligands at the coordinating site of at least 1 kind of metal among zinc, manganese, iron, molybdenum, tin and antimony. The aqueous lubricating agent forms a strong lubricating membrane on the metal surface on being applied on the metal surface. Since the lubricating membrane has the sulfur atom as the coordinating atom, the membrane is decomposed and forms sulfur radical by a tribo reaction when it is heavily compressed. The sulfur radical is rich in reactivity, and rapidly reacts with the metal surface to generate a metal sulfide having a lubricating effect. Further, the sulfur radical reacts with the metal ion formed by the decomposition of the metal chelate compound to form also the metal sulfide having the lubricating effect. In this way, the aqueous lubricating agent provides the good lubricating effect.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to at least one of the surface of a metal material and a molding surface of a metal mold to form a lubricating film on the metal surface, thereby reducing friction between the material and the mold to improve quality. The present invention relates to a water-based lubricant capable of performing flexible plastic working. The invention also relates to methods of using the water-based lubricant and chemicals particularly suitable for the manufacture of the water-based lubricant.

2. Description of the Related Art When a metal material is subjected to plastic working such as forging, extrusion, drawing, rolling, pressing, etc., a lubricating film is formed on the surface of the metal material and / or the molding surface of the metal mold, and the material and the mold are separated. It is necessary to reduce the friction between them and to prevent 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. Furthermore, it is necessary to surface-treat the entire amount of the metal which is to be plastically worked in the post-process within the processing time at once, which is not suitable for the production of many kinds of small quantities.
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.

According to this processing oil, many of the above-mentioned problems can be solved. However, since oil is a main component, oil adheres to peripheral machines and becomes dirty or oil mist is generated. Problems 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.

[0002]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and a lubricant film is formed on a 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 water-based lubricant itself, which is a metal chelate compound suspended or dispersed in water.
The metal chelate compound used here is a bidentate or polydentate chelate ligand in which at least one of the coordinating atoms is sulfur, zinc, manganese, iron, molybdenum, tin, and antimony. It is coordinated to the coordination locus.
The suspension referred to here means that the metal chelate compound is distributed in water by, for example, continuing stirring. The term "dispersion" means that the metal chelate compound is distributed in water in a state where precipitation does not occur due to a surfactant or the like. To disperse the metal chelate compound in water, an anionic or nonionic surfactant is preferably used. There are a plurality of coordination sites of the metal, and the chelate ligand may be coordinated in all of the plurality of coordination sites, but the chelate coordination is performed only in a part of the plurality of coordination sites. The other coordination site may be coordinated with a compound other than the above chelate ligand. This lubricant can be produced by dispersing a metal chelate compound prepared in advance in water, or by adding a chelate ligand to an aqueous solution in which a metal salt is dissolved. The kind of metal may be any number of one or more kinds, and as the number of kinds increases, the conditions that can be processed and the types of metals that can be processed increase. This water-based lubricant is applied to the surface of the metal material and / or the molding surface of the metal mold to form a strong lubricating film on the metal surface. This lubricating film is decomposed by a tribo-reaction to generate sulfur radicals when subjected to extreme pressure in order to make sulfur a coordinating atom. The sulfur radical is highly reactive and reacts quickly with the metal surface to produce a metal sulfide having a lubricating effect. In addition, this sulfur radical reacts with metal ions (one or more of zinc, manganese, iron, molybdenum, tin, and antimony) generated by decomposition of the metal chelate compound,
This also produces a metal sulfide which has a lubricating effect. In this way, the water-based lubricant provides a good lubricating effect. The invention described in claim 2 relates to a chemical substance particularly suitable for producing a water-based lubricant. This chemical substance is a mixed ligand metal chelate compound, and a bidentate or polydentate chelate ligand having at least one of coordination atoms as sulfur is zinc,
A ligand that partially fills and coordinates multiple coordination sites of one or more of manganese, iron, molybdenum, tin, and antimony, and does not use sulfur as a coordination atom in the remaining coordination sites Is coordinated. That is, a chelating ligand having sulfur as a coordinating atom does not satisfy all of the coordination sites of the metal and is not coordinated in some of the coordination sites. The mixed ligand metal chelate compound forms a very good lubricating film when suspended or dispersed in water and used as an aqueous lubricant. The invention described in claim 3 also relates to a chemical substance particularly suitable for producing a water-based lubricant. In this chemical substance, a chelating ligand having sulfur as a coordinating atom is coordinated in a part of a plurality of metal coordination sites, and a hydroxide ion, condensed phosphoric acid, Polycarboxylic acid type polymer activator and / or
Alternatively, a polyoxycarboxylic acid is 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. This mixed-ligand metal chelate compound forms a very good lubricating film when suspended or dispersed in water and used as an aqueous lubricant. The water-based lubricant according to claim 5, wherein the water-based lubricant is
A soluble condensed phosphate, a soluble polycarboxylic acid type polymer activator and / or a soluble polyoxycarboxylate are added. 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 6 relates to a method of 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 multidentate chelate ligand in which at least one of the coordination atoms is sulfur, and the chelate ligand and the A crystalline mixed ligand metal chelate compound is formed on the phosphoric acid film by reacting with zinc ions and / or iron ions in 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 7 also relates to a method for forming a lubricating film on a phosphoric acid film, in which a metal material previously coated with a phosphoric acid film is immersed in the aqueous lubricant according to claim 4 or 5. 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, 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 together. The invention of claim 8 relates to the invention of a method of using an aqueous lubricant. Prior to the 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 1, 4 or 5, and a lubricating film is formed on the surface. The metal material can be plastically processed in a state where a lubricating film is formed on the surface.
The present invention will be more clearly understood by considering the following description.

[0003]

DETAILED DESCRIPTION OF THE INVENTION First, zinc, manganese, iron, molybdenum, tin,
An embodiment of a metal chelate compound obtained by chelating at least one metal of antimony 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,
Or tetravalent or pentavalent molybdenum, divalent [(MoO
S) ₂ ] ²⁺ , divalent [Mo ₂ S ₄ ] ²⁺ , divalent or tetravalent tin, trivalent or pentavalent antimony, divalent MoO, or monovalent MoOS. Chemical formulas 1 to 12,
In 15, 16, 18, 19, and 28, n changes 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 when M is molybdenum.
= 1 or 2. For example, in the case of zinc, when n = 1, only two of the four coordination sites of zinc are coordinated with a chelating ligand having sulfur as a coordinating atom. 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 which case R 1
₁ (= R ₂ ) is H, 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 , third C ₄ H ₉
Or C ₆ H ₅ . R ₁ and R ₂ may be different,
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 , 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] Here, R is CH ₃ , C ₂ H ₅ , normal C ₃ H ₇ , or isoC ₃ H ₇ .

[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 l (ell) = 0, R₁~ R_Three, R₆
~ R₈Is H, R₁Is CH_ThreeIn R_Two~ R_Three, R₆~ R₈Is H,
R₁Is C_TwoH_FiveAt R_Two~ R_Three, R₆~ R₈Is H, R₁Is the quota
Le C_ThreeH_FiveOr iso C_ThreeH_FiveAnd R_Two~ R_Three, R₆~ R₈
Is H, R₁Is normal C_FourH₉, Iso C_FourH₉Or third
C_FourH₉And R_Two~ R_Three, R₆~ R₈Is H, R_TwoAnd R_ThreeIs
CH_ThreeAnd R₁, R₆~ R₈Is H, R_TwoAnd R₆Is CH_Threeso
Yes, R₁, R_Three, R₇~ R₈Is H, R_TwoAnd R_ThreeAnd R₆And R₇
Is CH_ThreeAnd R₁And R₈Is H, R ₁And R₈Is CH_ThreeIn
R_Two~ R_Three, R₆~ R₇Is H, R₁And R₈Is C_TwoH_FiveIn
R _Two~ R_Three, R₆~ R₇Is H, R₁And R₈Is normal C_Three
H_FiveOr iso C_ThreeH_FiveAnd R_Two~ R_Three, R₆, R₇Is
H, R₁And R₈Is normal C_FourH₉, Iso C_FourH₉Or the first
Three C_FourH₉And R_Two~ R_Three, R₆~ R₇ Is H, or
R_TwoAnd R₆Is C₆H_FiveAnd R₁, R_Three, R₇~ R₈Is H
You. When m = 1 and l (ell) = 1, R₁~ R₈H
Or R_FourAnd R_FiveIs CH_ThreeAnd R₁~ R_Three, R₆~ R₇Is H
It is. When m = 1 and l (ell) = 2 to 7, R₁~ R
₈Is H. When m = 2-9 and l (ell) = 0, R
₁~ R₈Is H or R_TwoIs CH_ThreeAnd R₁, R_Three, R₆
~ R₈Is H. When m = 2-9 and l (ell) = 1
If R₁~ R₈Is 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, 1 = 2 to 3,
m = 2-3.

[Chemical formula 14] Here, R _{1 to} R ₃ are H, m = 1, and R ₁ has 1 to 1 carbon atoms.
R _{2 to} R ₃ are H, m = 2 or R ₁
To R ₂ is H, R ₃ is NH _2, is m = 2.

[Chemical formula 15]

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

[Chemical formula 17] Where R ₁ and R ₂ are 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]Where R₁And R_TwoIs H, l = 1-2, m = 1-6
And n = 2-3 or R ₁Is C_TwoH_FourS^-And R_TwoIs H
Where m = 1 to 6 and n = 1.

[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 iso C ₃ H ₇ or R _1, the C ₂ H _5, R ₂ is C ₆ H _5. X is an anionic monodentate ligand, and n = 2
~ 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 and l = 1 to 4 or R is carbon number 1 to 1.
And 3 is an alkyl group, and l = 1 to 4. 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
It is. 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] Where m = 1-12, X is an anionic monodentate ligand, n
= 2-3.

[Chemical formula 28] Here, R is an alkyl group (C = 1 to 12). As evident from Chemical Formulas 1-28, these metal chelates have at least one of the coordinating atoms sulfur, zinc,
Chelates to one or more of manganese, iron, molybdenum, tin, and antimony. Although this metal chelate compound is hydrophobic fine particles, it is dispersed in water with an anionic or nonionic surfactant at pH 8.0 to 13.0, and continues to be stably dispersed in water. Alternatively, when the metal chelate compound is pulverized, it can be suspended so as not to precipitate for a considerable period of time without using a surfactant or the like, and can be physically suspended by applying stirring or vibration. 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. This lubricant has the 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 does not require a preparation step such as degreasing or cleaning. Furthermore, the lubricant does not require any special management, is recyclable, and usually only needs to replenish its consumption. Strict cleaning is not required even when electron beam welding is performed after plastic working. 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. Also, when applying to the molding surface of the mold,
Methods such as painting with a brush and 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,
It 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, iron,
A lubricant to which a salt, oxide or hydroxide of one or more metals of 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. Chemical formula 1
In the case of the metal chelate compounds of Nos. To 28, a chelate ligand having sulfur as a coordinating atom may be coordinated in all of a plurality of coordination sites of the metal. 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 chelating 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 a phosphoric acid film is provided on the metal surface, the chemical formula 1-28
When the metal is immersed in an aqueous solution of a chelating ligand (excluding M in the formula) shown in (1), the chelate coordination using sulfur as a coordinating atom to zinc ions or iron ions existing 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 above-described lubricant mainly adheres firmly to the surface of iron, especially steel, and iron alloys to form a lubricating film, 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, it is preferable to add a soluble condensed phosphate, a fatty acid sodium salt, a fatty acid potassium salt, a soluble polycarboxylic acid type polymer activator and / or a soluble polyoxycarboxylate. These enhance the dispersibility of the metal chelate compound in water,
Increases adhesion of lubricating film to metal surface. Next, an experimental example will be described.

EXAMPLES (First experimental example) In a solution in which 20 g of sodium stearate was previously dissolved in 1000 ml of warm water, bis-
150 g of (N, N-diethyldithiocarbamato) zinc was added and stirred gently to obtain an aqueous lubricant. The following can be pointed out as the same type of aqueous lubricant as in the first experimental example. Bis- (N, N-
Not limited to diethyldithiocarbamato) zinc, chemical formula 1
To 28, for example, N, N-dibutyldithiocarbamatooxymolybdenum sulfide. Although sodium stearate is used in this experiment as an anionic or nonionic surfactant, other well-known anionic or nonionic surfactants such as sodium salt of fatty acid and / or Alternatively, depending on the potassium salt of the fatty acid, pH 8.0 to 1
By adjusting to 3.0, 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) To a 78 g / 300 ml aqueous solution of sodium N, N-diethyldithiocarbamate trihydrate, a 50 g / 200 ml aqueous solution of zinc sulfate heptahydrate was added with stirring, and bis- (N, N-diethyldithiocarbamate was added. ) Prepare the zinc suspension. Separately, sodium stearate 2
0 g to a warm liquid (500 ml) containing 20 g of tri-condensed sodium phosphate and 20 g of polycarboxylic acid type polymer activator,
A suspension in which 100 g of N, 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 that 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 of the chelating ligands shown in Chemical Formulas 1 to 28 can be employed. 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, zinc sulfate heptahydrate 57.8 g / 30
In a 0 ml aqueous solution, 45.3 g of sodium N, N-diethyldithiocarbamate trihydrate and sodium hydroxide 8.
A solution of 5 g in 200 ml of water is gradually added with stirring to prepare a suspension of mono- (N, N-diethyldithiocarbamato) -hydroxyoxoaquazinc. 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-diethyldithiocarbamato) -hydroxoaquazinc can be dispersed in water with a sodium salt of a fatty acid such as sodium stearate and / or a potassium salt of a 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 chelates a part of a plurality of coordination sites of the metal, 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, zinc sulfate heptahydrate 57.8 g / 30
0g aqueous solution, 18g / 1
00 ml is gradually added with stirring to prepare a suspension of the tri-condensed zinc phosphate crystalline precipitate. N, N-
Sodium diethyldithiocarbamate trihydrate 45.3
By slowly adding g / 200 ml with stirring, a crystalline precipitate of mono- (N, N-diethyldithiocarbamato) -triposphatozinc (hereinafter referred to as G) is obtained. Separately, 20 g of sodium stearate, 10 g of tri-condensed pentasodium phosphate and 12 g of polycarboxylic acid type activator are added to 50 g of
100 g of N, N-dibutyldithiocarbamatooxymolybdenum sulfide in a solution dissolved in 0 ml of warm water
Is prepared (hereinafter referred to as H). 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 kinds of metals is used. In the above-described example, zinc and molybdenum are used. Instead of zinc,
Any two or more of 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 of the chelating ligands shown in Chemical Formulas 1 to 28 can be employed. (Fifth experimental example) In a warm solution (pH 10) of 5% -N, N-diethyldithiocarbamate sodium trihydrate,
A metallic mixed ligand zinc chelate compound formed on a phosphoric acid film by immersing a metal material previously coated with a phosphoric acid film is used as a 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 coordinating atom) is combined with zinc ions or iron ions in the phosphate film. After coordination, 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 is represented by Formulas 1 to 28
Any of the following may be used. (Sixth Experimental Example) Sodium N, N-diethyldithiocarbamate 3 in 40 g / 200 ml of zinc sulfate heptahydrate
A mixed aqueous solution (150 ml) of 31 g of water salt and 5.9 g of sodium hydroxide was gradually added with stirring to obtain a mono-
A suspension of (N, N-diethyldithiocarbamato) hydroxoaquazinc (hereinafter referred to as I) is obtained (pH 11.5).
１12.0). Metal material that has been pre-coated with phosphoric acid
When immersed in I at 40 to 50 ° 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 one 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 have 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 chelate compound is obtained. The lubricant prepared in each of the first to sixth examples was subjected to a test drilled billet (when the area reduction rate was 12%:
(Use a cylindrical member with an inner diameter of 15 mm, an outer diameter of 29.9 mm, and a length of 50 mm)) and apply hot air at 150 ° C for 60 minutes.
Dried for 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 treatment 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 baked 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. In addition, the processing time is only about 2 minutes, and the treatment can be performed in a very short time. In particular, the performance difference 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.

According to the lubricant liquid of the present invention, a simple operation of coating is equivalent to a troublesome and troublesome operation of forming a phosphoric acid film and forming a metal soap film thereon. A strong lubricating film that achieves the above performance 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.

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[Procedure amendment]

[Submission date] May 21, 2001 (2001.5.2)
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0002

[Correction method] Change

[Correction contents]

[0002]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and a lubricant film is formed on a 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 water-based lubricant itself, which is a metal chelate compound suspended or dispersed in water.
The metal chelate compound used here is a bidentate or polydentate chelate ligand in which at least one of the coordinating atoms is sulfur, zinc, manganese, iron, molybdenum, tin, and antimony. It is coordinated to the coordination locus.
The suspension referred to here means that the metal chelate compound is distributed in water by, for example, continuing stirring. The term "dispersion" means that the metal chelate compound is distributed in water in a state where precipitation does not occur due to a surfactant or the like. To disperse the metal chelate compound in water, an anionic or nonionic surfactant is preferably used. There are a plurality of coordination sites for the metal, and the chelate ligand is coordinated only in a part of the plurality of coordination sites, and the remaining coordination sites are sulfuric acid.
A ligand that does not make yellow a coordinating atom is coordinated. This lubricant can be produced by dispersing a metal chelate compound prepared in advance in water, or by adding a chelate ligand to an aqueous solution in which a metal salt is dissolved. The kind of metal may be any number of one or more kinds, and as the number of kinds increases, the conditions that can be processed and the types of metals that can be processed increase. This water-based lubricant is applied to the surface of the metal material and / or the molding surface of the metal mold to form a strong lubricating film on the metal surface. This lubricating film is decomposed by a tribo-reaction to generate sulfur radicals when subjected to extreme pressure in order to make sulfur a coordinating atom. The sulfur radical is highly reactive and reacts quickly with the metal surface to produce a metal sulfide having a lubricating effect. The sulfur radical reacts with metal ions (one or more of zinc, manganese, iron, molybdenum, tin, and antimony) generated by the decomposition of the metal chelate compound, which also produces a metal sulfide having a lubricating effect. Generate. In this way, the water-based lubricant provides a good lubricating effect. It billed aqueous lubricant according to claim 3 is the water-based lubricant above, soluble condensed phosphates, soluble polycarboxylic acid type polymeric activator and / or soluble polyoxyethylene carboxylic acid salt is added. 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. This invention will be more clearly understood by reference to the description below.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C10M 135/22 C10M 135/22 135/26 135/26 135/32 135/32 135/36 135/36 145/12 145 / 12 159/18 159/18 // C10N 10:04 C10N 10:04 10:08 10:08 10:10 10:10 10:12 10:12 10:14 10:14 10:16 10:16 20: 00 20:00 Z 30:00 30:00 A 30:06 30:06 40:24 40:24 Z (72) Inventor Masahiko Takeuchi 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Invention Person Tomio Ikesue 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Tokutoshi Kashimura 1 Toyota Town Toyota City, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Fumio Kawahara Toyota, Aichi Prefecture 7-16-1 Kakimotocho, Machi International Co., Ltd. (72) Inventor Mitsuru Banno 7-16-1, Kakimotomachi, Toyota City, Aichi Prefecture F-term in Mec International Co., Ltd. F-term (reference) 14C BG17A BG17C BG19A BG19C CB07 DB04A DB04C EA17C EB04 FA02 FA04 FA05 FA06 FA07 FA08 LA03 LA11 PA23

Claims (3)

[Claims] 1. A multidentate or multidentate chelating ligand in which at least one of the coordinating atoms is sulfur, zinc, manganese,
While partially filling and coordinating a plurality of coordination sites of one or more metals among iron, molybdenum, tin, and antimony,
An aqueous lubricant in which a mixed-ligand metal chelate compound in which a ligand not having sulfur as a coordinating atom is coordinated in the remaining coordination sites is suspended or dispersed in water. 2. The mixed ligand metal chelate compound,
2. The aqueous lubricant according to claim 1, wherein the aqueous lubricant is suspended or dispersed in water by an anionic or nonionic surfactant. 3. An aqueous lubricant in which a soluble condensed phosphate, a soluble polycarboxylic acid type polymer activator and / or a soluble polyoxydicarboxylate are added to the aqueous lubricant according to claim 1 or 2.