JP2000309793A - Water-based lubricant for plastic working of metallic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based lubricant desirable for the plastic working of a metallic material on which a film has been formed by chemical conversion. SOLUTION: This lubricant comprises (A) a water-soluble inorganic salt, (B) a fatty acid metal salt, and (C) a wax which are dissolved or dispersed in water in such amounts that the solid concentration ratio B/A is 0.06-10, and the solid concentration ratio CA is 0.06-6. Inorganic salt A used is exemplified by a silicate, a borate, a molybdate, or a tungstate, and metal salt B used is exemplified by calcium stearate or zinc stearate. The lubricant may additionally contain a solid lubricant such as molybdenum disulfide, graphite, BN, graphite fluoride, or mica and may further contain a sulfur-, molybdenum, phosphorus-, or chlorine-containing extreme pressure additive.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic working water used for a metal material after chemical conversion treatment for imparting excellent lubricity to the surface of the metal material such as steel, stainless steel, titanium, aluminum or the like. It relates to a system lubricant. More specifically, the present invention provides forging, wire drawing,
After the surface of a metal material such as steel, stainless steel, titanium, or aluminum used for performing plastic working such as drawing, the surface of which is subjected to chemical conversion treatment, applied by spraying or dipping, and immediately dried, a process excellent in said surface. The present invention relates to an aqueous lubricant for plastic working of a metal material after a chemical conversion treatment, which is used when forming a film having lubricity.

[0002]

2. Description of the Related Art Generally, when a metal material such as steel or stainless steel is subjected to plastic working, a lubricating film is formed on a metal surface for the purpose of preventing seizure or galling caused by metal contact between a workpiece and a tool. As a film to be formed on the metal surface, a substance that physically attaches a lubricant to the metal surface,
There is a method in which a chemical conversion film is formed on a metal surface by a chemical reaction, and then a lubricant is used.

[0003] Lubricants that are physically attached to the metal surface are generally used in cases where processing is light because of poor adhesion compared to those used by forming a chemical conversion coating on the metal surface. When a chemical conversion coating is used, a phosphate film or an oxalate film serving as a carrier is formed on the surface, and then a lubricating lubricant is used. This type has a two-layer structure consisting of a chemical conversion film as a carrier film and a lubricant, and exhibits extremely high seizure resistance. Therefore, it has been used in a very wide range in the field of plastic working such as drawing, drawing, and forging. Especially in the field where processing is severe even in plastic processing, phosphate film or oxalate film is used as a base,
In addition, a method of using a lubricant is often used.

[0004] Lubricants used on chemical conversion coatings can be broadly divided into two types depending on the method of use. One is to physically attach a lubricant to the chemical conversion coating, and the other is to make the lubricant react to and adhere to the chemical conversion coating.

[0005] The former lubricants include mineral oils, vegetable oils and synthetic oils as base oils with an extreme pressure agent added thereto.
Alternatively, a solid lubricant such as graphite and molybdenum disulfide is dissolved in water together with a binder component and used in the adhesion drying step. These lubricants have the advantage that they can be easily used by spray coating or dip coating, and there is little need for liquid management.However, they have low lubricity and can be used for relatively light lubrication. Many.

On the other hand, the latter is treated with a reactive soap such as sodium stearate as a lubricant. When particularly high lubricity is required, a reactive soap is used as a lubricant. Reactive soap has high lubricity by reacting with a chemical conversion coating.

However, since the use of reactive soap is a chemical reaction, it is necessary to manage the liquid, control the temperature for controlling the chemical reaction, and renew the waste due to deterioration of the liquid. In addition, since the reaction type soap erodes the chemical conversion treatment film by the reaction, lubricating properties are extremely deteriorated if there is a metal material to which the chemical conversion treatment film is not easily attached or a portion having a small amount of adhesion due to reaction unevenness. On the other hand, when a lubricant is physically attached to the chemical conversion coating, liquid management and disposal and renewal are not required as in the case of reactive soap, and processing is simple, but lubricity is often insufficient. .

In order to solve such problems, a lubricant composition comprising a water-soluble polymer or an aqueous emulsion thereof as a base material and a solid lubricant and a chemical conversion film-forming agent mixed therein (Japanese Patent Laid-Open No. 52-20967). JP-A No. 1993-75, but nothing comparable to chemical conversion coating treatment has been obtained.

[0009]

SUMMARY OF THE INVENTION Accordingly, the present invention is to solve the above-mentioned problems of the prior art, and is a water-based lubricant used for a metal material provided with a chemical conversion coating in plastic working. A water-based lubricant for plastic working of metal materials after chemical conversion treatment, which has a lubricity comparable to that of a reactive soap-coated film applied to a conventional chemical conversion coating by a simple method of being applied by dipping or spraying and then drying. The purpose is to provide.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the chemical conversion treatment film was formed using an aqueous solution containing a water-soluble inorganic salt, a metal salt of a fatty acid, and a wax. The present inventors have found that excellent lubrication performance is exhibited by attaching to the applied metal material, and have completed the present invention.

That is, the aqueous lubricant for plastic working of a metal material after the chemical conversion treatment of the present invention comprises (A) a water-soluble inorganic salt,
(B) a metal salt of a fatty acid and (C) a wax,
And these components are dissolved or dispersed in water, and the solid content weight ratio (B) / (A) is 0.06 to 10, (C)
/ (A) is in the range of 0.06-6.

In the aqueous lubricant for plastic working of a metal material according to the present invention, the water-soluble inorganic salt is at least one selected from the group consisting of sulfate, silicate, borate, molybdate and tungstate. Preferably it is.

The metal salt of the fatty acid is preferably obtained by reacting a C12-C26 saturated fatty acid with at least one metal selected from the group consisting of zinc, calcium, barium, aluminum, magnesium and lithium.

The wax component has a melting point of 7 dispersed in water.
It is preferably a natural wax at 0 to 150 ° C or a synthetic wax.

The aqueous lubricant for plastic working of the metal material of the present invention is further selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, acrylic resin, vinyl acetate resin, epoxy resin, urethane resin and phenolic resin. It is preferable that at least one resin is contained in an amount of 0.5 to 10% by weight.

The aqueous lubricant for plastic working of metallic materials of the present invention further comprises molybdenum disulfide,
It is preferable to contain 1 to 20% by weight of at least one solid lubricant selected from the group consisting of graphite, boron nitride, mica, fluorinated graphite and polytetrafluoroethylene.

Further, the aqueous lubricant for plastic working of the metal material of the present invention further includes a sulfur-based extreme pressure additive, an organic molybdenum-based extreme pressure additive, a phosphorus-based extreme pressure additive and a chlorine-based extreme pressure additive. It is preferable to contain at least one extreme pressure additive selected from the group consisting of 0.5 to 5% by weight.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in more detail. The (A) water-soluble inorganic salt used in the aqueous lubricant for plastic working of a metal material after the chemical conversion treatment of the present invention is for imparting hardness and strength to the film. Therefore, it is necessary that the selected water-soluble inorganic salt is uniformly dissolved in the solution and has a property of forming a strong film when dried. As the water-soluble inorganic salt having such properties, it is preferable to use at least one selected from the group consisting of sulfate, silicate, borate, molybdate and tungstate.

Examples include sodium sulfate, potassium sulfate, potassium silicate, sodium borate (sodium tetraborate), potassium borate (such as potassium tetraborate), ammonium borate (such as ammonium tetraborate), and ammonium molybdate. , Sodium molybdate, sodium tungstate and the like. These may be used alone or in combination of two or more.

The metal salt of the fatty acid (B) used in the present invention is for imparting lubricity, and its type is not specified, but a saturated fatty acid of C12 to C26 and zinc,
Calcium, barium, aluminum, magnesium,
And at least one metal selected from the group consisting of lithium and lithium.

Among them, it is preferable to use calcium stearate, zinc stearate, barium stearate, magnesium stearate, aluminum stearate, and lithium stearate. The metal salt of the fatty acid used in the present invention is present in a form dispersed in the aqueous lubricant for plastic working of a metal material of the present invention, and a known surfactant can be used if necessary.

The mixing ratio of the water-soluble inorganic salt (A) and the metal salt of the fatty acid (B) is preferably 0.06 to 10 as (B) / (A) (weight ratio of solid content). , 1
It is more preferably set to ５5. If the ratio is less than 0.06, the slipperiness of the film may be insufficient, and if the amount exceeds 10, the seizure resistance of the film may be insufficient. The amount of the water-soluble inorganic salt and the metal salt of the fatty acid in 100% by weight of the aqueous lubricant is preferably 1 to 20% by weight, preferably 5 to 15% by weight. Is more preferred.

Next, as the wax (C), it is preferable to use a natural wax or a synthetic wax although the structure and the type thereof are not specified. The wax component is added in order to melt by the heat generated during plastic working and improve the slipperiness of the film. Therefore, in order to exert an effect in the early stage of processing, it is desirable that the melting point is 70 to 150 ° C., and that it is stable in an aqueous solution and does not lower the film strength.

Specific examples include paraffin wax, microcrystalline wax, petrolatum wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, carnauba wax, montan wax and the like. These are preferably mixed with other components in the form of a water dispersion or a water emulsion and included in the plastic working aqueous lubricant of the present invention.

The compounding amount of the wax is preferably 0.06 to 6 as a weight ratio (C) / (A) of the solid content of the water-soluble inorganic salt (A) and the wax (C), and 0.07 to 6 More preferably, it is 2. If this ratio is less than 0.06, the slipperiness of the coating may be insufficient, and if it exceeds 6, the adhesion of the coating may be insufficient.

When used for plastic working in which high deformation is applied, it is preferable that the aqueous lubricant for plastic working of a metal material of the present invention further contain a resin. In such a case, it is desirable that the resin has adhesiveness and film strength enough to withstand plastic working. Such materials include polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, acrylic resins, vinyl acetate resins, epoxy resins, urethane resins and phenolic resins.

It is of course possible to use commercially available resins for these various resins. In such a case, generally, when the resins are water-soluble, they can be obtained as aqueous solutions, and when the resins are insoluble, surfactants are used. To obtain a dispersion in the form of a dispersion in water. The compounding amount of the resin is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on 100% by weight of the aqueous lubricant. If the amount is less than 0.5% by weight, the adhesion is poor, and if it exceeds 10% by weight, the slipperiness is inferior.

In the case of severe plastic working, it is preferable to further include a solid lubricant in the aqueous lubricant for plastic working of a metal material of the present invention. In such a case, the solid lubricant desirably exists stably in the film and has a function of assisting lubrication under a high load. Such materials include molybdenum disulfide, graphite, boron nitride, mica, graphite fluoride, polytetrafluoroethylene, and the like. Examples of polytetrafluoroethylene include polytetrafluoroethylene having a degree of polymerization of about 1,000,000 to 10,000,000.

The compounding amount of the solid lubricant is 10
It is preferable to set it to 1 to 20% by weight with respect to 0% by weight,
More preferably 1 to 10% by weight, 1 to 5% by weight
It is even more preferred that If the amount is less than 1% by weight, the seizure resistance may be insufficient, and the amount may be 20% by weight.
If it exceeds 300, the adhesion of the film may be reduced.

In the case of more severe plastic working,
It is preferable that an extreme pressure additive is further contained in the aqueous lubricant for plastic working of metal materials. As the extreme pressure additive in such a case, those which are stable in the film and exert an extreme pressure effect on the contact surface between the tool and the metal by processing are preferable. As such, sulfurized olefins, sulfurized esters, sulfides, thiocarbonates, chlorinated fatty acids, phosphates, phosphites, molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), zinc dithiophosphate (ZnDT
P) and other extreme extreme pressure additives, organomolybdenum extreme pressure additives, phosphorus extreme pressure additives and chlorine extreme pressure additives.

The amount of the extreme pressure additive is 10
It is preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight, based on 0% by weight. If the amount is less than 0.5% by weight, the extreme pressure effect may be insufficient, and if it exceeds 5% by weight, the adhesion of the film may be reduced.

When a surfactant is required for dispersing or emulsifying the above-mentioned metal salts of fatty acids, waxes, resins, solid lubricants and extreme pressure additives, nonionic surfactants and anionic surfactants may be used. Any of a surfactant, an amphoteric surfactant and a cationic surfactant can be used.

The nonionic surfactant is not particularly restricted but includes, for example, polyoxyethylene alkyl ether, polyoxyalkylene (ethylene and / or propylene) alkyl phenyl ether, polyethylene glycol (or ethylene oxide) and higher fatty acids (for example, carbon Polyoxyethylene alkyl ester, sorbitan, polyethylene glycol and higher fatty acid (for example, having 12 to 18 carbon atoms)
And polyoxyethylene sorbitan alkyl esters.

The anionic surfactant is not particularly restricted but includes, for example, fatty acid salts, sulfates, sulfonates, phosphates, dithiophosphates and the like. Examples of the amphoteric surfactant include, but are not particularly limited to, amino acid-type and betaine-type carboxylate, sulfate, sulfonate, phosphate ester salts and the like. Examples of the cationic surfactant include, but are not particularly limited to, fatty acid amine salts and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more.

The method for producing the aqueous lubricant for plastic working of metal materials of the present invention is not particularly limited. For example, a metal salt of a fatty acid and a wax are added to an aqueous solution of a water-soluble inorganic salt using a surfactant and water as needed to form a dispersion, and the mixture is added and stirred well. Further, the solid lubricant and / or extreme pressure additive as optional components can be produced by dispersing or emulsifying with a surfactant and water, if necessary, followed by adding and stirring.

The water-based lubricant for plastic working of the present invention can be used for forming a phosphate film (phosphoric acid) on a metal material such as iron or steel, stainless steel, copper or copper alloy, aluminum or aluminum alloy, titanium or titanium alloy by a known method. After coating with zinc, manganese phosphate, iron phosphate, tin phosphate, etc., oxalate film (iron oxalate, etc.), cryolite, calcium aluminate, cold plastic working (drawing,
It can be used as a lubricant for use in drawing, forging, etc.).

The shape of the metal material is not particularly limited, since not only materials such as bars and blocks, but also shapes (gears, shafts, etc.) after hot forging are considered. Since the water-based lubricant of the present invention applies a chemical conversion coating to a metal material to be processed and is applied thereon, it is necessary to apply the chemical conversion coating to the metal material prior to application.

Since the water-based lubricant used in the present invention is a non-reactive type, the type of chemical conversion coating is not particularly limited, and an appropriate chemical conversion coating is formed by a generally known method according to the type of metal and the difficulty of processing. Just do it. For example, for iron or steel, zinc phosphate, manganese phosphate, and iron phosphate coatings can be used. For stainless steel, an iron oxalate film can be used. For copper and copper alloys, zinc phosphate can be used. For aluminum and aluminum alloys, zinc phosphate, cryolite, and calcium aluminate films can be used. For titanium and titanium alloys, a titanium fluoride coating can be used.

The aqueous lubricant for plastic working of the metal material of the present invention is applied to the surface of the metal material provided with the chemical conversion coating by a conventional method such as immersion, spraying or pouring. The application may be performed as long as the surface is sufficiently covered with an aqueous lubricant for plastic working, and the application time is not particularly limited. After application, the aqueous lubricant for plastic working needs to be dried. Drying may be left at room temperature,
Usually, it is preferably performed at 60 to 150 ° C. for 10 to 60 minutes.

The coating weight of the aqueous lubricant for plastic working of the metal material of the present invention after application and drying is preferably 0.5 g / m ² or more in order to exhibit sufficient sliding performance, and 30 g / m ² from the viewpoint of cost. m ² or less, preferably 1 to 2
0 g / m ² , more preferably ² to 10 g / m ^2.
Is even more preferred.

[0041]

EXAMPLES Examples of the present invention will be described together with comparative examples, and the effects thereof will be described more specifically.

Examples 1 to 7, Comparative Examples 1 to 5: Water-based plastic working lubricants were prepared at the ratios shown in Table 1. The preparation was carried out by adding a water-soluble inorganic salt, a metal salt of a fatty acid, a wax and a surfactant (1% by weight of a nonionic type) to water and stirring the mixture well.
Further, a test piece (material: SPC steel plate was subjected to a chemical conversion treatment in dimensions 150 mm × 75 mm, thickness 1.
0 mm) for 30 seconds, dried at 100 ° C. for 30 minutes, and subjected to the Bowden test.

The Bowden test pieces were subjected to the following pretreatment steps (1) to (4) prior to the application of an aqueous lubricant for plastic working, followed by hot-air drying. (1) Degreasing (Nippon Parkerizing Alkaline Degreasing Agent Fine Cleaner 4360, concentration 20 g / L, temperature 60 ° C, immersion for 10 minutes) (2) Rinse normal temperature tap water spray for 30 seconds (3) Chemical formation Zinc phosphate film coating agent Palbond 181X Concentration 90 g / L Dipping treatment in a treatment solution at 80 ° C. for 10 minutes) (4) Washing Room temperature tap water spray for 30 seconds.

The film weight (g / m ² ) was calculated from the difference in weight before and after the application of an aqueous lubricant for plastic working. The Bowden test
Test load: 5 kg, Test temperature: Room temperature, Test steel ball: 5 mm
As φ, the friction coefficient and the number of seizures (the number of times of sliding until the friction coefficient becomes 0.25) were measured. The average coefficient of friction was an average of 10 times before and after the number of seizure times ×.

Next, in the backward piercing test, the test piece was immersed in an aqueous lubricant for plastic working for 30 seconds, and then heated at 100 ° C. for 3 seconds in an oven.
The test was carried out after allowing to stand for 0 minutes and completely drying. In addition, after performing the following pre-processing steps (1) to (6) on the test piece prior to the application of the aqueous lubricant for plastic working,
Hot air dried.

(1) Degreasing (Alkaline degreasing agent Fine Cleaner 4360, manufactured by Nippon Parkerizing Co., Ltd., concentration 20 g / L, temperature 60 ° C., immersion for 10 minutes) Concentration 17.5% by weight, temperature RT, immersion time 10 minutes (4) Rinse at normal temperature tap water spray 30 seconds (5) Chemical formation (Nippon Parkerizing Co., Ltd. zinc phosphate coating agent Palbond 181X concentration 90g / L 80 ° C (10 minutes immersion treatment in treatment liquid) (6) Rinse at room temperature Tap water spray for 30 seconds The material subjected to the backward drilling test is a commercially available S45C spheroidized annealed material.
It is changed in units of 2 mm up to 40 mm. (13 levels)

The backward drilling test was carried out using a 200-ton crank press, and a punch having a diameter of 50% and a punch having a diameter of 50% was placed on a cylindrical test piece in which a mold was set and the outer periphery was restrained. It was carried out by hitting and obtaining a cup-shaped molded product. At this time, the bottom dead center of the press was adjusted so that the margin at the bottom of the test piece was 10 mm. In the backward piercing test, the test pieces were machined in ascending order of height, and were tested until the machined surface was damaged. In the evaluation, the height in the cup of the test piece in which the inner surface was not damaged was defined as a good perforation depth.

Die: SKD11 Punch: HAP40, Land diameter: 21.21 mmφ Test piece: S45C spheroidized annealing material Reduction rate: 4, 6, 8, 10, 12, 14% Processing speed: 30 strokes / min. Is shown in FIG.

Comparative Example 6: The same Bowden test piece and rear drilling test piece as in Examples 1 to 7 were subjected to a chemical conversion treatment and a reactive soap lubrication treatment under the conditions shown in Table 1. The obtained test piece was subjected to the Bowden test and the backward drilling test in the same manner as in Examples 1 to 7.

[0050]

[Table 1]

Table 1 shows the results of the above test. As is clear from Table 1, it is understood that Examples 1 to 7 using the aqueous lubricant for plastic working for metal materials of the present invention exhibit excellent lubricity by a simple operation. On the other hand, the component ratio (B) / (A) of the present invention is out of the range, the comparative examples 1 and 2, the component (B).
In Comparative Example 3 having no fatty acid metal salt, Comparative Example 4 having no component (C), and Comparative Example 5 having no component (A), none of them simultaneously satisfied excellent lubricity and simple workability. In addition, the phosphate film of Comparative Example 6 subjected to the reaction soap treatment shows lubricity equivalent to that of the present invention, but requires wastewater treatment and liquid management and cannot be used with simple equipment.

[0052]

As is evident from the above description, the use of the aqueous lubricant plastic for plastic working of the metal material of the present invention makes it possible to produce a film having high lubricity by simple processing. In addition, since there is little waste and the working environment is good,
Its business value is extremely high.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a posterior perforation test.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 159: 06) C10N 10:02 10:04 10:06 10:12 20:00 30:06 30:08 40:24 50:02 80:00 (72) Inventor Yoshio Matsumura 1-15-1 Nihonbashi, Chuo-ku, Tokyo Japan F-term in Parkerizing Co., Ltd. (reference) 4H104 AA01C AA04A AA05A AA11C AA18C AA19A AA21C AA24A AA26C BA02A BA02C BB17A BD07C BG02C BG04C BG10C BG11C BH02C BH03C BH07C CA02A CA02C CA03A CA03C CB02C CB04C CB08C CB12C CB15C CD02A CE05C CE13C DA05A DA05C FA01 FA02 FA03 FA06 LA03 LA20 PA23 Q

Claims (7)

[Claims] 1. A composition comprising (A) a water-soluble inorganic salt, (B) a metal salt of a fatty acid, and (C) a wax, wherein these are dissolved or dispersed in water, and their solid content concentration ratio ( B) /
(A) is 0.06 to 10, (C) / (A) is 0.06 to
6. An aqueous lubricant for plastic working of metallic materials, which is in the range of 6. 2. The water-soluble inorganic salt is a sulfate, a silicate,
The aqueous lubricant for plastic working of a metal material according to claim 1, which is at least one selected from the group consisting of borate, molybdate and tungstate. 3. The method according to claim 1, wherein the metal salt of the fatty acid is C12 to C26.
The aqueous lubricant according to claim 1, wherein the saturated fatty acid is obtained by reacting at least one metal selected from the group consisting of zinc, calcium, barium, aluminum, magnesium and lithium. . 4. The method according to claim 1, wherein the wax has a melting point of 70 dispersed in water.
The aqueous lubricant for plastic working of a metal material according to claim 1, which is a natural wax or a synthetic wax at a temperature of ~ 150 ° C. 5. The method according to claim 1, wherein at least one water-soluble synthetic resin selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, an acrylic resin, a vinyl acetate resin, an epoxy resin, a urethane resin and a phenolic resin is used in an amount of 0.5 to 0.5. The aqueous lubricant for plastic working of a metal material according to any one of claims 1 to 4, which contains 10% by weight. 6. The composition further comprises 1 to 20% by weight of at least one solid lubricant selected from the group consisting of molybdenum disulfide, graphite, boron nitride, mica, graphite fluoride and polytetrafluoroethylene. The aqueous lubricant for plastic working of a metal material according to claim 1. 7. An at least one extreme pressure additive selected from the group consisting of a sulfur extreme pressure additive, an organic molybdenum extreme pressure additive, a phosphorus extreme pressure additive, and a chlorine extreme pressure additive. The aqueous lubricant according to any one of claims 1 to 6, which is contained in an amount of 5 to 5% by weight.