JP2006272461A - Metallic material for plastic working, method for manufacturing the same, and surface treating agent for metallic material for plastic working - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic material for plastic working which does not generate diffusion of phosphorus in a phosphate film formed with the phosphate film, and has the lubricity and corrosion resistance as excellent as or better than those of the metallic material for plastic working formed with the phosphate film and a method for manufacturing the same, and a surface treating agent for manufacturing the same. <P>SOLUTION: (1) The method for manufacturing the metallic material for plastic working comprises forming the film on the surface of the metallic material by immersing the metallic material for plastic working into an aqueous solution containing one kind or more of a silicate and a borate or a calcium hydroxide and a peroxide and then drying the film. (2) The surface treating agent comprises an aqueous solution of the same composition as that of the above aqueous solution. (3) The metallic material for plastic working comprises a first layer composed of iron, calcium and oxygen on the surface of steel products, and comprises a film composed of borate, calcium hydroxide, and peroxide as a second layer covering the first layer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention belongs to a technical field relating to a metal material for plastic working, a method for producing the same, and a surface treatment agent for the metal material for plastic working, and is particularly excellent in seizure resistance, lubricity and corrosion resistance, and during heat treatment. Belongs to the technical field related to metal materials for plastic working (drawing, wire drawing, forging, forging, etc.) capable of avoiding the immersion of phosphorus (diffusion of phosphorus in the phosphate film) and the manufacturing method thereof.

  In general, the metal wire obtained by cold drawing is further subjected to cold working (plastic working) such as cold forging for various applications, so that its surface has seizure resistance. It is necessary to form a film having a lubricity.

  When such a film is coated on the surface of a workpiece such as a metal wire, metal contact between the machining tool and the workpiece is avoided and processing heat generation is suppressed, thereby suppressing the occurrence of seizure, Since the friction coefficient on the surface of the workpiece is lowered, the machining load is reduced and the machining energy is reduced.

  By the way, as a lubricant for cold wire drawing, a powdery lubricant containing a metal soap such as calcium stearate and containing calcium hydroxide as a carrier agent is used.

  However, when cold wire drawing is performed using such a powdery lubricant, in a severe cold plastic working process such as cold forging after cold wire drawing, There is a problem that the film formed on the surface of the metal wire by the wire drawing process has insufficient lubricity and defects such as seizure occur.

  Therefore, for example, when a coating having high lubricity and seizure resistance is required, such as a material for cold forging, phosphate conversion is performed on the surface of the base material (wire for cold drawing) in advance. A chemical conversion film (phosphate film such as zinc phosphate film) is formed by the treatment, and a soap layer composed of zinc stearate and sodium stearate is formed thereon, and cold drawing is performed. A method of forming a film composed of a salt film and a soap layer (hereinafter, this film is referred to as a soap / phosphate film) has been adopted.

  This soap / phosphate film has high lubricity and seizure resistance that can sufficiently follow severe processing such as cold forging, and also has excellent rust resistance.

  However, when heat-treating the final product after cold wire drawing, diffusion of phosphorus in the soap / phosphate film (hereinafter referred to as immersion phosphorous) occurs. There was a problem that it occurred in tension bolts.

  Regarding high-tensile bolts, JIS-B1051 stipulates that “12.9 class strength male threaded parts must not have a white phosphorus-concentrated layer that can be confirmed with an optical microscope on the surface where tensile stress is applied”. .

  Therefore, a lubricant containing lime soap as a main component (Japanese Patent Laid-Open No. 9-3476), a lubricant film containing alkali metal borate as a main component (Japanese Patent Laid-Open No. 2002-192220), potassium silicate, stearic acid Lubricants composed of salts, fluorine-based resins, etc. (Japanese Patent Laid-Open No. 2003-53422) have been proposed, but these have sufficient performance in terms of lubricity, seizure resistance, moisture resistance and rust resistance. Not.

In addition, when using phosphate (zinc phosphate etc.), although it is excellent in lubricity (workability) and the corrosion resistance after a process, complicated liquid management and many processes are required. In addition, a large amount of sludge is generated due to a chemical reaction with the material to be treated, and labor and cost are required for the treatment.
JP-A-9-3476 JP 2002-192220 A JP 2003-53422 A

  The present invention has been made paying attention to such circumstances, and its purpose is to provide a metal material for plastic working formed with a soap / phosphate film (a film comprising a phosphate film and a soap layer). There is no occurrence of phosphorus immersion during heat treatment as in the case of the metal, and the metal material for plastic working that is excellent in lubricity and corrosion resistance equal to or higher than that of the metal material for plastic working formed with a soap / phosphate film. It is an object of the present invention to provide a production method and a surface treatment agent for the production.

  In order to achieve the above object, the present inventors have intensively studied, and as a result, completed the present invention. According to the present invention, the above object can be achieved.

  The present invention thus completed and capable of achieving the above object relates to a metal material for plastic working, a method for producing the same, and a surface treatment agent for the metal material for plastic working. 3. A method for producing a metal material for plastic working according to claim 3 (a method for producing a metal material for plastic working according to the first to third inventions), a metal material for plastic working according to claim 4 (a metal material for plastic working according to the fourth invention). ), A surface treatment agent for a metal material for plastic working according to claims 5 to 6 (a surface treatment agent for a metal material for plastic working according to the fifth to sixth inventions), and a metal material for plastic working according to claims 7 to 8 ( A metal material for plastic working according to the seventh to eighth inventions), and a method for producing a metal material for plastic working according to claim 9 (a method for producing a metal material for plastic working according to the ninth invention), which is as follows. It is a configuration.

  That is, in the method for producing a metal material for plastic working according to claim 1, the metal material for plastic working is added to an aqueous solution containing at least one of silicate and borate or calcium hydroxide and a peroxide. It is a method for producing a metal material for plastic working characterized by forming a film on the surface of the metal material after dipping [first invention].

  The method for producing a metal material for plastic working according to claim 2, wherein the concentration ratio of one or more of silicates and borates or calcium hydroxide and peroxide in the aqueous solution is 4: 1 to 200: 2. The method for producing a metal material for plastic working according to claim 1, which is 1 [second invention].

The method for producing a metal material for plastic working according to claim 3, wherein the amount of the coating formed on the surface of the metal material is 2 g / m ² or more. This is a method [third invention].

  The metal material for plastic working according to claim 4 is a metal material for plastic working produced by the method for producing a metal material for plastic working according to any one of claims 1 to 3 [fourth invention].

  The surface treatment agent for a metal material for plastic working according to claim 5 is composed of an aqueous solution containing at least one of silicate and borate or calcium hydroxide and a peroxide. [5th invention].

  The surface treatment agent for a metal material for plastic working according to claim 6 has a concentration ratio of one or more of silicate and borate or calcium hydroxide and peroxide in the aqueous solution of 4: 1 to 200. 6. The surface treating agent for a metal material for plastic working according to claim 5 [6th invention].

  The metal material for plastic working according to claim 7 has a first layer made of iron, calcium and oxygen on the surface of a steel material, and is made of borate, calcium hydroxide and peroxide as a second layer covering the first layer. A metal material for plastic working characterized by having a film [seventh invention]. The metal material for plastic working according to claim 8 is the metal material for plastic working according to claim 7, wherein the thickness of the first layer is 3 to 10 μm [8th invention].

  The method for producing a metal material for plastic working according to claim 9, wherein the metal material for plastic working is immersed in an aqueous solution containing borate, calcium hydroxide and peroxide, and then the surface of the metal material is dried. A method for producing a metal material for plastic working characterized in that a film is formed on [9th invention].

  According to the method for producing a metal material for plastic working according to the present invention, during the heat treatment as in the case of the metal material for plastic working formed with a soap / phosphate film (film comprising a phosphate film and a soap layer). In addition, the metal material for plastic working that is excellent in lubricity and corrosion resistance can be obtained as much as or more than the metal material for plastic working formed with a soap / phosphate film.

  According to the metal material for plastic working according to the present invention, it can be plastically processed with good lubricity and has lubricity equivalent to or better than that of the metal material for plastic working formed with a soap / phosphate film. Moreover, there is no occurrence of phosphorus immersion during heat treatment as in the case of metal materials for plastic working with a soap / phosphate coating, and it is equivalent to or equivalent to metal materials for plastic working with a soap / phosphate coating. As described above, a plastic working material excellent in corrosion resistance [that is, a plastic working material (for example, a bolt-shaped one) after plastic working] can be obtained.

  The surface treatment agent for a metal material for plastic working according to the present invention is suitable as a surface treatment agent in the production of the metal material for plastic work according to the present invention. By using it, the metal material for plastic working according to the present invention is used. Obtainable.

  As a result of intensive studies, the present inventors have immersed a metal material for plastic working in an aqueous solution containing one or more of silicates and borates or calcium hydroxide and a peroxide, When dried to form a film on the surface of the metal material, the lubricity and plasticity of the metal material for plastic working formed with a soap / phosphate film (a film composed of a phosphate film and a soap layer) or higher It has been found that a metal material for plastic working excellent in corrosion resistance can be obtained. That is, by adding one or more of silicates and borates or calcium hydroxide as a film forming agent, and adding a peroxide as a film adhesion improving agent, it is comparable to a soap / phosphate film. It has been found that lubricity and corrosion resistance can be improved up to (to the same or higher level as in the case of soap / phosphate coating).

  The present invention has been completed based on such findings. The method for producing a metal material for plastic working according to the present invention (first invention) thus completed contains at least one of silicates and borates or calcium hydroxide and a peroxide. A method for producing a metal material for plastic working, which comprises immersing the metal material for plastic working in an aqueous solution (hereinafter also referred to as a surface treatment liquid) and then drying to form a film on the surface of the metal material. [First invention]. As can be seen from the foregoing, the metal material for plastic working obtained by this production method is excellent in lubricity and corrosion resistance as much as or better than the metal material for plastic working formed with a soap / phosphate film. Moreover, the film formed on the surface of the metal material by this manufacturing method contains at least one of silicate and borate or calcium hydroxide and peroxide, and does not contain phosphorus. It does not generate immersion phosphorus during heat treatment.

  Therefore, according to the method for producing a metal material for plastic working according to the present invention, there is no occurrence of immersion phosphorus during heat treatment as in the case of a metal material for plastic working formed with a soap / phosphate film, and the soap A plastic working metal material having excellent lubricity and corrosion resistance equal to or higher than that of a plastic working metal material on which a phosphate film is formed can be obtained.

  As conventional non-phosphorous lubricants, lime soap, borate, silicate, and the like are known, but they do not have sufficient performance. This is considered to be because the adhesiveness with the surface of the metal material is insufficient as compared with the soap / phosphate film. That is, in a soap / phosphate film, a phosphate film such as a zinc phosphate film is formed by a chemical reaction with a metal material and adheres firmly, whereas in a non-phosphorous lubricant, There is almost no chemical reaction, and the film components are relatively weakly attached simply by contacting the metal surface.

  In the method for producing a metal material for plastic working according to the present invention, the adhesion between a film formed of a non-phosphorous lubricant (one or more of silicate, borate or calcium hydroxide) and the metal material is obtained. In order to improve, an oxidizing agent (peroxide) is added to the lubricant. Oxidizing agents (peroxides) act on the metal surface to generate metal ions, which ion forms lubricating components (one or more of silicates, borates or calcium hydroxide) and insoluble film components. Newly formed. The insoluble component becomes a chemical conversion film such as a phosphate film such as a zinc phosphate film, and adhesion is improved.

  In the method for producing a metal material for plastic working according to the present invention, as the oxidizing agent (peroxide), since it is used by mixing with basic silicate or borate, or calcium hydroxide, Those having an oxidizing action under basic conditions are preferred. For example, peroxides such as peroxosulfate, peroxocarbonate and peroxoborate are suitable. The presence of peroxide in the film can be confirmed by IR (infrared spectroscopy).

  The amount of peroxide present can be quantified by iodometry. Add 100 ml of 10 g / L (liter) aqueous potassium iodide solution to 25 ml of the solution in which the lubricating film is dissolved in dilute sulfuric acid, and let stand for 15 min. Next, the produced iodine is titrated with 0.1 N sodium thiosulfate aqueous solution and starch as an indicator.

  As the silicate, various alkali metal silicates can be used, for example, sodium orthosilicate, sodium metasilicate, and the like. The presence of silicate in the film can be confirmed by XRD (X-ray diffraction analysis).

  As the borate, various alkali metal borates can be used. For example, sodium metaborate, sodium tetraborate and the like can be used. The presence of borate in the film can be confirmed by XRD (X-ray diffraction analysis).

  Calcium hydroxide can be used regardless of properties such as particle size, and calcium oxide may be used as a raw material with water added thereto.

  In the method for producing a metal material for plastic working according to the present invention, at least one of silicate and borate in a surface treatment liquid (aqueous solution used for immersing the metal material for plastic working) or calcium hydroxide (film forming agent) ) And peroxide (film adhesion improver) is not particularly limited, but it is 4 from the viewpoint of adhesion between the metal material for plastic working and the film formed on the surface thereof. : 1 to 200: 1 is preferable [second invention].

  The surface treatment liquid may contain molybdate, vanadate, polyacrylic acid, silica, or benzotriazole as a rust inhibitor. When such a rust preventive agent is included, the corrosion resistance of the metal material for plastic working after being immersed in the surface treatment solution to form a film can be further improved.

  The treatment temperature (temperature of the surface treatment liquid) when the metal material is immersed in the surface treatment liquid is preferably 30 to 70 ° C. If the temperature is lower than 30 ° C, it takes time to dry the treatment solution attached to the metal material after the metal material is immersed and removed from the treatment solution. If the temperature is higher than 70 ° C, decomposition of the oxidant may occur. Because there is sex. From such a point, it is more preferably 40 to 60 ° C.

  The form of the metal material immersed in the surface treatment liquid is not particularly limited as long as it is a metal material for plastic working. For example, bolts, nuts, springs, PC (prestressed concrete) steel, steel cords, bead wires For example, a wire rod or a bar rod for producing the above-mentioned material may be used. Moreover, the component of a metal material is not specifically limited, Various metal materials, such as steel materials (iron and steel, stainless steel), aluminum, titanium, copper, can be used. A preferable metal material is a steel material.

  In addition, a solid lubricant can be added to reduce the coefficient of friction. Examples of the solid lubricant include molybdenum disulfide, graphite, boron nitride, mica, graphite fluoride, polytetrafluoroethylene, and paraffin.

The amount of the coating formed on the surface of the metal material by the method for producing a metal material for plastic working according to the present invention is preferably 2 g / m ² or more [third invention]. This is because a large amount of continuous wire drawing is difficult when the coating amount is less than 2 g / m ² . From this point, it is more desirable that the coating amount is 4 g / m ² or more. On the other hand, the adhesion amount of the coating: The 40 g / m ² greater saturation effect of improving the lubricity, the adhesion amount of the coating: since no improvement in the above case of 40 g / m ^2, the adhesion amount of the coating: 40 g / m ² The following is desirable. From such a point (degree of improvement in lubricity / point of coating amount), it is more desirable that the coating amount is 20 g / m ² or less.

  The immersion time of the metal material in the surface treatment liquid is not particularly limited, but since this immersion time is related to the amount of coating film, it can be appropriately determined so as to be the above-mentioned preferable coating amount of film.

  As described above, the metal material for plastic working according to the present invention (fourth invention) is a method for producing a metal material for plastic working according to any one of claims 1 to 3 (that is, according to the first to third inventions). A metal material for plastic working produced by any one of the methods for producing a metal material for plastic working) (fourth invention). According to the metal material for plastic working according to the present invention, it can be plastically processed with good lubricity and has lubricity equivalent to or better than that of the metal material for plastic working formed with a soap / phosphate film. Moreover, there is no occurrence of phosphorus immersion during heat treatment as in the case of metal materials for plastic working with a soap / phosphate coating, and it is equivalent to or equivalent to metal materials for plastic working with a soap / phosphate coating. As described above, a plastic working material excellent in corrosion resistance [that is, a plastic working material (for example, a bolt-shaped one) after plastic working] can be obtained.

  The surface treatment agent for a metal material for plastic working according to the present invention (the fifth invention) comprises an aqueous solution containing at least one of silicates and borates or calcium hydroxide and a peroxide. A surface treatment agent for a metal material for plastic working as described in [5th invention]. Since the surface treatment agent for a metal material for plastic working according to the present invention has the same composition as the surface treatment liquid in the method for producing a metal material for plastic working according to the present invention, the production of the metal material for plastic working according to the present invention is performed. It is suitable as a surface treatment liquid at the time, and by using it, the metal material for plastic working according to the present invention can be obtained.

  When the concentration ratio of one or more of silicates and borates or calcium hydroxide and peroxide in the aqueous solution (surface treatment agent) is 4: 1 to 200: 1, the invention relates to the second invention. The manufacturing method of the metal material for plastic working can be performed, the adhesion of the film formed on the surface of the metal material becomes more excellent, and the metal material for plastic processing that is superior in the adhesion of the film can be obtained. [Sixth Invention].

  As a result of further research following the above-described research, the present inventors have immersed the metal material for plastic working in an aqueous solution containing borate, calcium hydroxide, and peroxide, and then dried the metal material. It has been found that when a film is formed on the surface of a metal material, it is possible to obtain a metal material for plastic working that is equivalent to or better than a metal material for plastic working formed with a soap / phosphate film, and that has excellent lubricity and corrosion resistance. . That is, borate and calcium hydroxide are used as film forming agents, and as a film adhesion improving agent, peroxide is added to a level comparable to soap / phosphate films (soap / phosphate film). It has been found that lubricity and corrosion resistance can be increased (to the same or better level).

  The seventh to ninth inventions of the present invention have been completed based on this finding. Of the seventh to ninth inventions thus completed, the method for producing a metal material for plastic working according to the ninth invention is characterized in that plasticity is applied to an aqueous solution containing borate, calcium hydroxide and peroxide. A method for producing a metal material for plastic working, wherein the metal material for processing is dipped and then dried to form a film on the surface of the metal material [9th invention]. As can be seen from the foregoing, the metal material for plastic working obtained by this production method is excellent in lubricity and corrosion resistance as much as or better than the metal material for plastic working formed with a soap / phosphate film. Moreover, the film formed on the surface of the metal material by this manufacturing method contains borate, calcium hydroxide, and peroxide, and does not contain phosphorus. It is not a thing.

  Therefore, according to the method for producing a metal material for plastic working according to the ninth aspect of the present invention, there is no occurrence of phosphorus immersion during heat treatment as in the case of the metal material for plastic working formed with a soap / phosphate film. Moreover, it is possible to obtain a metal material for plastic working excellent in lubricity and corrosion resistance equal to or higher than that of a metal material for plastic working formed with a soap / phosphate film.

  In the conventional non-phosphorous lubricant, as described above, there is almost no chemical reaction with the metal material, and the coating component is weakly attached simply by contacting the metal surface.

  In the method for producing a metal material for plastic working according to the ninth aspect of the present invention, in order to improve the adhesion between the film formed of a non-phosphorous lubricant (borate, calcium hydroxide) and the metal material, An oxidizing agent (peroxide) is added to the lubricant. The oxidizing agent (peroxide) acts on the metal surface to generate metal ions, which react with the lubricating components (borate, calcium hydroxide), and this metal (for example, Fe), Ca, O A new reaction layer (insoluble) is formed. The reaction layer works as a chemical conversion film such as a zinc phosphate film, and adhesion is improved.

  According to the method for producing a metal material for plastic working according to the ninth aspect of the present invention, the metal working material has a first layer made of metal, calcium, and oxygen as main components of the metal material, A metal material for plastic working having a film made of borate, calcium hydroxide and peroxide can be obtained as the second layer covering. At this time, if the metal material is a steel material, it has a first layer made of iron, calcium and oxygen on the surface of the steel material, and a film made of borate, calcium hydroxide and peroxide as the second layer covering it. A metal material for plastic processing (steel material) having According to these plastic working metal materials, the plastic working metal material with the same or better than the plastic working metal material on which the soap / phosphate film is formed can be plastically processed with good lubricity. There is no generation of immersion phosphorus during heat treatment as in the case of metal materials for plastic processing with a soap / phosphate coating, and it is equal to or higher than metal materials for plastic processing with a soap / phosphate coating. It is possible to obtain a plastic work material excellent in corrosion resistance [that is, a plastic work material (for example, a bolt shape) after the plastic work].

  The metal material for plastic working according to the seventh aspect of the present invention is the metal material for plastic working as described above, and the metal material is a steel material. Namely, a plastic working characterized by having a first layer made of iron, calcium and oxygen on the surface of a steel material, and having a film made of borate, calcium hydroxide and peroxide as a second layer covering the first layer. [7th invention].

  According to this metal material for plastic working, it can be plastically processed with good lubricity with a lubricity equivalent to or better than that of a metal material for plastic working formed with a soap / phosphate film, There is no generation of immersion phosphorus during heat treatment as in the case of metal materials for plastic processing with a soap / phosphate coating, and corrosion resistance equal to or better than that of metal materials for plastic processing with a soap / phosphate coating. Excellent plastic working material [that is, a material after plastic working (for example, a bolt-shaped one) can be obtained.

  In the seventh aspect of the present invention, the thickness of the first layer is preferably 3 to 10 μm [seventh aspect]. When the thickness of the first layer is less than 3 μm, the metal-to-metal contact cannot be sufficiently prevented, and seizure tends to occur during processing. It is difficult to increase the thickness to 10 μm or more, and the film tends to crack.

  The thickness of the first layer can be measured by Auger spectroscopy. Examples of the measurement conditions are described below. In the obtained profile, for example, the depth from which the Fe content is 5 (atmic%) or more to the depth at which Ca is 5 (atmic%) or less is defined as the thickness of the reaction layer (first layer). .

・ Device ---- PHI650 scanning Auger electron spectrometer manufactured by Parkin Elmer ・ Primary electron energy, current ---- 10 keV, 300 nA
・ The incident angle ---- 30 degrees to the sample normal ・ The beam diameter ---- <5μmφ
・ Analysis area ---- Same as above (point analysis)
・ Ion sputtering energy, current ---- 3 keV, 25 mA
・ The incident angle ---- About 58 degrees to the sample normal ・ The sputtering speed ---- About 31 nm / min

  In the method for producing a metal material for plastic working according to the ninth aspect of the present invention, the oxidizing agent (peroxide) is used as a mixture with a borate that is basic. Those having are preferred. As in the case of the method for producing a metal material for plastic working according to the first invention of the present invention, for example, peroxides such as peroxosulfate, peroxocarbonate and peroxoborate are suitable. The presence of peroxide in the film can be confirmed by IR (infrared spectroscopy).

  As the borate, borates of various alkali metals can be used as in the method for producing a metal material for plastic working according to the first invention of the present invention. For example, sodium metaborate, sodium tetraborate, etc. are used. be able to. The presence of borate in the film can be confirmed by XRD (X-ray diffraction analysis).

  As the rust preventive agent, molybdate, vanadate, polyacrylic acid, silica, and benzotriazole can be appropriately included.

The kind of applicable metal material, the ability to add a solid lubricant, etc. are the same as in the case of the method for producing a metal material for plastic working according to the first invention of the present invention described above. Adhesion amount of film formed on the metal material surface, as in the manufacturing method of plastic working a metal material according to the first aspect of the present invention, it is desirably 2 g / m ² or more, further 4g / m ² On the other hand, it is preferably 40 g / m ² or less, and more preferably 20 g / m ² or less.

  Examples of the present invention and comparative examples will be described below. The present invention is not limited to this embodiment, and can be implemented with appropriate modifications within a range that can be adapted to the gist of the present invention, all of which are within the technical scope of the present invention. include.

[Example A]
Hot-rolled wire made of steel grade SCM435 is heat treated, the heat treated wire is pickled and descaled, then washed with water, neutralized with lime milk, and immersed in a surface treatment solution (aqueous solution) As a result, a wire rod for drawing (diameter φ = 10 mm) was obtained. The composition of the surface treatment liquid, the immersion temperature (temperature of the surface treatment liquid), and the immersion time during this immersion treatment are shown in Table 1 (No. 1 to 14). In addition, it was left to dry in the air after the immersion treatment. The coating amount is about 8 g / m ² .

In addition, the wire after heat treatment, pickling, and water washing similar to the above is subjected to phosphate treatment / soap treatment (phosphate treatment, then soap treatment) to form a soap / phosphate film. To obtain a wire rod for drawing (diameter φ = 10.3 mm) (No. 15). This phosphate treatment / soap treatment was performed as follows. The washed wire is immersed in 15% hydrochloric acid at 50 ° C for 10 minutes and then washed with water. Next, the washed wire is adjusted to an aqueous solution having a concentration of 90 g / L using a zinc phosphate chemical conversion treatment agent [Palbond 181X (manufactured by Nippon Parkerizing Co., Ltd.)]. The water-washed wire is immersed for 10 minutes and then subjected to chemical conversion treatment (phosphate treatment) under the condition of washing with water. Next, the wire after the chemical conversion treatment is adjusted to an aqueous solution having a concentration of 70 g / L using a soap lubricant [Palube 235 (manufactured by Nippon Parkerizing Co., Ltd.)], and the aqueous solution is brought to 80 ° C. Soap is treated under the condition that the treated wire is immersed for 5 minutes. The amount of the soap / phosphate coating (the total amount of the phosphate coating and the soap layer) is about 8 g / m ² .

The composition of the film thus formed was confirmed. This confirmation was performed as follows. For peroxides, the film is peeled off with a piece of SUS, and its components are measured as tablets together with KBr. Since a peak is observed at a wave number of 890 to 830 cm ⁻¹ , the presence of peroxide can be confirmed. As for the lubricant, X-ray (Kα) targeting Cu is used, and the film peeled off with a SUS piece or the like is measured. 2θ = 18.1, 33.5, 47.0 deg for Ca (OH) ₂ , 2θ = 34.9, 31.3, 18.2 deg for Na ₂ B ₄ O ₇ · 10H ₂ O, 2θ = 33.5, 39.5, 18.2 deg for Na ₂ SiO ₃ The presence of each peak can be confirmed from each peak.

  The thus obtained wire for drawing (film formed) and the wire after drawing the wire were examined for lubricity and rust prevention (corrosion resistance). The lubricity was investigated as follows. Without using an auxiliary lubricant, the above wire rod (diameter φ = 10.3 mm) can be used in φ9.5, φ8.3, φ7.45, φ6.3, φ5.6, φ4.9, φ4.2, φ3 .6, φ3.2, φ2.8, φ2.5, φ2.2, and wire drawing in stages, measuring the wire drawing load at this time, and the surface condition of the wire after drawing ( The surface skin) was observed and the lubricity was investigated. The corrosion resistance was investigated as follows. The wire rod for drawing (film-formed) was left in a constant temperature and humidity chamber at a temperature of 40 ° C. and a humidity of 90% for 2 weeks, and then the area ratio of rust generated on the surface of the wire was visually measured.

  The results of the investigation are shown in Table 2. No.15 (Comparative example) Soap / phosphate film forming material has a large wire drawing load during wire drawing at φ3.6, and the surface of the wire after wire drawing due to seizure. Is not good and has poor lubricity. Nos. 1 to 13 (Examples of the present invention) are smaller in wire drawing load at the time of wire drawing than the soap / phosphate film forming material of No. 15 (Comparative Example). The surface skin of the wire after processing is also good, it is excellent in lubricity, the rust area ratio is small, and the corrosion resistance is also excellent. In addition, No. 1 to 13 could be drawn up to φ2.2, while No. 15 was seized at φ3.6. No.14 (comparative example) with no oxidizer (peroxide) added is No.15 (comparative example) soap / phosphate film forming material or No.1-13 (examples of the present invention) Compared with the case where an oxidizing agent (peroxide) is added, the wire drawing load during wire drawing is large and inferior in lubricity, and the rust area ratio is large and the corrosion resistance is also inferior.

  From the above, it was confirmed that lubricity and corrosion resistance can be improved by adding an oxidizing agent (peroxide). That is, the above is the metal material for plastic working obtained by the method for producing a metal material for plastic working according to the first to third inventions of the present invention, and the metal material for plastic working according to the fourth invention of the present invention is soap. -It is proved that the lubricant and corrosion resistance are equal to or better than those with a phosphate film.

[Example B]
A hot rolled wire rod (wire diameter: 10 mm) made of steel type SCM435 is heat treated (spheroidizing annealing) at 760 ° C., the wire rod after this heat treatment is pickled and descaled, then washed with water, and then surface treated liquid (aqueous solution) ) To obtain a wire rod for drawing (diameter φ = 10 mm). The composition of the surface treatment liquid, the immersion temperature (temperature of the surface treatment liquid), and the immersion time during this immersion treatment are shown in Table 3 (No. 1a to 7a). In addition, it was left to dry in the air after the immersion treatment. The coating amount is about 8 g / m ² .

In addition, the wire after heat treatment, pickling, and water washing similar to the above is subjected to phosphate treatment / soap treatment (phosphate treatment, then soap treatment) to form a soap / phosphate film. To obtain a wire rod for drawing (diameter φ = 10.3 mm) (No. 8a). This phosphate treatment / soap treatment was performed as follows. The washed wire is immersed in 15% hydrochloric acid at 50 ° C for 10 minutes and then washed with water. Next, the washed wire is adjusted to an aqueous solution having a concentration of 90 g / L using a zinc phosphate chemical conversion treatment agent [Palbond 181X (manufactured by Nippon Parkerizing Co., Ltd.)]. The water-washed wire is immersed for 10 minutes and then subjected to chemical conversion treatment (phosphate treatment) under the condition of washing with water. Next, the wire after the chemical conversion treatment is adjusted to an aqueous solution having a concentration of 70 g / L using a soap lubricant [Palube 235 (manufactured by Nippon Parkerizing Co., Ltd.)], and the aqueous solution is brought to 80 ° C. The soap is treated under the condition that the treated wire is immersed for 5 minutes. The amount of the soap / phosphate coating (the total amount of the phosphate coating and the soap layer) is about 8 g / m ² .

  The composition of the film thus formed was confirmed. This confirmation was performed in the same manner as in Example A. Further, the thickness of the first layer (Fe—Ca—O layer, that is, a reaction layer made of Fe, Ca, and O) was measured. This thickness was measured by Auger spectroscopy under the following conditions. In the obtained profile, the thickness from the depth at which the Fe content was 5 (atmic%) or more to the depth at which Ca was 5 (atmic%) or less was defined as the thickness of the first layer.

・ Device ---- PHI650 scanning Auger electron spectrometer manufactured by Parkin Elmer ・ Primary electron energy, current ---- 10 keV, 300 nA
・ The incident angle ---- 30 degrees to the sample normal ・ The beam diameter ---- <5μmφ
・ Analysis area ---- Same as above (point analysis)
・ Ion sputtering energy, current ---- 3 keV, 25 mA
・ The incident angle ---- About 58 degrees to the sample normal ・ The sputtering speed ---- About 31 nm / min

  About the said wire for wire drawing (film-formed thing) and the wire after drawing this wire, lubricity and rust prevention property (corrosion resistance) were investigated. The lubricity was investigated as follows. Without using an auxiliary lubricant, the above wire rod (diameter φ = 10mm) can be used for φ9.5, φ8.3, φ7.45, φ6.3, φ5.6, φ4.9, φ4.2, φ3. 6 The wire drawing was performed step by step in order, the wire drawing load at this time was measured, and the surface condition (surface skin) of the wire after the wire drawing was observed to investigate the lubricity. The corrosion resistance was investigated as follows. Rust generated on the surface of the wire after the wire for wire drawing (film formed) was left in a constant temperature and humidity tester (SH-221 made by Tabai Espec) at a temperature of 40 ° C and a humidity of 90% for 2 weeks. The area ratio was measured visually.

  The results of the above survey are shown in Table 4. No.8a (Comparative example) Soap / phosphate film forming material has a large wire drawing load during wire drawing at φ3.6, and the surface of the wire after wire drawing due to seizure. Is not good and has poor lubricity. No. 1a to 6a (Examples of the present invention) are smaller in wire drawing load during wire drawing than the soap / phosphate film forming material of No. 8a (Comparative Example). The surface skin of the wire after processing is also good, it is excellent in lubricity, the rust area ratio is small, and the corrosion resistance is also excellent. No.7a (comparative example) with no oxidizer (peroxide) added is soap / phosphate film forming material of No.8a (comparative example) or No.1a-6a (examples of the present invention) Compared with the case where an oxidizing agent (peroxide) is added, the wire drawing load during wire drawing is large and inferior in lubricity, and the rust area ratio is large and the corrosion resistance is also inferior.

  As can be seen from Table 3, in the case of No. 8a (comparative example) soap / phosphate film forming material, no Fe—Ca—O layer (reaction layer comprising Fe, Ca, O) is formed. . In the case of No. 7a (comparative example), the surface treatment liquid does not contain an oxidizing agent (peroxide) and an Fe—Ca—O layer is formed, but its thickness is as thin as 2 μm. In the case of No. 1a to 6a (Example of the present invention), the surface treatment liquid contains calcium hydroxide and an oxidizing agent (peroxide), and is thick (thickness: 3 to 8 μm) Fe—Ca—O A layer is formed.

  From the above, when a steel material is immersed in an aqueous solution containing borate, calcium hydroxide and an oxidizing agent (peroxide) and then dried, a Fe—Ca—O layer is formed as a first layer on the surface of the steel material. A film made of borate, calcium hydroxide and peroxide is formed as the second layer, and the thickness of this Fe—Ca—O layer (first layer) is as thick as 3 μm or more, thereby improving lubricity and corrosion resistance. It was confirmed that the lubricity can be improved. That is, the above is the metal material for plastic working obtained by the method for producing the metal material for plastic working according to the ninth invention of the present invention, and the metal material for plastic working according to the seventh to eighth inventions of the present invention is soap. -It is proved that the lubricant and corrosion resistance are equal to or better than those with a phosphate film.

  According to the method for producing a metal material for plastic working according to the present invention, during the heat treatment as in the case of the metal material for plastic working formed with a soap / phosphate film (film comprising a phosphate film and a soap layer). In the present invention, there can be obtained a metal material for plastic working that is superior in lubricity and corrosion resistance to the metal material for plastic working formed with a phosphate film, or that is equivalent to or better than the metal material for plastic working formed with a phosphate film. Such a method for producing a metal material for plastic working can be suitably used as a method for producing a metal material for plastic working and is useful. According to the metal material for plastic working according to the present invention, there is no generation of immersion phosphorus during heat treatment, and the plastic working material is superior in corrosion resistance to or more than the metal material for plastic working formed with a soap / phosphate film. Since [the one after plastic working (for example, one having a bolt shape)] can be obtained, the metal material for plastic working according to the present invention is useful as a metal material for plastic working.

Claims (9)

  A metal material for plastic working is immersed in an aqueous solution containing at least one of silicates and borates or calcium hydroxide and a peroxide, and then dried to form a film on the surface of the metal material. A method for producing a metal material for plastic working, characterized in that:   2. The metal material for plastic working according to claim 1, wherein the concentration ratio of one or more of silicate and borate in the aqueous solution or calcium hydroxide and peroxide is 4: 1 to 200: 1. Method. The method for producing a metal material for plastic working according to claim 1 or 2, wherein an adhesion amount of a film formed on the surface of the metal material is 2 g / m ² or more.   The metal material for plastic processing manufactured by the manufacturing method of the metal material for plastic processing in any one of Claims 1-3.   A surface treatment agent for a metal material for plastic working, comprising an aqueous solution containing at least one of silicates and borates or calcium hydroxide and a peroxide.   The surface of the metal material for plastic working according to claim 5, wherein the concentration ratio of at least one of silicate and borate in the aqueous solution or calcium hydroxide and peroxide is 4: 1 to 200: 1. Processing agent.   A metal for plastic working characterized by having a first layer made of iron, calcium and oxygen on the surface of a steel material and having a coating made of borate, calcium hydroxide and peroxide as a second layer covering the first layer. material.   The metal material for plastic working according to claim 7, wherein the thickness of the first layer is 3 to 10 µm. A metal material for plastic working, characterized in that a metal material for plastic working is immersed in an aqueous solution containing borate, calcium hydroxide and peroxide and then dried to form a film on the surface of the metal material. Manufacturing method.