WO2015146466A1 - Tige de fil d'acier ayant un film de revêtement qui a d'excellentes résistance à la corrosion et aptitude au façonnage et son procédé de production - Google Patents

Tige de fil d'acier ayant un film de revêtement qui a d'excellentes résistance à la corrosion et aptitude au façonnage et son procédé de production Download PDF

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Publication number
WO2015146466A1
WO2015146466A1 PCT/JP2015/055679 JP2015055679W WO2015146466A1 WO 2015146466 A1 WO2015146466 A1 WO 2015146466A1 JP 2015055679 W JP2015055679 W JP 2015055679W WO 2015146466 A1 WO2015146466 A1 WO 2015146466A1
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Prior art keywords
film
steel wire
water
tungsten
silicon
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PCT/JP2015/055679
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English (en)
Japanese (ja)
Inventor
弘高 伊藤
柳澤　佳寿美
敬祐 小澤
慶太 椎橋
小見山　忍
豪 畠山
Original Assignee
株式会社神戸製鋼所
日本パーカライジング株式会社
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Application filed by 株式会社神戸製鋼所, 日本パーカライジング株式会社 filed Critical 株式会社神戸製鋼所
Priority to KR1020167026474A priority Critical patent/KR101811165B1/ko
Priority to CN201580015991.3A priority patent/CN106133196B/zh
Priority to MX2016012581A priority patent/MX2016012581A/es
Priority to US15/129,231 priority patent/US20180187119A1/en
Publication of WO2015146466A1 publication Critical patent/WO2015146466A1/fr

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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/023—Multi-layer lubricant coatings
    • C10N2050/025—Multi-layer lubricant coatings in the form of films or sheets

Definitions

  • the present invention relates to a steel wire having a film containing no phosphorus on its surface and a method for producing the same.
  • a technique of previously coating a metal material surface with a solid film such as an inorganic film is commonly used.
  • a composite film composed of a zinc phosphate film and a soap layer (hereinafter sometimes referred to as a chemical conversion film) has high processability and corrosion resistance and is widely used.
  • Patent Document 1 discloses a composition in which (A) a water-soluble inorganic salt and (B) wax are dissolved or dispersed in water, and the solid content weight ratio (B) / (A) is in the range of 0.3 to 1.5.
  • An aqueous lubricating film treating agent for plastic working of metal materials and a method for forming the film are disclosed.
  • Patent Document 2 discloses an aqueous lubricant film treatment agent containing an alkali metal borate (A), wherein the alkali metal borate (A) contains lithium borate, The molar ratio of lithium to alkali metal is 0.1 to 1.0, and the molar ratio (B / M) of boric acid B to alkali metal M of the alkali metal borate (A) is 1.5.
  • An aqueous lubricating film treating agent for plastic working of metal materials and a method for forming the film are disclosed. This technique can form a film having not only workability but also high corrosion resistance by suppressing the crystallization of the film that occurs when the film absorbs moisture.
  • Patent Document 3 contains an A component: an inorganic solid lubricant, a B component: a wax, and a C component: a water-soluble inorganic metal salt, and a solid content mass ratio between the A component and the B component (A component / B component). ) Is 0.1 to 5, and the solid content mass ratio of the C component to the total amount of the A component, the B component, and the C component (C component / (A component + B component + C component)) is 1 to 30%
  • a water-soluble lubricant for non-phosphorous plastic working is disclosed. This technique is a lubricant that does not contain phosphorus, and is said to be able to realize corrosion resistance equivalent to that of a chemical conversion coating.
  • Patent Document 4 contains a water-soluble inorganic salt (A), one or more lubricants (B) selected from molybdenum disulfide and graphite, and a wax (C), and these are dissolved in water or Aqueous lubrication in which (B) / (A) is 1.0 to 5.0 in terms of solids weight ratio and (C) / (A) is in the range of 0.1 to 1.0 in terms of solids weight ratio A film treatment agent and a method for forming the film are disclosed.
  • high workability equivalent to that of a chemical conversion coating can be realized by blending molybdenum disulfide or graphite with a conventional water-based lubricant coating.
  • Patent Document 5 discloses silicate (A), polycarboxylate (B), water-compatible polymer and / or water-compatible organic lamellar structure (C), molybdate and / or tungstate. (D) and the film formation agent whose mass ratio of each said component is a predetermined
  • a water-soluble inorganic salt is an essential component of a solid film of a water-based lubricating film treatment agent.
  • a lubricating film composed of a water-soluble inorganic salt has a sufficient film strength, and as described above, it is difficult to cause the lubricating film to break by intervening at the interface between the die and the workpiece even under high surface pressure. This is because direct contact can be avoided. Therefore, in the case of a water-based lubricating film treatment agent, a good lubricating state can be maintained during plastic processing by combining a solid film made of a water-soluble inorganic salt or a water-soluble resin with an appropriate lubricant capable of reducing the friction coefficient.
  • the film formation mechanism of the water-based lubricating film composed of water-soluble components will be described.
  • the water-soluble inorganic salt of the water-soluble component is in a state of being dissolved in water in the lubricant treatment liquid.
  • the solvent water evaporates to form a lubricating film.
  • the water-soluble inorganic salt is deposited as a solid on the surface of the metal material to form a solid film.
  • the solid coating formed in this way has a coating strength that can withstand plastic processing, and exhibits good lubricity during plastic processing by incorporating an appropriate lubricant that reduces the friction coefficient.
  • Patent Documents 1 to 5 are significantly inferior in long-term rust prevention for 4 months or more as compared with the chemical conversion coating described above, and cannot be increased to a practical level. This is because the main component of the film is a water-soluble component, so that moisture in the atmosphere can be easily absorbed or permeated, and the steel material can easily come into contact with moisture.
  • Patent Document 2 although corrosion resistance is improved by suppressing crystallization of the film due to moisture absorption, moisture absorption itself is not suppressed, and sufficient corrosion resistance is not obtained.
  • the water-based lubricating film described in Patent Document 3 exhibited a corrosion resistance equivalent to or higher than that of the chemical conversion coating film in a corrosion resistance test in a laboratory in which rusting was accelerated using a thermo-hygrostat.
  • the actual environment in which the lubricant film is used is usually in a state where dust, dust, and pickling chemical mist can adhere, and in such a harsh environment, the corrosion resistance is better than the chemical conversion film.
  • the actual situation is inferior.
  • the non-uniformity of the film is mentioned as a point where the water-based lubricating film is inferior to the chemical conversion film.
  • the coating treatment liquid does not reach the portion, and the coating becomes thin. Since the thickness of the film has a significant effect on the corrosion resistance, for example, a phenomenon is observed in which rust starts to be generated from the coil binding site.
  • the decrease in corrosion resistance due to the non-uniformity of the film is a big problem for the conventional water-based lubricating film.
  • Water-soluble silicate has a property that it hardly permeates moisture in water-soluble inorganic salt and has very high adhesion to the material. Because of this property, it is a material that can exhibit relatively high corrosion resistance, although not as much as the chemical conversion coating. This is because the water-soluble silicate is crosslinked and forms a network structure in the process of forming a film in which water as a solvent of the lubricant volatilizes. However, because of this network structure, the water-soluble silicate film is too brittle as a lubricating film. For this reason, when a base material is processed, a film
  • the adhesiveness is too high, film removal failure may occur, and various problems may be caused in subsequent processes.
  • film removal failure may occur, and various problems may be caused in subsequent processes.
  • plating is performed in a subsequent process, not only does the film component enter and contaminates the plating solution, but also causes defective plating in the portion where the film component remains.
  • water-soluble tungstate does not easily absorb moisture from the outside air when a film is formed. This is because when the water-soluble tungstate forms a film, it forms particulate crystals. Furthermore, water-soluble tungstate has the property of forming a passive film having a self-repairing function on the metal surface, and it can be expected to form a highly corrosion-resistant film by using it as a film component. Moreover, since water solubility itself is high, it can be easily removed with an aqueous solution. However, since the water-soluble tungstate is crystalline, it has poor adhesion to the material and cannot form a uniform film, so that the expected corrosion resistance and workability cannot be obtained. For example, the adhesion and uniformity of the film can be improved by adding a synthetic resin component to the lubricant, but the corrosion resistance is still inferior to that of the chemical conversion film.
  • the water-based lubricating film treatment agents containing water-soluble inorganic salts described in Patent Documents 1 to 3 have in common poor processability compared to the chemical conversion film. This is particularly noticeable in severe processing where the surface area expansion ratio is several tens of times (hereinafter sometimes referred to as “strong processing”), such as insufficient deformation of the material, reduction in mold life, and seizure. Occur.
  • the water-based lubricating film treating agent described in Patent Document 4 contains molybdenum disulfide and graphite, so that it is possible to obtain a workability equivalent to or higher than that of the chemical conversion film even during strong working.
  • molybdenum disulfide and graphite are liable to settle, and over time, they may harden at the bottom of the treatment tank and become difficult to redisperse, making stable operation difficult.
  • these two components are factors that greatly reduce the corrosion resistance, and the corrosion resistance is inferior to that of the lubricating film of Patent Documents 1 to 3 as well as the chemical conversion coating.
  • Patent Document 5 a coating material containing silicate (A) as a main component and containing too much corrosion-resistant agent (D) or the like has seizure when the extrusion load is high. Since it is inferior, stable work becomes difficult, and long-term rust prevention is not sufficient.
  • the water-based lubricating film could not form a film having both high corrosion resistance over a long period of about 4 months or more and workability at the time of strong processing, comparable to the chemical conversion film even in a practical environment.
  • corrosion resistance since the film tends to be non-uniform, rusting from the thin film portion becomes a problem.
  • the silicate is contained in the water-based lubricating film treating agent, defective film removal becomes a problem.
  • the present invention provides a steel wire having a lubricating film capable of achieving both workability such as wire drawing, spikeability, ball ironing, and corrosion resistance such as long-term rust prevention, and a method for producing the same. It was raised as an issue.
  • the present inventors have found that if a later-described upper layer film and lower layer film are formed on a steel wire as a lubricating film, both workability and corrosion resistance can be achieved. It is. Specifically, a film made of zirconium oxide and / or hydroxide is formed as the lower layer film, and a specific ratio of silicate and tungstate, that is, a mass ratio of tungsten / silicon is set as a predetermined ratio. It was found that by forming a composite upper film, high corrosion resistance and workability that could never be achieved with these components alone were obtained.
  • the present invention is configured as follows to solve the above-mentioned problems.
  • the steel wire rod of the present invention is a steel wire rod having a coating containing no phosphorus, and the coating is made of zirconium oxide and / or hydroxide in order from the steel wire side, and has a film thickness of 1.0 to It is summarized in that it includes a lower layer film having a thickness of 200 nm and an upper layer film including silicon and tungsten and having a mass ratio of tungsten / silicon of 1.3 to 18.
  • the silicon is derived from a water-soluble silicate and the tungsten is derived from a water-soluble tungstate.
  • the silicon is derived from at least one selected from lithium silicate, sodium silicate, and potassium silicate, and the tungsten is at least selected from lithium tungstate, sodium tungstate, potassium tungstate, and ammonium tungstate. It is preferably derived from one or more.
  • the upper layer film contains a resin and the mass ratio of resin / (silicon + tungsten) is 0.01 to 3.2.
  • the resin is preferably at least one selected from vinyl resins, acrylic resins, epoxy resins, urethane resins, phenol resins, cellulose derivatives, polymaleic acid, and polyester resins.
  • the upper layer film contains a lubricant, and the mass ratio of the lubricant / (silicon + tungsten) is 0.01 to 3.2.
  • the lubricant is preferably at least one selected from wax, polytetrafluoroethylene, fatty acid soap, fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, and melamine cyanurate.
  • the film mass per unit area of the upper film is preferably 1.0 to 20 g / m 2 .
  • the method for producing a steel wire according to the present invention is that the lower layer film is formed by bringing a water-based chemical conversion solution in which a water-soluble zirconium compound is dissolved into contact with the surface of a steel wire in the range of pH 2.5 to 5.0.
  • the lubricating film including the upper layer film and the lower layer film is configured as described above, it has excellent workability such as wire drawability, spike property, ball ironing property, and corrosion resistance such as long-term rust prevention property. Steel wire rod is obtained.
  • their performance is superior to that of a conventional water-based lubricant film in that all of the performance is equal to or higher than that of a steel wire having a chemical conversion coating.
  • the conventional water-based lubricating film does not have in that high corrosion resistance can be obtained even when the water-based lubricating film becomes thin due to external factors such as overlapping or binding of materials.
  • the present invention relates to a steel wire having a film containing no phosphorus, wherein the film is composed of an oxide and / or hydroxide of zirconium in order from the steel wire side, and has a thickness of 1 to 200 nm.
  • a steel wire material comprising an upper film containing silicon and tungsten and having a tungsten / silicon mass ratio in the range of 1.3-18.
  • the steel used for the steel wire includes carbon steel, alloy steel, special steel and the like.
  • carbon steel having a carbon content of 0.2% by mass or less (excluding 0% by mass) to carbon steel having a carbon content of more than 0.2% by mass and not more than 1.5% by mass, and depending on the use of carbon steel Alloy steel or special steel containing at least one selected from silicon, manganese, phosphorus, sulfur, nickel, chromium, copper, aluminum, molybdenum, vanadium, cobalt, titanium, zircon and the like.
  • the steel wire generally refers to steel processed into a wire by hot working.
  • the steel wire material of the present invention includes a steel wire. With steel wire, steel wire was further processed, such as steel wire drawn to a specified size (wire diameter, roundness, etc.), steel wire or drawn steel wire plated, etc. Say things.
  • the steel wire of the present invention comprises at least two layers of a lubricating film, that is, a lower layer film and an upper layer film in order from the surface of the steel wire.
  • a lubricating film that is, a lower layer film and an upper layer film in order from the surface of the steel wire.
  • Each of the upper layer film and the lower layer film may be a single layer or two or more layers. Further, if necessary, further layers may be formed on the upper film, between the upper film and the lower film, and between the steel wire and the lower film.
  • None of the coatings contains phosphorus, and the composition used for forming the coating does not contain a component containing phosphorus. However, in the present invention, it is not excluded that a component containing phosphorus is inevitably mixed in the coating on the surface of the steel wire in the operation process or the like.
  • the upper layer film should contain silicon and tungsten, and the film should have a tungsten / silicon mass ratio in the range of 1.3-18. By containing in this range, it is possible to form a film having high corrosion resistance, workability and sufficient adhesion, which could not be achieved with silicate or tungstate alone or other water-soluble inorganic salts described later.
  • the tungstate is taken into the network structure formed by the silicate.
  • the disadvantage of the tungstate is largely due to the formation of a crystalline film, but the tungstate can be present uniformly and finely by being incorporated into the silicate network structure. become able to.
  • the properties of the silicate that hardly permeate moisture and the passive film having the self-repairing function of the tungstate are compatible, and the corrosion resistance is remarkably improved.
  • the cause of poor processability and film removal of the silicate is due to the formation of a strong continuous film by polymerizing the silicate. Is moderately hindered from forming a strong network structure and can improve processability and film removal properties.
  • the mass ratio of tungsten / silicon is 1.3 or more, preferably 1.8 or more, more preferably 2.0 or more.
  • the mass ratio is 18 or less, preferably 10 or less, more preferably 5.4 or less.
  • the mass ratio of tungsten / silicon is preferably based on the ratio of the tungsten element derived from the water-soluble tungstate and the silicon element derived from the water-soluble silicate in the film. It can be calculated as follows.
  • the lower layer film is made of zirconium oxide and / or hydroxide, preferably zirconium oxide.
  • the lower layer film may be referred to as a zirconium film.
  • the film thickness of the lower layer film is 1.0 nm or more, preferably 5 nm or more, more preferably 20 nm or more.
  • the film thickness is 200 nm or less, preferably 150 nm or less, more preferably 130 nm or less.
  • the film thickness is larger than 200 nm, there is no influence on the corrosion resistance, but the adhesion failure of the film occurs and the workability is lowered.
  • the corrosion resistance can be improved by forming the zirconium film.
  • a zirconium film as a lower layer film changes the network structure of the silicate by the zirconium film and strengthens the bond.
  • the zirconium film is much thinner than the upper film, it is easy to form a uniform film even in a place where a normal water-based lubricating film tends to be a thin film, which leads to improvement in corrosion resistance.
  • the network structure of the upper layer film and the bond strengthened portion of the zirconium film are important for improving the corrosion resistance, so that it is hardly affected by the film thickness of the entire upper layer film.
  • the corrosion resistance can be sufficiently exhibited even at a location where the water-based lubricating film as described above tends to be a thin film.
  • a single zirconium film causes defects in the film and becomes a failure because it becomes a starting point of corrosion and processing performance cannot be obtained.
  • the silicon is derived from a water-soluble silicate and the tungsten is derived from a water-soluble tungstate.
  • water-soluble silicate examples include sodium silicate, potassium silicate, lithium silicate, and ammonium silicate. These may be used alone or in combination of two or more.
  • water-soluble tungstate examples include sodium tungstate, potassium tungstate, lithium tungstate, and ammonium tungstate. These may be used alone or in combination of two or more.
  • zirconium supply source in the coating agent for forming a zirconium film according to the present invention examples include zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, ammonium zirconium nitrate, zirconium acetate, zirconium lactate, and chloride.
  • zirconium, fluorozirconic acid, fluorozirconium complex salt and the like can be mentioned. These may be used alone or in combination of two or more.
  • the resin is blended in the upper layer film for the purpose of binder action, improvement of adhesion between the substrate and the film, imparting leveling property by thickening action, and stabilization of the dispersed component.
  • resins having such functions and properties include vinyl resins, acrylic resins, epoxy resins, urethane resins, phenol resins, cellulose derivatives, polymaleic acid, and polyester resins. These may be used alone or in combination of two or more.
  • the upper layer film contains a resin
  • the mass ratio of resin / (silicon + tungsten) is preferably 0.01 or more, more preferably 0.1 or more.
  • the mass ratio is preferably 3.2 or less, more preferably 2.1 or less. If it is less than 0.01, the above-mentioned action is not sufficiently exerted, and if it exceeds 3.2, the amounts of silicon and tungsten are relatively reduced, and the high corrosion resistance and workability characteristic of the present invention are exhibited. become unable.
  • the lubricant itself is slippery and has a function of reducing the frictional force. In general, when the frictional force increases during plastic processing, processing energy increases, heat generation, seizure, etc. occur.However, when a lubricant is included in the upper layer coating of the steel wire of the present invention, it exists in a solid form in the lubricating coating. An increase in frictional force is suppressed.
  • the lubricant having such functions and properties include wax, polytetrafluoroethylene, fatty acid soap, fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, and melamine cyanurate. These may be used alone or in combination of two or more.
  • the wax include polyethylene wax, paraffin wax, microcrystalline wax, polypropylene wax, and carnauba wax.
  • Specific examples of the fatty acid soap include sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, sodium stearate, and potassium stearate.
  • Specific examples of the fatty acid metal soap include calcium stearate, zinc stearate, barium stearate, magnesium stearate, and lithium stearate.
  • the fatty acid amide is, for example, an amide compound having two fatty acids.
  • ethylene bislauric acid amide ethylene bis stearic acid amide, ethylene bisbehenic acid amide, N, N′-distearyl adipic acid amide, ethylene bis oleic acid.
  • Amide ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide.
  • the upper layer film contains a lubricant
  • the mass ratio of lubricant / (silicon + tungsten) is preferably 0.01 or more, more preferably 0.1 or more, and the mass ratio is 3. It is preferably 2 or less, more preferably 2.1 or less.
  • the mass ratio of the lubricant / (silicon + tungsten) is less than 0.01, the above performance cannot be exhibited because the lubricant is too small.
  • it exceeds 3.2 the amounts of silicon and tungsten are relatively small, and the high corrosion resistance and workability that are the characteristics of the present invention cannot be expressed.
  • the upper layer film of the steel wire rod of the present invention is intended to impart leveling and thixotropy to ensure a uniform coating state when a lubricant treatment liquid is applied to a substrate.
  • a viscosity modifier can be blended. Specific examples of such viscosity modifiers include smectite clay minerals such as montmorillonite, saconite, beidellite, hectorite, nontronite, saponite, iron saponite and stevensite, and inorganic thickening such as finely divided silica, bentonite and kaolin. Agents.
  • the upper film may contain an inorganic salt such as a sulfate or borate, or a water-soluble salt such as an organic salt in order to improve adhesion and workability.
  • an inorganic salt such as a sulfate or borate
  • a water-soluble salt such as an organic salt in order to improve adhesion and workability.
  • the sulfate include sodium sulfate and potassium sulfate.
  • the borate include sodium metaborate, potassium metaborate, and ammonium metaborate.
  • Organic salts include formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid, ascorbic acid, tartaric acid, citric acid, malic acid, malonic acid, maleic acid, phthalic acid, etc., and alkali metals, alkaline earth metals, etc. Of the salt.
  • the film of the steel wire rod of the present invention can provide high corrosion resistance before and after processing, but may further contain other water-soluble rust preventives and inhibitors for the purpose of further improving the corrosion resistance.
  • specific examples include various organic acids such as oleic acid, dimer acid, tartaric acid and citric acid, various chelating agents such as EDTA, NTA, HEDTA and DTPA, mixed components of alkanolamine such as triethanolamine, and pt-butylbenzoic acid.
  • Known amines such as carboxylic acid amine salts, dibasic acid amine salts, alkenyl succinic acid and water-soluble salts thereof, and aminotetrazole and water-soluble salts thereof can be used. These may be used alone or in combination of two or more.
  • the upper film treatment agent used in the present invention contains the water-soluble silicate and the water-soluble tungstate as essential components, and contains the resin, the lubricant, and the water-soluble salt as necessary.
  • the water-soluble silicate is preferably more than 5% by mass in 100% by mass of the upper layer film treating agent, more preferably 10% by mass or more, still more preferably 15% by mass or more, and 58% by mass or less. It is preferable that it is preferably 52% by mass or less, and more preferably 45% by mass or less.
  • the water-soluble tungstate is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and 91% by mass or less, in 100% by mass of the upper film treatment agent.
  • the content is 85% by mass or less, more preferably 80% by mass or less.
  • the amount of the water-soluble silicate is 5% by mass or less and the amount of the water-soluble tungstate is more than 91% by mass, sufficient long-term rust preventive property cannot be obtained, and wire drawing property and ball ironing property are obtained.
  • the film is inferior. This is due to the fact that the amount of water-soluble silicate is relatively reduced, so that moisture easily permeates, and tungsten crystals are precipitated, resulting in a decrease in the adhesion and uniformity of the film.
  • the amount of the water-soluble silicate is more than 58% by mass and the amount of the water-soluble tungstate is less than 10% by mass, a film with insufficient corrosion resistance and workability cannot be obtained. This is because a relatively thin passive film is not formed due to a relatively small amount of tungsten, and a strong network structure is formed due to a relatively large amount of water-soluble silicate.
  • the lower layer coating of the steel wire of the present invention can be used as a base lubricating coating for dry lubricants. By using it as an undercoat of a dry lubricant, the lubricity, seizure resistance, and corrosion resistance can be raised.
  • the type of dry lubricant is not particularly limited, and general lubricating powders and wire drawing powders mainly composed of higher fatty acid soap, borax, lime, molybdenum disulfide, etc. can be used.
  • the liquid medium (solvent, dispersion medium) in the upper film treatment agent and the zirconium film treatment agent is water.
  • the upper layer film treatment agent may be blended with alcohol having a boiling point lower than that of water in order to shorten the drying time of the lubricant in the drying step.
  • the upper layer film treatment agent may contain a water-soluble strong alkali component in order to increase the stability of the solution.
  • a water-soluble strong alkali component include lithium hydroxide, sodium hydroxide, and potassium hydroxide. These may be used alone or in combination of two or more. The blending amount of these is preferably 0.01 to 10% by mass relative to the total solid mass.
  • the method of the present invention includes a steel wire rod cleaning step, a manufacturing step of an upper layer coating agent and a lower layer coating agent (aqueous chemical conversion treatment liquid) as a water-based lubricating coating agent, and a drying step.
  • a manufacturing step of an upper layer coating agent and a lower layer coating agent aqueous chemical conversion treatment liquid as a water-based lubricating coating agent
  • a drying step a drying step.
  • ⁇ Cleaning process (pretreatment process)> Before forming the film on the steel wire, it is preferable to perform at least one cleaning treatment selected from the group consisting of shot blasting, sand blasting, wet blasting, peeling, alkali degreasing and acid cleaning.
  • the purpose of cleaning is to remove oxide scales and various types of dirt (oil, etc.) grown by annealing or the like.
  • the lower layer film has a pH in the range of 2.5 to 5.0, and is formed by bringing an aqueous chemical conversion treatment solution in which a water-soluble zirconium compound is dissolved into contact with the surface of the steel wire.
  • the aqueous chemical conversion treatment liquid only needs to contain the zirconium supply source.
  • the pH is preferably 2.8 to 4.8, more preferably 3.1 to 4.6, and still more preferably 3.4 to 4.4. If the pH is less than 2.5, the etching becomes excessive, and not only the deposition efficiency of the film is lowered, but also the uniform formation of the film may be hindered.
  • the aqueous chemical conversion treatment liquid may be a commercially available zirconium chemical conversion treatment agent, and the zirconium concentration (by mass) is preferably 10 ppm or more, more preferably 30 ppm or more, preferably 500 ppm or less, more preferably 300 ppm. It is as follows.
  • the contact method for forming the zirconium film is not particularly limited, and examples thereof include spray treatment, immersion treatment, and pouring treatment.
  • the temperature of the aqueous chemical conversion solution at the time of contact that is, the treatment temperature is preferably 20 to 60 ° C., more preferably 30 to 50 ° C.
  • the contact time depends on the material and structure of the steel wire, the concentration of the chemical conversion treatment liquid, and the treatment temperature, but is preferably about 2 to 600 seconds, and can be appropriately adjusted according to the coating amount.
  • a water washing step is provided after the chemical conversion treatment so that the aqueous chemical conversion treatment liquid adhering to the steel material is not brought into the upper layer film treatment liquid.
  • an upper layer film is formed on the zirconium film obtained as described above.
  • the step of applying the upper layer coating to the steel wire is not particularly limited, but application such as dipping, flow coating, and spraying can be used.
  • the application is not limited as long as the surface is sufficiently covered with the upper film treatment agent as a water-based lubricating film treatment agent.
  • the steel wire may be heated to 60 to 80 ° C. and brought into contact with the water-based lubricating film treating agent. Further, an aqueous lubricating film treating agent heated to 40 to 70 ° C. may be contacted. By these, drying property improves significantly and drying may be attained at normal temperature, and the loss of heat energy can also be reduced.
  • Drying may be performed at room temperature, but may be performed at 60 to 150 ° C. for 1 to 30 minutes.
  • the film mass of the upper film formed on the surface of the steel wire is appropriately controlled depending on the degree of subsequent processing, but the film mass is preferably 1.0 g / m 2 or more, more preferably 2. It is 0 g / m 2 or more, preferably 20 g / m 2 or less, more preferably 15 g / m 2 or less.
  • the film mass is small, the lubricity is insufficient.
  • the coating mass exceeds 20 g / m 2 , there is no problem in lubricity, but clogging of the dies and the like are not preferable.
  • the film mass can be calculated from the mass difference and surface area of the steel wire before and after the treatment.
  • solid content mass (concentration) of a water-system lubricating film processing agent is adjusted suitably.
  • a high-concentration lubricant is often diluted with water and used in the treatment liquid.
  • the water to be diluted is not particularly limited. For example, pure water, deionized water, tap water, ground water, industrial water, and the like can be used.
  • the upper layer film can be removed by dipping in an aqueous alkaline cleaning agent or by spray cleaning.
  • the alkaline detergent is a solution in which common alkaline components such as sodium hydroxide and potassium hydroxide are dissolved in water.
  • the upper layer film dissolves in the cleaning solution, so that the film is easily removed. be able to.
  • it is a film that is easily removed by heat treatment after processing. Therefore, it is possible to prevent contamination and plating defects in the subsequent process due to defective film removal by alkali cleaning.
  • a method for analyzing the zirconium film there is a method of directly observing the film thickness in cross-sectional SEM (Scanning Electron Microscope) observation or cross-sectional TEM (Transmission Electron Microscope) observation.
  • a method of producing a cross section by CP (Cross-section Polisher) processing or FIB (Focused Ion Beam) processing is effective.
  • CP Cross-section Polisher
  • FIB Fluorused Ion Beam
  • XRF fluorescent X-ray analysis
  • the upper layer film is preferably peeled off with an alkaline aqueous solution or the like.
  • the measurement of the film thickness of the lower layer film is performed by randomly selecting three areas for measuring the film thickness on the surface of the steel material after the upper layer film is peeled off, and measuring the film thickness in all the selected areas. And let the average value of the thickness measured in the said 3 places be the film thickness of the base film of steel materials.
  • the film composition can be analyzed by dissolving the film on the steel material in a strong alkaline aqueous solution or the like and measuring the amount of dissolved silicon and tungsten by ICP.
  • the film composition can also be analyzed by a method in which the amount of silicon and tungsten on the surface of the steel wire is directly analyzed by fluorescent X-ray analysis (XRF: X-ray Fluorescence).
  • XRF fluorescent X-ray analysis
  • the film thickness of the zirconium film was measured by performing fluorescent X-ray analysis (XRF) on the test material from which the upper layer coating was peeled off. The measured values are listed in Table 1. Moreover, the thickness of the lower layer film was measured by carrying out cross-sectional SEM analysis, and the film thickness was measured. In the film thickness measurement, the measurement of the film thickness of the lower layer film (that is, the zirconium film) is performed by randomly selecting three areas for measuring the film thickness on the surface of the steel material after peeling off the upper layer film. In all cases, the film thickness was measured. And the average value of the thickness measured in the said 3 places was made into the film thickness of the base film of steel materials.
  • XRF fluorescent X-ray analysis
  • (1-3) Film treatment The film treatment method is shown below.
  • the to-be-processed material is a steel wire rod of ⁇ 3.2 mm
  • the processing was performed in a state of being bundled with a plastic binding band.
  • Evaluation standard A Remarkably superior to phosphate / soap film (rust area less than 5%) ⁇ : superior to phosphate / soap film (rust area 5% or more and less than 15%) ⁇ : Equivalent to phosphate / soap film (rust area 15% or more and less than 25%) ⁇ : Inferior to phosphate / soap film (rust area 25% or more and less than 35%) X: Remarkably inferior to phosphate / soap film (rust area 35% or more)
  • Comparative Example 3 In Comparative Example 3 in which the film thickness of the zirconium film was too thin, the corrosion resistance decreased, and in Comparative Example 4 in which the film thickness of the zirconium film was too thick, the workability tended to decrease.
  • Comparative Examples 5 to 12 the mass ratio of silicon and tungsten was set outside the range of the present invention, but the workability was poor and the corrosion resistance was poor because the remaining amount of the film after wire drawing was small.
  • Comparative Examples 13 to 15 contain components other than water-soluble silicate and water-soluble tungstate as water-soluble inorganic salts. However, since the remaining amount of the film after wire drawing is small, workability is inferior and corrosion resistance is increased. Was also inferior.
  • Comparative Example 16 a water-soluble silicate film was applied as the lower layer film, but the corrosion resistance as high as that of the example could not be obtained.
  • Comparative Example 17 a phosphate film was formed as the lower film.
  • this film is not preferable because it contains phosphorus and has the problem of immersion phosphorus such as bolts as described above.
  • the sample obtained by subjecting the phosphate coating of Comparative Example 18 to the reaction soap treatment has a problem of phosphorus immersion such as bolts as in Comparative Example 17, and the phosphate coating is not preferable.
  • phosphoric acid is contained as a water-soluble salt as in Comparative Examples 12 and 13. Further, even when the materials are bundled with a binding band and the water-based lubricating film becomes thin at the bundled portion, high corrosion resistance can be imparted.
  • Test piece for evaluation S45C spheroidized annealing material 25 mm ⁇ ⁇ 30 mm
  • Evaluation standard A Remarkably superior to phosphate / soap film
  • B Superior to phosphate / soap film
  • ⁇ Equivalent to phosphate / soap film
  • B Inferior to phosphate / soap film
  • X Phosphate / soap Remarkably inferior to film
  • Test piece for evaluation S10C spheroidized annealing material 14 mm ⁇ ⁇ 32 mm Bearing ball: 10mm ⁇ SUJ2 Evaluation criteria It was evaluated how much area burned with respect to the entire area of the ironing surface.
  • ⁇ Remarkably superior to phosphate / soap coating
  • ⁇ Equivalent to phosphate / soap coating
  • ⁇ Inferior to phosphate / soap coating
  • Test piece SPCC-SD 75mm x 35mm x 0.8mm Evaluation standard A: Remarkably superior to phosphate / soap film (rust area less than 5%) ⁇ : superior to phosphate / soap film (rust area 5% or more and less than 15%) ⁇ : Equivalent to phosphate / soap film (rust area 15% or more and less than 25%) ⁇ : Inferior to phosphate / soap film (rust area 25% or more and less than 35%) X: Remarkably inferior to phosphate / soap film (rust area 35% or more)
  • Comparative Example 19 was a film having only a zirconium film, but the workability and corrosion resistance were greatly inferior.
  • the film thickness of the zirconium film is set outside the range of the present invention.
  • the comparative example 20 is a case where the film thickness of a lower layer film
  • membrane is made thin too much, it resulted in inferior corrosion resistance.
  • Comparative Example 21 was a case where the film thickness of the lower layer film was made too thick, but the processability was inferior.
  • Comparative Examples 22 to 29 the mass ratio of silicon and tungsten was set outside the range of the present invention, but the results of ball ironing and corrosion resistance tended to be inferior.
  • Comparative Examples 30 to 33 contain components other than water-soluble silicate and water-soluble tungstate as water-soluble inorganic salts, but there was a tendency that the results of ball ironing and corrosion resistance were inferior.
  • Comparative Example 34 a silicate film was applied as the lower layer film, but the corrosion resistance as high as that of the example could not be obtained.
  • Comparative Example 35 a phosphate film was formed as the lower film.
  • this film is not preferable because it contains phosphorus and has the problem of immersion phosphorus such as bolts as described above. What performed the reaction soap process to the phosphate membrane
  • a steel wire having a film containing no phosphorus, The coating comprises, in order from the steel wire side, an oxide and / or hydroxide of zirconium, and has a lower layer coating having a thickness of 1.0 to 200 nm, silicon and tungsten, and has a mass ratio of tungsten / silicon.
  • a steel wire material comprising an upper film in the range of 1.3 to 18.
  • Aspect 2 The steel wire according to aspect 1, wherein the silicon is derived from a water-soluble silicate and the tungsten is derived from a water-soluble tungstate.
  • Aspect 3 The silicon is derived from at least one selected from lithium silicate, sodium silicate, and potassium silicate, and the tungsten is at least selected from lithium tungstate, sodium tungstate, potassium tungstate, and ammonium tungstate.
  • the steel wire rod according to the aspect 1 or 2 derived from one or more kinds.
  • Aspect 4 The steel wire according to any one of aspects 1 to 3, wherein the upper layer film includes a resin, and a mass ratio of resin / (silicon + tungsten) is 0.01 to 3.2.
  • Aspect 5 The steel wire according to aspect 4, wherein the resin is at least one selected from vinyl resins, acrylic resins, epoxy resins, urethane resins, phenol resins, cellulose derivatives, polymaleic acid, and polyester resins.
  • Aspect 6 The steel wire according to any one of embodiments 1 to 5, wherein the upper layer film contains a lubricant, and the mass ratio of the lubricant / (silicon + tungsten) is 0.01 to 3.2.
  • Aspect 7 The steel wire according to aspect 6, wherein the lubricant is at least one selected from wax, polytetrafluoroethylene, fatty acid soap, fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, and melamine cyanurate. .
  • Aspect 8 The steel wire rod according to any one of embodiments 1 to 7, wherein a film mass per unit area of the upper layer film is 1.0 to 20 g / m 2 .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Lubricants (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : une tige de fil d'acier ayant un film de revêtement lubrifiant, qui permet d'obtenir un bon équilibre entre l'aptitude au façonnage, telle que l'aptitude au tréfilage, des propriétés de formation de pointes et des propriétés de chaudronnage à billes, et la résistance à la corrosion, telle que des propriétés antirouille sur le long terme ; et un procédé pour la production de cette tige de fil d'acier. La tige de fil d'acier comprend un film de revêtement qui ne contient pas de phosphore et est caractérisée en ce que le film de revêtement est composé, l'un après l'autre à partir du côté de la tige de fil d'acier, d'un film de revêtement inférieur qui est constitué d'un oxyde de zirconium et/ou d'un hydroxyde de zirconium et qui a une épaisseur de film de 1 à 200 nm et d'un film de revêtement supérieur qui contient du silicium et du tungstène de sorte que le rapport massique silicium/tungstène est dans la plage de 1,3 à 18. Le procédé pour la production de cette tige de fil d'acier est caractérisé en ce que le film de revêtement inférieur est formé par la mise en contact d'un liquide aqueux de conversion chimique avec la surface de la tige de fil d'acier, ledit liquide de conversion chimique ayant un pH dans la plage de 2,5 à 5,0 et étant obtenu par dissolution d'un composé hydrosoluble du zirconium.
PCT/JP2015/055679 2014-03-28 2015-02-26 Tige de fil d'acier ayant un film de revêtement qui a d'excellentes résistance à la corrosion et aptitude au façonnage et son procédé de production WO2015146466A1 (fr)

Priority Applications (4)

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KR1020167026474A KR101811165B1 (ko) 2014-03-28 2015-02-26 내식성 및 가공성이 우수한 피막을 갖는 강선재 및 그의 제조 방법
CN201580015991.3A CN106133196B (zh) 2014-03-28 2015-02-26 具有优异的耐蚀性和加工性的皮膜的钢线材及其制造方法
MX2016012581A MX2016012581A (es) 2014-03-28 2015-02-26 Barra de alambre de acero que tiene pelicula de recubrimiento que tiene excelente resistencia a la corrosion y capacidad de trabajo, y metodo para producir la misma.
US15/129,231 US20180187119A1 (en) 2014-03-28 2015-02-26 Steel wire rod having coating film that has excellent corrosion resistance and workability, and method for producing same

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JP2014070445A JP6362379B2 (ja) 2014-03-28 2014-03-28 耐食性及び加工性に優れた皮膜を有する鋼線材及びその製造方法
JP2014-070445 2014-03-28

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JP6162853B1 (ja) * 2016-05-11 2017-07-12 株式会社ニッケンビルド 組立式ボックスパレット
CN110355224A (zh) * 2019-06-27 2019-10-22 南京华舜润滑制品有限公司 一种具有自动上料结构的金属线材拉拔润滑粉制备方法
JP7329472B2 (ja) * 2020-03-18 2023-08-18 日本ペイント・サーフケミカルズ株式会社 スケールおよび／またはカーボン除去方法、および金属材の製造方法
JP7428746B2 (ja) 2022-04-19 2024-02-06 日本パーカライジング株式会社 金属線材の潤滑処理方法

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JP2002363593A (ja) * 2001-06-07 2002-12-18 Kobe Steel Ltd 皮膜形成剤及び皮膜
JP2007262488A (ja) * 2006-03-28 2007-10-11 Nippon Steel Corp 金属（水）酸化物被覆めっき線材

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JPS51123231A (en) * 1975-04-22 1976-10-27 Kansai Paint Co Ltd An inorganic composition for use in forming surface coating film
JP5682021B2 (ja) * 2010-05-25 2015-03-11 日本パーカライジング株式会社 難結晶性を有し、耐吸湿性、耐食性及び加工性に優れる金属材料塑性加工用水系潤滑剤及びその潤滑皮膜を形成させた金属材料
ES2928160T3 (es) * 2014-03-28 2022-11-15 Nihon Parkerizing Agente de recubrimiento lubricante acuoso que tiene resistencia a la corrosión y trabajabilidad excelentes, y material metálico

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JP2002363593A (ja) * 2001-06-07 2002-12-18 Kobe Steel Ltd 皮膜形成剤及び皮膜
JP2007262488A (ja) * 2006-03-28 2007-10-11 Nippon Steel Corp 金属（水）酸化物被覆めっき線材

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JP2015190046A (ja) 2015-11-02
CN106133196B (zh) 2019-01-18
KR101811165B1 (ko) 2018-01-25
MX2016012581A (es) 2017-04-27
KR20160125505A (ko) 2016-10-31
US20180187119A1 (en) 2018-07-05
CN106133196A (zh) 2016-11-16

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