WO1998022472A1

WO1998022472A1 - Water-base lubricant containing sulfur as coordinate atom, and use thereof

Info

Publication number: WO1998022472A1
Application number: PCT/JP1997/004197
Authority: WO
Inventors: Heijiro Ojima; Masahiko Takeuchi; Fumio Ikesue; Noritoshi Kashimura; Fumio Kawahara; Mitsuru Tomono
Original assignee: Toyota Jidosha Kabushiki Kaisha; Mec International Corporation
Priority date: 1996-11-18
Filing date: 1997-11-18
Publication date: 1998-05-28
Also published as: EP0947519A4; EP0947519A1; JP3217072B2; DE69722658T2; EP0947519B1; DE69722658D1

Abstract

An oil-free water-base lubricant which can form a lubricating film necessary for heavy working of metal only by applying it on the surface of a metal. This water-base lubricant is one prepared by suspending or dispersing a metal chelate compound in water with a surfactant or the like, and the metal chelate compound is one composed of at least one metal atom selected from among zinc, manganese, iron, molybdenum, tin and antimony and a multidentate chelate ligand wherein at least one of the coordinate atoms is sulfur. The lubricant can form a tough lubricating film when applied on the surface of a metal. Since the lubricating film contains sulfur as the coordinate atom, it can give free sulfur radicals through decomposition caused by a triboreaction under extreme-pressure conditions. The sulfur radicals react speedily with the surface of the metal owing to their high reactivity to form a metal sulfide having a lubricating effect. Alternatively, the sulfur radicals react also with the metal ions formed by the decomposition of the metal chelate compound to form another metal sulfide having a lubricating effect. Thus, the water-base lubricant can attain excellent lubrication.

Description

Description Aqueous lubricant having sulfur as a coordinating atom and method of using the same

The present invention forms a lubricating film on at least one of the surface of a metal material and the molding surface of a 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 working 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. It is necessary to prevent the occurrence of galling, seizure, etc.

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 converted to sodium stone or the like. Submerges to form a metal stone layer on the surface. According to this method, a high-quality surface protective film can be obtained, and heavy processing (processing in which the elongation rate of the material surface is large) can be performed. However, implementing this method requires various types of equipment since it may require washing treatment such as water washing, hot water washing, and pickling. Also, 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 processing. Furthermore, within the processing time, it is necessary to surface-treat the entire amount of metal that will be plastically processed in the post-process at once, making it unsuitable for the production of small quantities of many kinds.

In order to overcome these problems, the use of processing oil is being studied. For example, Japanese Unexamined Patent Publication No. 7-118682 discloses that zinc or molybdenum such as zinc dithiophosphate and molybdenum dithiocarbamate having a higher alkyl group introduced into a mineral oil to impart lipophilicity. A processing oil in which a salt of (i) is dispersed has been proposed. This processing oil solves many of the above-mentioned problems, but since it is mainly composed of oil, it causes problems such as adhesion of oil to peripheral machines and generation of oil mist. Sand Deterioration of work environment is inevitable. In addition, many issues remain, such as the need to degrease the material surface after plastic working.

DISCLOSURE OF THE INVENTION

The present invention has been made to solve the above-mentioned problems, and an oil-free water-based lubricant is applied to form a lubricating film on a surface. This would solve the problem of not using oil, deteriorating the working environment and requiring degreasing later. 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, and the water-based lubricant is obtained by suspending or dispersing a metal chelate compound in water. The metal chelate compound used herein is a compound in which a bidentate or polydentate chelate ligand having at least one of coordination atoms as sulfur is at least one of zinc, manganese, iron, molybdenum, tin, and antimony. It is coordinated to the genus 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 no precipitation occurs due to a surfactant or the like. In order to disperse the metal chelate compound in water, an anionic or nonionic surfactant is suitably used.

There are a plurality of metal coordination sites, and the chelate ligand may be coordinated in all of the plurality of coordination sites. However, the chelate ligand may be present only in a part of the plurality of coordination sites. A ligand other than the above-mentioned chelate ligand may be coordinated to the remaining coordination site after the ligand 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 type of metal may be any number of one or more types, and as the number of types increases, the processable conditions and the types of metal that can be processed increase.

The water-based lubricant is applied to the surface of the metal material and the surface of the Z or metal mold to form a strong lubricating film on the metal surface. This lubricating film is decomposed by a tripo reaction when subjected to extreme pressure to generate thio radicals, because sulfur is a coordinating atom. This ゥ The radical is highly reactive and reacts quickly with the metal surface to produce metal sulfide which has a lubricating effect. In addition, this radical reacts with metal ions (one or more of zinc, manganese, iron, molybdenum, tin and antimony) generated by the decomposition of a metal chelate compound, which also has a lubricating metal sulfide. Generate. 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 is a mixed-ligand metal chelate compound in which a multidentate or multidentate chelating ligand with at least one of the coordinating atoms as sulfur is formed of zinc, manganese, iron, molybdenum, tin, and antimony. One or more of these metals partially co-ordinates multiple coordination sites, and the remaining coordination sites coordinate ligands that do not use sulfur as a coordination atom. 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.

This mixed ligand metal chelate compound forms an excellent 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 and a condensed phosphoric acid are in the remaining coordination sites. It is characterized in that a polycarboxylic acid-type polymer activator and a polycarboxylic acid or polycarboxylic acid are coordinated.

In this 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 Z Or, the polyoxycarboxylic acid weakly coordinates to the metal via the oxygen anion.

This mixed-ligand metal chelate compound forms an excellent lubricating film when suspended or dispersed in water and used as an aqueous lubricant. The aqueous lubricant according to claim 5, wherein the aqueous lubricant is a soluble condensed phosphorus. W 7

-4-acid salt, soluble polycarboxylic acid type polymer activator and / or soluble polyoxycarbonate are added.

The addition of these auxiliaries improves the performance of the lubricating film. The soluble condensed phosphate, together with the surfactant present in the system, enhances the dispersibility of the metal chelate compound, which is a hydrophobic fine particle. Soluble polycarboxylic acid type polymer activators and soluble polyoxycarboxylates increase the adhesion of the lubricating film to the metal surface. The use of an aqueous lubricant to which this auxiliary has been added enables severe heavy working. The invention of claim 6 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 multidentate chelate ligand in which at least one of the coordination atoms is sulfur, and the chelate coordination is performed. The crystal reacts with zinc ions and Z or iron ions in the phosphoric acid film to produce a crystalline mixed ligand metal chelate compound 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 both used. The invention of claim 7 also relates to a method of 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 aqueous lubricant according to claim 4 or 5. And reacting a ligand other than the 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 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 forming surface of the metal mold is coated with the water-based lubricant described in claim 1, 4, or 5 to lubricate the surface. Formed film P 5-This enables the metal material to 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. 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 at least one metal selected from zinc, manganese, iron, molybdenum, tin, and antimony is chelated will be described. Chemical formulas 1 to 28 shown below exemplify this kind of metal chelate compound, and the chelating ligands (excluding M in the formulas) shown in chemical formulas 1 to 28 are used in aqueous solution or water. 'Reacts with the above-mentioned metal ions in an organic solvent (alcohols, ketones and dioxane) 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. The crystalline precipitate of the metal chelate compound is refined, and one, two, or three or more of these different metal chelate compounds are suspended or dispersed in water to form an aqueous lubricant.

In the chemical 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 +} , divalent or tetravalent tin, trivalent or pentavalent antimony or divalent Mo or monovalent Mo OS.

In the chemical formulas 1 to 12, 15, 16, 16, 18, 19, and 28, n changes depending on 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 = l or 2 when M is molybdenum. For example, in the case of zinc, when n = l, 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 other than chelating ligands having sulfur as a coordinating atom, for example, hydroxide ion, condensed phosphoric acid, polycarboxylic acid type polymer activator and / or Lioxycarboxylic 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, Is a metal that is not coordinated with a chelating ligand having sulfur as a coordinating atom, such as a hydroxide ion, a condensed phosphoric acid, a polycarboxylic acid type polymer activator and / or a polyoxycarboxylic acid. It means that a ligand having no sulfur is coordinated. [Chemical formula 1]

Where and R ₂ may be equal, where R, (= R ₂ ) is H, CHa, C ₂ H ₅ , normal C ₃ H ₇ , iso C ₃ H ₇ , normal C ₄ H _n iso C ₄ H _9, a third CII9 or Cells. R, and R ₂ may be different, and when R, is H, R ₂ is CH ₃ , C2H5, normal C ₃ H ₇ , iso CsH ₇ , normal C ₄ H «, iso C ₄ H9, third C ₄ H ₉ or C ₄ i −. When R, is CH ₃ or C ₂ H ₅ , R ₂ is C ₆ H ₅ .

[Chemical formula 2]

n

In two this, R is H, CH3, or C ₂ H.

[Chemical formula 3]

[Chemical formula 4]

M

n [Chemical formula 5]

Wherein R is ortho N0 _2, para N0 _2, meta OCH _3, meta _{CH:! I} or meta C ₂ I - I is.

[Chemical formula 6]

R is CH: C 2 H 5, normal C ₃ H ₇ , or iso C ₃ H ₇ , [Formula 7]

R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[Chemical formula 8]

Where m = l and 1 (el) = 0,

R, ~ R ₃ , R _r '~ R ₈ are G,

R, is CH ₃ and R _{2 to} R ₃ , Rs to R ₈ are H,

R, the scale ₂ ~ ¾ in _{_{_{C 2:! ¾, R R}}} ~R 8 is H,

R, is a normal CaHs or iso _{_{_{C 3 H 5, R 2 ~R}}} : i, R n ~R 8 are H, R, is n-CI _9, iso C ₄ H ₉ or tertiary C ₄ H _9, Yes, R _{2 to} R ₃ , R _fi R "Ma H

R ₂ and R ₃ are CH ₃ , R, R ₆ R ₈ is H

R 2 and R ₆ are CH ₃ and RR ₃ R ₇ R ₈ is H

R ₂ and R ₃ and R ₆ and R ₇ is CH _3, R, and R ₈ is H

R, and R ₈ are CH ₃ , R ₂ R ₃ R _r 'R ₇ is H

R, is C ₂ IK and R ₂ R ₃ R _fi R ₇ is H

R, and R ₈ are normal C ₃ H ₅ or iso C ₃ Hs, and RR ₃ RH R ₇ is H

Ri and R ₈ are normal C ₄ H ₉ , iso C ₄ H ₉ or tertiary C ₄ I-I »and RR ₃ R _fi R ₇ is H, or

R ₂ and Re are Ceil ₅ and Ri R ₃ R ₇ R ₈ is II.

If m = 1 and 1 (ell) = 1, then

R and Rs are H or

R ₄ and Rs is _{C II 3, R, R 3} R 6 R 7 is H.

If m = l and 1 (el) = 27,

R and R ₈ are H.

If 111 = 2 9 and 1 (ell) = 0,

R and R ₈ are H or

R iCH ₃ and R and R ₃ RR << are H.

If m = 2 9 and 1 (ell) = 1, then

R and R ₈ are H.

[Chemical formula 9]

[Chemical formula 10]

H

Cis one or S

M / \

Toransu C-NH R

n //

S

R = H or NH—C

[Chemical formula 1 1]

[Chemical formula 1 2]

R is a straight or branched chain alkyl group having 1 to 12 carbon atoms, [Chemical Formula 13]

R

Where R is I-1, 1 (ell) = 2-3, m = l or

R is an alkyl group having 1 to 12 carbon atoms, 1 = 2 to 3, and m = 2 to 3 <[Formula 14]

R, ~ R ₃ is H, m = l,

R is an alkyl group having 1 to 12 carbon atoms, R _{2 to} R ₃ are H, m = 2 or

R, RR ₂ is H, R ₃ is NH ₂ , m = 2.

[Chemical formula 15]

[Chemical formula 16]

n Where R is H, 1 = 1-6, n = 2-3 or

R is COOH, 1 = 1-6, n = 2-3 <

[Chemical formula 17]

Where R, and R ₂ are H, 1 = 2 to 12,

R! In H, with R ₂ is CH _3, 1 = 2~ 12,

R, pima C ₂ H ₄ S—, where R ₂ is H, 1 = 2 to 12 or

R, is C ₂ I-I ₄ S—, R ₂ is CH ₃ , 1 = 2-12.

[Chemical formula 18]

, And R ₂ is H, 1 = :! With ~ 2, m = l ~ 6, n = 2 ~ 3 or R! Is C ₂ Ii ₄ S—, R ₂ is H, m = l to 6 and n = l. [Chemical formula 19]

S

M

C

M

N N

n

C C

S

, _M z

n

[Chemical formula 20]

Where 1 is 0, 1, 2 or 3;

When R2 is _{_{II, CH 3, C 2 H}} 5, n-C ₃ H ₇ or iso C ₃ H _7.

R, is H, R2 _{_{is-I CI 3, C 2 Hr}} ,, n C ₃ H ₇ or iso C ₃ H or R, is a C l _5, R ₂ is C ₆ H _5.

X is an anionic monodentate ligand and n = 2 to 3.

[Chemical formula 21]

Two, 1 p, 0, 1, 2 or 3;

X is an anionic monodentate ligand, where n = 2-3

[Chemical formula 22]

MXn, where R is H, 1 =:! ~ 4 or

R is an alkyl group having 1 to 3 carbon atoms, and〗 = 1 to 4.

X is a monodentate anionic ligand, where n = 2-3.

[Chemical formula 23]

〇

Where X is an anionic monodentate ligand and n = 2-3

[Chemical formula 24]

Wherein, R is H, CH3, OCH: _¾, OH or C _R II _5.

X is an anionic monodentate ligand and n = 2 to 3. [Chemical formula 25]

MXn, where R is II, CH ₃ , OCH 3, or OH <

X is an union monodentate ligand, where n = 2-3.

[Chemical formula 26]

〇〇

[Chemical formula 27]

CmH2in + i S, —— S CmH 2m + i

MXn where m = 1 to 12, X is an anionic monodentate ligand and n = 2 to 3 <[Formula 28]

Where R is an alkyl group (C = l ~ 12), As is evident in Chemical Formulas 1-28, these metal chelates have at least one of the coordinating atoms sulfur and chelate to one or more of the metals zinc, manganese, iron, molybdenum, tin, and antimony. are doing. Although this metal chelate compound is hydrophobic fine particles, it is dispersed in water with an anionic or nonionic surfactant at a pH of 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 considerably long time without using a surfactant or the like. It can be suspended. 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. This 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. In addition, this lubricant has the advantage that it adheres well to the surface of the metal to be applied as long as there is no oil on the surface, and it does not require any preparatory steps such as degreasing and cleaning. In addition, the lubricant does not require any special controls, is recyclable, and usually requires only replenishment of consumption. Strict cleaning is not required when performing electron beam welding after plastic working.

Various methods can be used for application.For example, when applying to the surface of a material, use any method such as immersing the material in a lubricant, applying with a brush, or spraying. Can be. When applying to the molding surface of the mold, a method such as painting with a brush or spraying can be adopted.

Further, the lubricant or the mold coated with the lubricant may be left as it is, and the lubricant may be naturally dried, or may be forcedly dried as required. In the case of forced drying, any method such as a method of applying hot air, a method of preheating materials and molds, and a method of drying by high frequency heating can be adopted. In addition, the degree of drying can be adjusted as necessary, and can be completely dried or semi-dried. The degree of drying can be arbitrarily adjusted depending on the drying temperature and the drying time.

Also, instead of adjusting the metal chelate compound in advance and adding it to water, A metal chelate compound may be generated in the liquid. That is, one or more chelating agents in which at least one of the coordinating atoms is sulfur, one or more metal salts, oxides or hydroxides of zinc, manganese, iron, molybdenum, tin, and antimony; A lubricant to which an ionic or nonionic surfactant is 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 coordination sites of the metal. Instead, a chelating ligand having sulfur as a coordinating atom is coordinated only in a part 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. Suitable examples of the ligand which does not have sulfur as a coordinating atom include hydroxide ion, condensed phosphoric acid, polycarboxylic acid type high molecular weight activator, and poly- or polyoxycarboxylic acid. Chemical formulas 1 to 28 also include those in which a chelating ligand having a sulfur atom as a coordinating atom is coordinated only in a part of a plurality of metal coordination sites. Is shown.

If the metal surface is coated with a phosphoric acid film, if the metal is immersed in an aqueous solution of the chelating ligand shown in Chemical Formulas 1-28 (excluding M in the formula), it will be present in the phosphoric acid film. A chelating ligand having sulfur as a coordinating atom is coordinated with the zinc ion or iron ion to form a crystalline mixed-ligand metal chelate compound on the phosphoric acid film, which provides a lubricating effect.

In addition, when a phosphoric acid film is applied to the metal surface, a chelating ligand having sulfur as a coordinating atom is coordinated in a part of the plurality of metal coordination sites, and the other coordination sites are in other coordination sites. When the metal is immersed in an aqueous solution of the metal chelate compound to which the ligand is coordinated, a crystalline dinuclear chelate compound is formed on the phosphoric acid film, which also has a lubricating effect.

When the lubricating film contains two or more metal chelate compounds, the respective lubricating actions are synergistically obtained, 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.

This lubricant contains various additives such as PH adjuster, viscosity adjuster, preservative, defoamer An agent can be added. 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 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.

[First experimental example]

In a solution in which 20 g of sodium stearate had been dissolved in 1000 ml of warm water in advance, 150 g of bis- (N, N_getyldich talented rubamato) zinc was added, followed by gentle stirring 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 bis- (N, N-getylditi talent rubamato) zinc, but various compounds exemplified in Chemical Formulas 1 to 28, for example, N, N-dibutyl citrus rubamatoximolybdenum sulfate It can be replaced with an eye or the like. 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 a fatty acid are used. The metal chelate compound can be well dispersed in water by adjusting the pH to 8.0 to 13.0 with and / or the potassium salt of a fatty acid. Approximately the same water-based lubricant can be obtained by pulverizing a metal chelate compound, adding it to water, stirring and suspending.

[Second experimental example]

N, N—Jetilditch Talent Sodium rubamate trihydrate 78 g / 300 ml In a water solution, zinc sulfate heptahydrate 50 gZ200m 1 Add an aqueous solution with stirring, and add bis- (N, N_Jetildit talent Rubamat) Prepare the zinc suspension. Separately, a hot liquid (500 ml) containing 20 g of sodium stearate, 20 g of 3-condensed sodium phosphate and 20 g of a polycarboxylic acid type polymer activator was added to N, N_dibutyldithiocarbamoxamolybdenum sulfate. Prepare a suspension in which 100 g of the eye is dispersed. 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.

The aqueous solution of zinc sulfate, which produces a metal chelate compound in addition to the aqueous solution of sodium N, N-getylditirubium rubamate trihydrate, 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 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 chelate ligand to be used, any one of those shown in Chemical Formulas 1 to 28 can be adopted.

The sodium condensed phosphate may be omitted, but adding it 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 metal. A soluble polyoxycarboxylic acid salt may be added in place of the polycarboxylic acid type polymer activator.

[Third experimental example]

First, 57.8 g of zinc sulfate heptahydrate, 55.3 g of sodium N, N-getyl dithiolrubamate trihydrate and 8.5 g of sodium hydroxide were added to an aqueous solution of Z3Om1 in water. The solution dissolved in 20 Om1 is gradually added with stirring to prepare a suspension of mono- (N, N-Jetyldich talented lubamato) -hydroxoaqua zinc. Mono (N, N-getylditi talent rubamato) —Hydroxyaqua zinc has a strong coordination chelate ligand with sulfur as a coordinating atom in some of the multiple coordination sites of zinc. Sodium hydroxide ion is weakly coordinated at the coordination site. Mono- (N, N-getyldich talented rubamato) -Hydroxyaqua zinc 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 metal coordination sites, can be replaced with any of the ligands shown in Chemical Formulas 1-28. Hydroxyl coordinating to the remaining coordination sites Sodium ion 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 of sodium triphosphate condensed into a 77.8 g / 30 Om1 aqueous solution of zinc sulfate 7 Prepare a suspension of zinc crystalline precipitate. Into this, N, N-Jetildich talented sodium rubamate trihydrate 45.3 g Z2Om1 was slowly added with stirring to obtain mono- (N, N-Jetildich talented rubamat) — A crystalline precipitate of tribospato zinc (hereinafter referred to as G) is obtained.

Separately, in a solution of 20 g of sodium stearate, 10 g of pentasodium 3-condensed phosphate and 12 g of a polycarboxylic acid activator in 50 Om1 of warm water, N, N-dibutyldithiol was added. Prepare a liquid (hereinafter referred to as H) in which 100 g of carbamatoximolybdenum sulfide is dispersed. The yellow dispersion obtained by stirring and mixing G and H is used as the lubricant.

Mono- (N, N _ getylditi talent rubamato)-Tribosphato-zinc has a strong coordination of a chelating ligand with sulfur as a part of the zinc coordination, and the remaining coordination In addition, pentasodium triphosphate is weakly coordinated via an oxygen anion. Those weakly coordinating to the remaining coordination sites via oxygen anions are not limited to condensed phosphoric acids such as 3 condensed phosphoric acid and 5 sodium, and polycarboxylic acid type polymer activators and / or polyoxycarboxylic acids Can be replaced by

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, any two or more of zinc, manganese, iron, molybdenum, tin, and antimony can be used in combination. In two or more metal chelate compounds, both chelate ligands having sulfur as a coordinating atom are one of multiple metal coordination sites. However, as described above, in one metal chelate compound, a chelate ligand having sulfur as a coordinating atom may be coordinated in all of a plurality of metal coordination sites. Good. 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]

5% -N, N-Jetilditi A crystal formed on a phosphoric acid film by immersing a metal material, which has been previously coated with a phosphoric acid film, in a hot solution of sodium rubamate trihydrate (pH 10). The mixed chelating ligand zinc chelate compound is used as the lubricant.

If the pH is adjusted to the range of 6.5 to 13.5, sodium N, N-getyldithiocarbamate (a ligand having sulfur as a coordinating atom) will cause zinc ions or iron ions in the phosphoric acid film. To form a crystalline mixed ligand zinc or iron chelate compound on the phosphoric acid film, which becomes a lubricating film. The chelating ligand may be any of those shown in Formulas 1-28.

[Sixth experimental example]

In a mixture of zinc sulfate heptahydrate 40 g / 20 Om 1, a mixed aqueous solution (150 ml) of N, N-getylditi talented sodium rubamate trihydrate 31 g and sodium hydroxide 5.9 g was slowly stirred. Add to this to obtain a suspension of mono- (N, N_getyldici talented lubamato) hydroxoaquazinc (hereinafter referred to as I) (pH 1.5-12.0).

When a metal material previously coated with a phosphoric acid film is 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, which has been 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, and in particular, a chelating ligand having sulfur as a ligand coordinates a part of the metal coordination site and the remaining coordination sites include Preferably, a ligand containing no sulfur is coordinated. In this case, the chelate containing sulfur The ligand coordinates to the metal, and the sulfur-free ligand coordinates to the zinc or iron ions in the phosphate coating, yielding a crystalline dinuclear metal chelate compound. A test drilled with the lubricant prepared in the first to sixth examples (in the case of a reduction of area of 12%: a cylinder with an inner diameter of 15 thighs, an outer diameter of 29.9 mm, and a length of 50 mm) (The member was used.)), And dried with hot air of 150 ° C. for 60 seconds. The time required for this treatment was about 2 minutes.

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

For further comparison, the same billet was prepared by applying a processing oil (with lubrication aid added) (Comparative Example 2). The time required for this treatment was about 30 seconds. Each ballet was subjected to a ball-through test. In this test, the load required for forcibly passing an iron ball having a diameter larger than the diameter of the hole of the billet through the hole of the billet to plastically deform the billet was measured, and the surface of the inside diameter of the billet was measured. The lubrication performance is evaluated based on the properties, and 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 area reduction rate in the table indicates the rate of change in the diameter of the hole in the billet before and after deformation. The larger the number, the higher the degree of deformation, ie, the heavier the work. In addition, it can be seen that the smaller the length of the surface property that does not cause seizure or even if it occurs, the better the lubrication.

The numbers in the table indicate the load (unit: t) Area reduction 6% 8¾ 10¾ 12% Treatment time Experimental example 1 19.625 NG NG NG 2 minutes Experimental example 2 11. 676 15.858 20.721 NG 2 minutes

In the table, NG indicates that the iron ball and billet were baked and good surface properties could not be obtained. Although not all experimental examples of the present invention enable heavy working, light processing is possible in all experimental examples, and better lubrication performance than when oil is used in all experimental examples. Was obtained. In addition, by appropriately selecting from the lubricants of the present invention, heavy working becomes possible.

In the case of this example, the same performance as that of Comparative Example 1 can be obtained only by forming a lubricating film by coating, and it is confirmed that it can be sufficiently put to practical use. In addition, the processing time is about 2 minutes, and the treatment can be performed in a very short time. In particular, there is a remarkable difference in performance as compared with Comparative Example 2, and it is confirmed that even when processing cannot be performed with Comparative Example 2, processing can be performed according to this example.

【The invention's effect】

According to the lubricant liquid of the present invention, a simple operation of coating achieves the same performance as a troublesome and troublesome operation of forming a phosphoric acid film and forming a film of metal stone on it. A strong lubricating film can be formed. No oil used in this invention Therefore, it does not cause problems such as deteriorating the working environment or requiring degreasing later. In addition, the problem that large-scale equipment is required and a large amount must be processed at one 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 a lubricating film is formed following the cycle of the plastic working device, and extra inventory is required between both processes. If you do not do so, or if you realize a short lead time, you can do something.

Claims

The scope of the claims

A metal in which a bidentate or polydentate chelating ligand having at least one of its coordinating atoms as sulfur coordinates at least one of zinc, manganese, iron, molybdenum, tin and antimony. An aqueous lubricant in which a chelate compound is suspended or dispersed in water.

A multidentate or multidentate chelating ligand in which at least one of the coordinating atoms is sulfur partially binds multiple coordination sites of one or more metals of zinc, manganese, iron, molybdenum, tin, and antimony. A mixed-ligand metal chelate compound in which a ligand that does not have sulfur as a coordinating atom is coordinated in the remaining coordination sites while being filled.

A multidentate or multidentate chelating ligand in which at least one of the coordinating atoms is sulfur partially binds multiple coordination sites of one or more metals of zinc, manganese, iron, molybdenum, tin, and antimony. And a co-ligand metal chelate compound in which a hydroxide ion, condensed phosphoric acid, a polycarboxylic acid-type polymer activator, and a di- or polyoxycarboxylic acid are coordinated in the remaining coordination sites.

An aqueous lubricant in which the mixed ligand metal chelate compound according to claim 2 or 3 is not suspended or dispersed in water.

An aqueous lubricant comprising the aqueous lubricant according to claim 1 and a soluble condensed phosphate, a soluble polycarboxylic acid type polymer activator and Z or a soluble polyoxycarboxylate.

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 coordinating atoms is sulfur. A method of producing a crystalline mixed ligand metal chelate compound on a phosphoric acid film by reacting with zinc ions and phosphorus or iron ions in the phosphoric acid film.

A metal material previously coated with a phosphoric acid film is immersed in the aqueous lubricant according to claim 4 or 5, and a ligand which is not a chelate ligand having sulfur as a coordinating atom and which is contained in the phosphoric acid film. Reacting with a zinc ion and / or an iron ion to form a crystalline dinuclear metal chelate compound on the phosphoric acid film.

Prior to the plastic working of the metal material, the water-based lubricant according to claims 1, 4 or 5 is applied to at least one of the surface of the metal material and the forming surface of the metal mold. 6. The method for using a water-based lubricant according to claim 1, 4 or 5, wherein a lubricating film is formed on the surface, and the metal material can be subjected to plastic working with the lubricating film formed on the surface.