KR20130124148A - Lubricant composition for metal material plasticity processing, lubricating film and coated metal material provided therewith, and method for manufacturing coated metal material - Google Patents

Abstract

(A) at least one inorganic salt selected from the group consisting of sulfates, borates, silicates, phosphates, molybdates and tungstates, (B) a lubricating substance having an average particle diameter of 20 μm or less, (C) an average molecular weight of 5000 to 100000 And a water-soluble resin material of (D) and (D) water, wherein the weight ratio of the components (A) :( B) :( C) is 1: 0.01 to 20: 0.01 to 20, wherein the lubricant composition for plastic working It provides a lubricating film, a coated metal material having the same, and a method for producing the same.

Description

A lubricant composition for plastic processing of metal materials, a lubricating film, and a coated metal material having the same, and a method for producing the coated metal material.

The present invention relates to a lubricant composition for plastic processing of metal materials used in various metal materials for processing to be provided for cold or warm processing, a lubricating film formed from the composition and a coating metal material coated with the coating, and a method for producing the coating metal material. It is about.

Conventionally, special metal materials such as stainless steel, titanium, and nickel-based alloys have many excellent properties such as corrosion resistance, heat resistance, and mechanical properties, compared to other conventional metals, and are indispensable for today's technological progress. These special metal materials are widely used in mechanical element products such as screws, bolts, nuts, pins, ropes, bearings or springs, and various mechanical components.

By the way, since the said special metal material is high strength, hard, and lacks toughness, it is considered a hard-working material. For example, when these hard-working metal materials are processed to make the said various products, processing troubles, such as a material crack, a disconnection, or a fracture, are easy to produce. Therefore, in order to suppress these troubles and to prolong the life of machining tools such as dies, rolls, and punches, an optimum lubrication technique is required.

For example, in the case of drawing a wire for fine-hardening the special metal material, or applying the obtained thin wire to header pressing or spring forming, conventionally, the surface of the metal material is plated with Cu, Ni or another metal. And various lubricating coatings of organic and inorganic materials such as resin materials, lime, oxalate or phosphate have been performed. In addition to forming such a coating, an auxiliary lubricant including, for example, an auxiliary lubricant such as metal soap, molybdenum disulfide, graphite, borax, and lime, or various additives added as necessary, immediately before the processing thereof, The lubrication method of the combined type used is also known.

In particular, the lubrication method of the combined type is effective for severe processing such as pressure forming of strength for forming screws, bolts, nuts, etc. by the hard-working metal material, and spring forming using hard wires. However, these lubricating films, in addition to the above-described processing lubrication performance, there is a necessity of examining the composition considering the recent global environment.

For example, Patent Literature 1 below proposes a lubricant for release processing of a metal material containing a carboxylic acid amide wax obtained by a reaction of a higher aliphatic monocarboxylic acid and a diamine, or a mixture of a higher aliphatic monocarboxylic acid and a polybasic acid and a diamine. It is.

In addition, Patent Document 2 below is subjected to Ni plating having a thickness of 1 µm or more and 5 µm or less on a stainless steel wire, further coating a synthetic resin containing halogen on the surface thereof, and applying a wire drawing of 60% or more in cross-sectional reduction rate to the surface. It is proposed to use a steel wire for automatic coiling, in which the roughness is adjusted to 0.8 s to 12 s, thereby improving the lubricating performance and improving die life and coiling speed during drawing.

Further, in Patent Document 3, as an environmentally compatible processing film, 75 to 90% by weight of K2SO4 and Na2SO4 or a mixture thereof, 3 to 25% by weight of Na2B4O7, and 2 to 10 nonionic surfactants. The stainless steel wire which performed the sulfate coating which consists of weight% is proposed.

Moreover, in patent document 4, in order to provide the stainless steel wire for spring excellent in the coiling characteristic, the nitride layer is provided by the nitriding process on the surface of a stainless steel wire, it is drawn, and the island of the nitride layer by a crack is prescribed | regulated on the surface. It is proposed to increase the storage capacity of the auxiliary lubricant to be provided thereby.

Patent Document 1: Japanese Patent Application Laid-Open No. 4-202396 Patent Document 2: Japanese Unexamined Patent Publication No. Hei 6-226330 Patent Document 3: Japanese Unexamined Patent Publication No. Hei 10-88179 Patent Document 4: Japanese Unexamined Patent Publication No. Hei 9-85332

However, in the case of chemical conversion treatment with oxalate or phosphate, or a lubrication coating in which a solid lubricant such as metal soap is further adhered thereon, after the plastic working of the metal material, treatment such as acid washing or water washing is performed to remove the lubrication coating. It is necessary and there is an environmental problem.

Moreover, the lubricant proposed by patent document 1 has a problem that it is inferior in heat resistance.

Moreover, in patent document 2, since the structural film contains halogen-containing synthetic resin, specifically, it is a fluorine-type resin and chlorine-type resin, such as tetrafluoroethylene resin, it is difficult to remove, or the organic solvent is needed for the removal. Shall be. For this reason, the technique of patent document 2 also has a problem from an environmental point of view.

Although the patent document 3 respond | corresponds to a global environment, lubrication property is insufficient in sulfate and borate itself, and sufficient problem solution is not aimed at these lubricating films.

Moreover, as the stainless steel wire of patent document 4, since the island of the said nitride layer formed in the surface remains as it is, there exists a problem of reducing the surface state of a metal material and reducing product value.

Therefore, in this invention, it was devised in order to solve the problem of the conventional lubricating film, and it is excellent in lubrication performance, and can remove easily, without reducing the surface state of a metal material, improving the processing performance of a metal material. It is an object of the present invention to provide a highly versatile lubricating film effective for environmental conservation and inlineable, a coated metal material coated with the film, and a method for producing the coated metal material.

Moreover, an object of this invention is to provide the lubricant composition for metal-material plastic working which can form such a lubricating film, and is excellent in the dispersion stability and environmental conservation of a solid lubricant.

The invention according to claim 1 is at least one inorganic salt selected from the group consisting of (A) sulfate, borate, silicate, phosphate, molybdate and tungstate salt, (B) a lubricating material having an average particle diameter of 20 μm or less, (C) A water-soluble resin material having an average molecular weight of 5000 to 100000, and (D) water, wherein the weight ratio of the components (A) :( B) :( C) is 1: 0.01 to 20: 0.01 to 20 It is a lubricant composition for metal materials plastic working.

Since the resin material (C) used as a dispersing agent of a solid lubricating material is water-soluble, the lubricating agent composition of Claim 1 is excellent in dispersion stability because it is easy to prepare and excellent in the ability to disperse a solid lubricating material. Moreover, the film formed by this invention can be removed easily with water, without requiring an organic solvent. In addition, since the inorganic salt (A) and the lubricating substance (B) are held firmly on the surface of the metal material by the water-soluble resin material (C), no base treatment such as chemical conversion treatment with oxalate, phosphate, or the like is required. By applying the composition directly to the metal material surface and drying, a lubricating film excellent in lubrication performance can be easily provided.

As said resin material (C), it is water-soluble resin which has at least 1 sort (s) of electrical property chosen from the group which consists of acrylic acid resin and other carboxylic acid group containing resin, sulfonic acid resin, and polyvinyl alcohol, and averages It is preferable that molecular weight is 8000-50000.

Moreover, the said resin material (C), More preferably, it is an anionic group containing acrylic acid alkylester copolymer which has an alkyl acrylate ester as a main component.

The invention according to claim 4 is at least one inorganic salt selected from the group consisting of (A) sulfate, borate, silicate, phosphate, molybdate and tungstate, (B) a lubricating substance having an average particle diameter of 20 μm or less, And (C) a solid containing a water-soluble resin material having an average molecular weight of 5000 to 100000 for fixing and holding the inorganic salt (A) and the lubricating substance (B), wherein at least part of the inorganic salt (A) It has a crystal part which crystallized, It is a lubricating film characterized by the above-mentioned.

The lubricating film according to claim 4 is composed of an inorganic salt (A), a lubricating substance (B) having a particle diameter of 20 µm or less, and a water-soluble resin material (C) that is bonded and held by a metal material, and is improved in terms of environment. In the lubricating film, the inorganic salt (A) and the lubricating substance (B) are firmly held on the surface of the metal material by the resin material (C), and further, a crystal part in which at least a part of the inorganic salt (A) is crystallized. Since it has a further improved lubrication performance, it is especially suitable as a lubricating film of steel processing or hard-working metal material.

It is preferable that the weight ratio of the said structural raw material (A) :( B) :( C) of the said lubricating film is 1: 0.01-20: 0.01-20.

In addition, it is preferable that the crystal part is formed as a protrusion having a shape of at least one of granular, monofiber, and leaf veins and provided convexly on the outer surface of the lubricating film.

Moreover, it is preferable that the area ratio of the said crystal | crystallization part is 20 to 80% from the surface of a lubricating film.

Moreover, it is preferable that the said crystal part is a thing with a fine structure of 0.5 mm or less.

Further, the resin material (C) is more preferably at least one water-soluble resin selected from the group consisting of acrylic acid resins and other carboxylic acid group-containing resins, sulfonic acid resins and polyvinyl alcohol. Moreover, it is preferable that molecular weights are 8000-50000.

Moreover, the coating metal material in which the said lubricating film is formed in the adhesion amount of 0.3-12 g / m <2> on the surface of a to-be-processed metal material is preferable.

In the coating metal material provided with such a lubricating film, the auxiliary lubricant such as metal soap, molybdenum disulfide, graphite, borax or lime may be used in combination as the second lubricating material in the molding process by plastic deformation. The second lubricating material is effectively held between the crystal parts, and further improvement in lubrication performance is achieved. Moreover, the minute unevenness | corrugation formed by protrusion of a crystal | crystallization part is formed in a lubricating film, and has an effect which raises the storage efficiency of a lubrication agent, without providing an abnormality like the nitride layer in the said patent document 4 daringly. . For this reason, the metal material which remove | eliminated the surface lubricant suppresses fall of surface property, and also contributes to cost reduction, such as reducing a finishing process.

In addition, the metal material to be processed is preferably in the shape of any one of linear, rod, strip, sheet and block according to the end use for cold rolling, pressing, rolling or spring.

The metal material to be processed is preferably a hard-working metal wire selected from the group consisting of stainless steel, titanium, titanium alloys, nickel, nickel alloys, niobium and niobium alloys.

In addition, the invention according to claim 13 of the present invention is in the group consisting of (1) the raw material metal material for processing according to the form of the final product, and (2) sulfate, borate, silicate, phosphate, molybdate and tungstate A lubricant composition containing at least one inorganic salt (A) selected, a lubricating substance (B) having a particle diameter of 20 µm or less, a water-soluble resin material (C) having an average molecular weight of 5000 to 100000, and water (D) is prepared. (3) immersing the raw material metal material in the preparation step, (3) the lubricant composition heated to a predetermined temperature, and heating the raw material metal material; (4) the inorganic salt (A) and the lubricating material (B). ) And a film formation step of crystallizing or filmifying the resin material (C) on the material metal material, and (5) a drying step of drying and solidifying the lubricating film obtained with the crystal part to fix the crystal part. Featuring A method for manufacturing a coated metal material.

The method may further include an intermediate processing step of performing plastic working of the raw material metal material after the drying step, in which the second lubricating material different from the lubricating film is applied to the raw material material. It is preferable to carry out.

Moreover, it is preferable that the said coating metal material is a coating metal wire for pressure vessel processing, and the said intermediate | middle process is the drawing or rolling process of hardness of 30% or less of the processing rate.

In addition, it is preferable that the said coating metal material is a coating metal wire for spring work, and the said intermediate | middle process is the drawing or rolling process of the strength of 60% or more of processing rate.

According to the manufacturing method of the coating metal material of this invention, the formation of a uniform and stable coating process can be set as a continuous system similarly to the formation of the conventional lubricating film, and the continuous operation which reduced the work load by inlining becomes possible.

1 is an enlarged perspective view showing an example of the coating metal material according to the present embodiment.
Fig. 2A is a micrograph showing an enlarged outer surface of the lubricating film, and shows the distribution state of the crystal part in which the crystal part is formed as a protrusion in which point and short fiber phases are mixed.
2B is an enlarged micrograph of the outer surface of the lubricating film, and shows an example of a distribution state in which the crystal part is formed as a lobed protrusion.
3 is a process diagram illustrating a manufacturing process of the coated metal material.
4 is a relational diagram showing the relationship between the area ratio of the crystal portion and the processing life in the pressure vessel processing.
It is an enlarged photograph which shows the surface state of the processed product of a metal material after removing a lubricating film.

EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of this invention is described based on drawing.

As shown in FIG. 1, the covering metal material 1 has a long metal wire 2 and a lubricating film 3 covering almost the entire outer surface thereof, and the metal wire 2 and the lubricating film 3. Silver is integrated, and the lubricating film 3 has the crystal part K by crystallization of the one part composition.

The metal wire 2 is a wire rod of a metal material selected according to its purpose and use. As this metal material, what has conventionally been applied to plastic working can be used. As such a metal material, for example, a hard-working metal material such as stainless steel, titanium or titanium alloy, nickel or nickel alloy, niobium or niobium alloy is suitable, and among them, the stainless steel or titanium alloy having a large work hardening property is preferable. Do. In addition, the plastic working includes various things such as pressure working, press working, bending, rolling, or spring working.

In particular, the above-mentioned pressure vessel work and press work pressurizes a metal material momentarily and greatly protrudes and deforms the deformation. Therefore, the lubricating film of the present invention is effective for suppressing deformation cracking of materials and defects of tools. In addition, the lubricating film of the present invention is also effective for plastic working using high-strength metal thin wires having predetermined spring elasticity even in spring molding.

As the metal wire 2 for cold rolling, for example, the wire diameter is about 0.01 to 20 mm, preferably 0.5 to 10 mm, and a metal wire rod having a soft finish of 900 MPa or less in tensile strength thereof is suitable. . On the other hand, as the metal wire 2 for a spring, the cold drawn metal wire material which has a high diameter characteristic of about 0.01-10 mm of wire diameter, and about 1600-2600 Mpa of tensile strength is used suitably, for example. In the case where the metal material is stainless steel, in order to obtain the above-described strength characteristics, for example, as the metal wire for electronic rolling process, a solid solution heat treatment finish, for example, a hardness of 30% or less (preferably 3 to 20%) It is preferable to carry out skin pass finishing by the wire drawing process and the rolling process. In the latter metal wire for spring, it is preferable that the final finish is work hardened by, for example, cold wire working of 60% or more of work rate.

The cross-sectional shape of the metal wire 2 may be either circular or noncircular. In addition, the surface roughness and the shape of the metal wire 2 are also arbitrarily set. For example, the metal wire 2 may be a wavy shape in which the outer diameter is periodically changed along the longitudinal direction. The metal material covered with the lubricating film can be widely applied to various shaped articles such as rods, strips, sheets, or blocks in addition to long wire rods, and the present invention includes these shapes.

The lubricating film 3 covering such a metal material (in this embodiment, the metal wire 2) is formed of a lubricating composition for metal material plastic working in the present invention containing the following three types of constituent materials. As the first constituent material, at least one inorganic salt (A) selected from the group consisting of sulfates, borates, silicates, phosphates, molybdates and tungstates is used. As the second constituent material, a particulate lubricating substance (B) having an average particle diameter of 20 µm or less is used. In addition, as the third constituent material, a water-soluble resin material (C) is used, which has a function of fixing and holding the inorganic salt (A) and the lubricating substance (B). The lubricating film 3 is obtained by apply | coating the aqueous lubricant composition which mix | blended these structural materials (A)-(C) in a predetermined ratio to the said metal material, and drying and solidifying. And this invention is characterized by having the crystal part K in which at least one part of the said inorganic salt (A) crystallized in the lubricating film 2 which consists of these structural materials.

The inorganic salt (A) of the said 1st structural material improves the carrier property and pressure resistance of a lubricating film, is water-soluble, and melt | dissolves in water easily by heating to predetermined temperature with the resin material (C) used together with this. . It is preferable that an inorganic salt (A) can crystallize at least one part with drying of a coating film.

Examples of the inorganic salt (A) include sulfates such as sodium sulfate and potassium sulfate, borate salts such as sodium borate, potassium borate and ammonium borate, silicates such as sodium silicate and potassium silicate, phosphates such as zinc phosphate and calcium phosphate, and molybdate Molybdate salts such as ammonium and sodium molybdate or tungstate salts such as sodium tungstate. These may be used independently or may be used in combination of 2 or more type. In particular, potassium sulfate and sodium borate are suitable for the present invention because they bring about excellent carrier effect with freshness, and are water-soluble and crystals have excellent internal pressure.

The second structural member is a lubricating substance (B) constituting the lubricating film 3 together with the inorganic salt (A), and has a function of lowering the frictional resistance in the lubricating film. As the lubricating substance (B), for example, graphite, molybdenum disulfide, boron nitride, tungsten disulfide, graphite fluoride, PTFE or the like is suitably used. These lubricating substances can be used individually or in combination of 2 or more types arbitrary. Although the average particle diameter of a lubricous substance (B) is 20 micrometers or less, it is preferable that the minimum is 1 micrometer or more. The shape of the lubricating substance (B) is not particularly limited, but for example, fine particles are preferable.

It is estimated that the said lubricous substance (B) changes shape according to the coating | covering process and subsequent processing. However, in the coarse thing whose average particle diameter exceeds 20 micrometers, when mixing this in a liquid as a lubricant, it becomes easy to deposit at a bottom part, and it is difficult to obtain a constant coating state. Moreover, as coarse particle, film surface shaping | molding is reduced. In this respect, the more preferable average particle diameter of the lubricating substance (B) is 15 µm or less. In addition, the said average particle diameter shall mean the average of the largest dimension of each particle | grain which measured the some particle | grains extracted arbitrarily in the said group.

Graphite is particularly excellent in sliding properties, leading to good lubricating performance, and can be easily finely grained by hardness impact, and also excellent in heat resistance and conductivity. For this reason, graphite is especially suitable as said lubricating substance (B) of this invention. Therefore, the lubricating film including the same absorbs the load pressure and prevents burning due to generated heat when used for processing such as instantaneous high pressure, such as forging processing. In addition, the lubricating film containing graphite facilitates heating at the time of warm working performed by direct energization, and contributes to increase of tool life and trouble reduction such as work cracking.

Moreover, the water-soluble resin material (C) which is a 3rd component material exhibits the adhesiveness which adhere | attaches the said inorganic salt (A) and the lubricous substance (B) firmly to the metal material 2 in the state which solidified as a lubricating film. The resin material (C) generates repulsive force in the lubricating substance (B) in a solution state, raises the viscosity of the aqueous solution to prevent sedimentation of the lubricating substance (B), or uses the lubricating substance (B) as a surfactant. The property of stabilizing dispersion by making it hydrophilic is necessary. In addition, the lubricating film is often removed after the processing. In this case, the resin material (C) is made of a resin material having an electrical property of 5000 to 100,000 with an average molecular weight that causes water solubility so that it can be easily dissolved in water or hot water without using a special solvent or the like. have.

That is, when the said average molecular weight is less than 5000, the viscosity of a lubricating agent composition falls, the adhesion amount decreases, adhesive strength falls, and it is difficult to obtain a favorable film, ie, a suitable lubrication state. In contrast, the polymer having an average molecular weight of more than 100,000 is not suitable for the present invention because it exceeds the water-soluble region. Moreover, it cannot be said that it is structurally preferable, for example, to raise viscosity and to reduce the wettability of the said lubricous substance (B), or to form a micropore inside. More preferably, the average molecular weight of the said resin material (C) is 8000-50000, More preferably, it is 10000-35000.

As said more preferable water-soluble resin material (C), For example, acrylic acid resin, such as acrylamide resin and acrylate resin, other carboxylic acid group containing resin, sulfonic acid resin, polyvinyl resin, such as polyvinyl alcohol, etc. And those having a hydrophilic functional group. It is preferable that especially these resin materials are equipped with the electrical property of description demonstrated below, More preferably, the relative dielectric constant is 2-12, More preferably, it is 2.0-8.0, and it promotes the electrical property. Since it is planed, it is preferable. Some of the acrylic acid-based resins may form a rigid film by thermosetting. For example, in the case where no film removal is necessary after the plastic working, a coating film in which the inorganic salt (A) and / or the lubricating material (B) are hard to fall off may be formed by heat drying or heat treatment. As an especially preferable resin material (C), the anionic group containing acrylic acid alkylester copolymer which has an alkyl acrylate ester as a main component is mentioned.

In addition, the said resin material (C) having an electrical property means that it is a resin material which has an electric charge and / or a polarity, and the verification can be performed from the structural formula calculated by chromatograph, FT-IR, etc., for example. . Moreover, such a characteristic can be achieved by having a hydrophilic functional group including O and H, in particular in its molecular structure, whereby it can be a water-soluble resin material. Similarly, the relative dielectric constant is also shown in JIS-K6911. For example, various methods are proposed, such as a condenser, a parallel plate method by its capacitance, and a free space method for measuring reflection by touching radio waves. Such a resin material (C) is wound around the particulate lubricating material (B) to generate a repulsive force due to the attractive force to be aggregated and the charge to be separated, and to generate a water-soluble viscosity to raise the viscosity of the lubricating material (B). It may be possible to prevent sedimentation or to stabilize the dispersion by making the lubricating material (B) hydrophilic as a surfactant, resulting in a stable and uniform good lubricant composition.

The said resin material (C) used for this invention is water-soluble, and melt | dissolves easily in water, warm water, etc. For this reason, in order to remove a film after a coating process step and final processing, there exists a merit that use of a hazardous chemical liquid, such as an organic solvent, is suppressed, and it is also environmentally preferable.

The lubricant composition for metal material plastic working of the present invention is prepared by dissolving or dispersing the components (A) to (C) in water, and the water is finally removed by a drying means after coating. A lubricating film made of C) is formed. The compounding ratio of each component (A)-(C) is 1: 0.01-20: 0.01-20 (solid content weight ratio) in conversion of the weight in the solidified state, Preferably it is 1: 0.1-12: 0.1-10. More preferably, for example, for cold rolling, the ratio is 1: 0.5 to 3: 0.5 to 8, and for spring, the ratio is 1: 1 to 6: 1 to 10, and the adhesion amount is 0.3 to solid, for example. It adjusts and uses the density | concentration and a viscosity of a lubricating composition so that it may be about 12 g / m <2>. Usually, a lubricant composition is prepared so that solid content concentration may be 3-30 weight%.

If the adhesion amount is less than 0.3 g / m 2, the lubrication performance is not sufficiently exhibited, and even if an amount of more than 12 g / m 2 is given, a lubrication performance suitable for this is not obtained, and it causes a problem such as clogging of the mesh during processing. do. Moreover, when the said solid content concentration is less than 3 weight%, sufficient adhesion amount is hard to be obtained by one coating operation, and when it exceeds 30 weight%, problems in application | coating operation generate | occur | produce, such as solution viscosity becoming too high.

The coating metal material of this invention is obtained by apply | coating the said lubricant composition to the metal wire 2, and drying a coating film. Application of a lubricant composition can be performed by arbitrary methods, such as immersion coating or spray coating. In the drying step, crystal precipitation of the inorganic salt (A) and film formation of the water-soluble resin material (C) occur, and a lubricating film in close contact with the surface of the metal material is formed by completing evaporation of water. The lubricant composition is preferably heated to 40 to 100 ° C., preferably 60 to 100 ° C. in advance, so that the crystallization of the inorganic salt (A) can be promoted by providing a lubricating substance (B).

Although the temperature and time in the said drying process are not specifically limited, Usually, heating about 1 to 1000 second is performed at room temperature-150 degreeC normally. Drying is suitably performed, for example, by hot air drying of 80 ° C or more, preferably 100 ° C or more so that the time is short. The lubricating film thus obtained contains an inorganic salt (A), a lubricating substance (B) and a water-soluble resin material (C) in the blending ratio. When the compounding ratio of the lubricating substance (B) and the resin material (C) is less than 0.01, respectively, the area ratio of the crystal portion K becomes too large, or a hard film is difficult to cover. On the other hand, when these compounding ratios exceed 20, since the area ratio of the crystal | crystallization part K becomes small and the ratio of the resin material (C) is too large, sufficient lubrication performance is not exhibited.

3 is an example of a manufacturing process of the coated metal wire (coated metal material 1). The process is

(1) a preparation step of preparing the raw material metal wire [material metal material 11] and the lubricant composition 12 for processing, (2) a material metal wire 11 in the lubricant composition 12 heated to a predetermined temperature. Immersing and applying the lubricant composition 12, and heating the surface of the material metal wire 11;

(3) a film forming step in which the constituent materials (A) to (C) crystallize or filmify on the material metal wire 11, and (4) a drying step of drying and solidifying a lubricating film having a crystal part to fix the crystal part. It is made.

In the present embodiment, the raw material metal wire 11 is prepared by winding a long material having, for example, a reel or a carrier 10 having a dimension, a shape, and a characteristic adjusted according to its purpose and use, and this is a guide roll R1. R2 and R3 are continuously released, and the aqueous lubricant composition 12 is introduced into the bath 13 in a heated state. Thereby, the raw material metal wire 11 is apply | coated the predetermined amount of the said lubricant composition 12 on the surface.

The lubricant composition 12 is an aqueous dispersion in which the lubricating substance (B) is dispersed in the aqueous solution of the constituent materials (A) and (C), and is preferably heated to a predetermined temperature by suitable heating means (not shown). Heating temperature is suitably set according to the kind and crystal amount of the said resin material (C), For example, what contains the said alkyl acrylate ester copolymer is set to 60-100 degreeC, and the said lubricating film after film solidification is The crystal of inorganic salt (A) can be precipitated effectively.

For example, when the constituent material (C) contains a sulfonic acid resin or an acrylic acid resin having an amide group, the set temperature in the drying or subsequent heat treatment is, for example, heated above the glass transition temperature (TG) of the resin material. By setting it as temperature, thermosetting property can be increased and the firming firmness as a lubricating film can also be raised.

Moreover, the said reservoir 13 has a sufficient volume which has the strand length adjusted with the feeding speed of the metal wire 11 so that the said long metal wire 11 may become predetermined temperature. And the said metal wire 11 which exited the liquid level of the storage tank 13 produces | generates the said crystal | crystallization and a film on the outer surface by the heat of the lubricating composition 12, and is dried by the dryer 15. FIG. Thereafter, the metal wire 11 is wound around the winding reel 14. Moreover, in this embodiment, the hot air dryer 15 is arrange | positioned in the preset position so that the amount of adhesion of a lubricant may be settled in the state which reached a predetermined range, for example, a lubricant is fixed by hot air supply of temperature 100 degreeC or more.

In this step, the dipping and heating steps are performed in the storage tank 13, and the film forming step of crystallization of the inorganic salt (A) and film formation of the resin material (C) is carried out from the liquid level of the storage tank (13). In the area up to. Therefore, by a series of processes, continuous processing is attained and inlining becomes possible. In addition, of course, the supply speed | rate of the metal wire 11 can be suitably adjusted according to the composition of the lubricant composition 12, and its drying conditions.

In addition, when intermediate processing is further performed after the lubricating film 3 is formed, a type of lubricating material different from the lubricating material B included in the formed lubricating film 3 is applied to the coating metal material as the second lubricating material. Also good. Examples of the second lubricating substance include metal soap, molybdenum disulfide, graphite, boron nitride, tungsten disulfide, graphite fluoride, borax, lime or PTFE powder. As intermediate | middle processing, the drawing of the hardness of 30% or less of hardness, or rolling, and the drawing of the strength of 60% or more of processing, or rolling are mentioned, for example. Since the coating metal material of this invention has fine unevenness | corrugation on the surface of a lubricating film as mentioned above, the holding performance of the applied 2nd lubrication material is high, and shows the outstanding lubrication performance.

2A and 2B show an example of the distribution state of the crystal part K formed in the lubricating film 3, and these are micrographs magnified 35 to 80 times. The crystal part K differs in the crystal state according to the kind and quantity ratio of the constituent material of a lubricating film, and the thing of FIG. 2A forms a viscous to short-fiber protrusion part by using sulfate etc. as an inorganic salt. In addition, in the thing of FIG. 2B, the lobes-shaped protrusion part is formed by using a borate salt.

As shown in the above figures, on the outer surface of the lubricating film, each crystal portion K is uniformly distributed in a protruding state provided convexly from the surface thereof, and is planarly concave between the crystal portions K. A part is provided. For this reason, the outer surface of the coating metal material is formed as a minute uneven surface having the convex portion and the concave portion formed by the crystal portion K, and contributes to the improvement of lubricity.

The said crystal part K may not only be formed in the single layer in the lubricating film 3, but may be formed in several laminated distribution state in the thickness direction. In addition, the directionality of the crystal | crystallization part K does not need all the crystal parts to be in parallel with the planar direction of the lubricating film, and includes the case where it cross | intersects the diagonal direction, for example.

In addition, the said crystal part K is based on the inorganic salt (A) of the component, Comprising: The structural pattern of each element and its determination part (by image analysis using a scanning electron microscope or X-ray analysis) It is confirmed by the sign of K). By the image analysis of such a pattern, the area ratio of the crystal part K can be calculated | required easily. The area ratio of the crystal part K is defined as a ratio of the total area of the crystal part K per unit area of a lubricating film in plan view, and it is preferable that it is 20 to 80%. In this case, the area ratio is represented by the average value of the result of the measurement visual field of the arbitrarily selected several points.

According to the observation in the image diffraction, it is recognized that the lubricating substance B is substantially detected in the portions other than the crystal portion K, and the portion is a concave portion. Therefore, such a fine uneven surface can receive the said auxiliary lubricant provided at the time of subsequent processing efficiently, for example, and can improve lubricity. That is, by optimizing the area ratio of the crystal part K, it is possible to give excellent lubricity to severe processing such as pressing and machining of difficult materials, and it is also confirmed that there is a relationship between the area ratio and lubricity. It is.

4 is an example of the result, where the horizontal axis represents the area ratio (%) of the crystal part K, and the vertical axis represents the relationship between the processing life (the number of processings) in the above-mentioned pressure vessel machining. In this embodiment, it is preferable that area ratio is set to 20 to 80%. As is apparent from FIG. 4, when the area ratio is less than 20%, the holding retention force of the auxiliary lubricant applied to the coated metal material in the intermediate processing suitably performed decreases the tool life. On the contrary, when the area ratio exceeds 80%, sufficient storage space for the auxiliary lubricant cannot be obtained, and since the crystal portion K is very hard, the surface of the metal material to be processed is contained if it is contained in a large amount more than necessary. It lowers the properties and causes a decrease in the life of the machining tool. Therefore, the area ratio of the crystal | crystallization part K becomes like this. More preferably, it is 30 to 80%, More preferably, it is 40 to 70%, Especially preferably, it is set to 40 to 60%.

In addition, the size and shape of the crystal part K change suitably according to the processing conditions, the kind of component, etc. Although the shape of the crystal | crystallization part K is not specifically limited, It is preferable to have any 1 or more types of shapes, such as powder form, short fiber form, and a leaf vein shape, as shown to FIG. 2A and 2B, and the magnitude | size (constitutional dimension) is 0.5 The fine thing of mm or less is preferable. Here, the structural dimension of the crystal | crystallization part K is represented by the average value of the largest diameter in a powdery crystal | crystallization, and is represented by the average value of the maximum thickness of the single element (each single line | wire) which comprises this in a fibrous to leaf vein-like thing.

In the case where the dimension of the crystal part K exceeds 0.5 mm, the surface roughness will be brought about in the subsequent shaping | molding process, and in the said single-fiber or leaf vein shape, by the small space of the recessed part between crystal parts, , The storage efficiency of the auxiliary lubricant decreases. The dimension of the crystal | crystallization part K becomes like this. More preferably, it is 0.1 mm or less.

In the case where the crystal portion K is short-fiber or lobed, the single element of the crystal portion has a predetermined length L (for example, 0.01 to 1 mm) and an aspect ratio (L / D) of the length L and the thickness D. ) Is preferably in the range of 1.5 to 50 on average. In particular, when the crystal part K is longer than necessary, since the mesh determined by the random distribution becomes large, it is not preferable. Regarding the crystal portion K, a more preferable aspect ratio is 2 to 20. Such aspect ratio adjustment can be performed, for example, by setting the drying conditions.

In this embodiment, the case where the to-be-processed metal material is a lubrication coating wire material used for cold pressure forming and spring shaping | molding is demonstrated. In addition, it demonstrated centering around the case where the lubricating composition was apply | coated uniformly to the whole surface of a metal material, and coating | cover formation process was carried out. However, this invention is not limited to these, For example, the selection of various shaped articles, such as a rod-shaped material, a strip | belt-shaped material, a sheet | seat material, a bulk material, and the application of the kind and size of the material as a metal material is carried out by those skilled in the art. It can be easily achieved and should be included as one embodiment of the present invention.

Example

Next, the present invention will be described in more detail with reference to the following examples.

Example  One

[Production of test article]

In this embodiment, three kinds of austenitic stainless steels for cold rolling of steel types SUS304, 316, and XM7 type were selected as the material to be treated, and cold-drilled steel wires of 3.65 mm in diameter were used as materials. And these were solid-solution heat-treated by the strand-type heat processing apparatus at the temperature of 1000-1100 degreeC, it coat | covered using the following lubricant composition, and the coated stainless steel wire was obtained. In this processing step, the heat treatment apparatus is configured as a series of inline apparatuses so as to connect the coating apparatus having the structure shown in FIG. 3 to the outlet side thereof and simultaneously perform the solid solution heat treatment and the coating treatment. The lubricant composition used the following composition.

[Lubricant composition]

(A) 10% by weight sodium sulfate

(B) 2% by weight sodium borate

(C) 10 weight% of boron nitride (average particle diameter 5 micrometers)

10% by weight of acrylic acid resin (D)

(Anionic alkyl acrylate ester copolymer / dielectric constant 3.8 with charge and polarity)

(E) 68% by weight of water

(A) :( B) :( C) :( D) = 5: 1: 5: 5 (solid weight ratio)

Solid content 32 wt%

The lubricant composition which mixed these (A)-(E) is introduce | transduced into the storage tank of width 200 * depth 600 * 300mm in height, and it stirs well, heating with an external heater in the range of 80-95 degreeC, and it makes it an aqueous dispersion liquid. It was. In this state, the inorganic salt and the water-soluble resin material were dissolved in water of the solvent, and boron nitride was uniformly dispersed in this aqueous solution.

[Film Formation and Crystallization Treatment]

A film formation process is performed so that the coating film adhesion amount may become a predetermined | prescribed range by adjusting the supply rate of a to-be-processed wire rod (stainless steel wire) based on the composition of the said lubricating composition, heating temperature, and storage tank volume. In the present Example, by adjusting the wire feed rate to 3-7 m / min, it adjusted so that an average adhesion amount might be in the range of 6-12 g / m <2>. Replenishment of evaporated water was performed by the automatic adjustment performed suitably. For this reason, the coating | coating state of the said lubrication agent was good in all, and the fluctuation | variation of the adhesion amount was also suppressed little.

The treated wire rod immersed and coated in this manner is completely discharged from the liquid surface, and the applied lubricant composition is completely dried at 100 ° C. by a cylindrical hot air dryer disposed at a position of about 0.8 m from the liquid surface, thereby providing a lubricating film. Was settled in the wire rod. Moreover, since the said storage tank was heated at 80-95 degreeC, it was observed that moisture evaporates and precipitates an inorganic salt crystal | crystallization from the wire rod to the warm air dryer.

By performing such a series of heat treatment and film formation treatment of the metal wire at the above speed, each stainless steel wire is coated with a lubricating film having an adhesion amount of 6 to 12 g / m 2 on the surface thereof, and has a single fiber-like crystal part as shown in Fig. 2A. A soft stainless steel wire having a lubricating coating was obtained. The crystal part calculated | required by the image analysis by the X-ray analyzer (Horiba Seisakusho make) is 10-50 micrometers in width, and the short-fiber thing of average aspect ratios 2-15 is randomly distributed, and the area ratio is 49.6-average on average. It was 52.1%.

Moreover, although the protrusion part provided convexly is confirmed by the magnification observation by the magnification microscope, it supports also from the following measurement result of surface roughness Rz with or without the lubricant in the predetermined position of the coated steel wire. This was done.

Surface roughness of 9.6 to 10.4 μm on the surface of the lubricating coating

Surface roughness of lubricant removal surface 7.6 μm

[Comparative lubricant]

As a comparative lubricating film (comparative example), the oxalate film was formed in each of the said 3 types of stainless steel wires with the adhesion amount 6-12 g / m <2>, and was used as a comparative wire rod. In addition, the oxalate coating has conventionally been used abundantly for cold working of stainless steel, but there is a problem of sludge and waste acid containing harmful heavy metals such as generation of hexavalent Cr and mist including harmful substances. Tends to shrink.

[Intermediate processing]

To the coated soft stainless steel wire of the present example, skin pass drawing was further performed at a processing rate of 4% to obtain a stainless steel wire for cold rolling shown in Table 1. This skin path process used what used metal soap together as an auxiliary lubricant, and it was recognized that this auxiliary lubricant is hold | maintained in the recessed part of the said steel wire surface.

Lubrication Test

Next, using each stainless steel wire of Table 1 of the said Example, the pressure test which evaluated the workability was done. In the test, cold milling of the cross head screw was carried out by cold working while dropping spindle oil. The processing conditions were a total of 25,000 header moldings at a feed rate of 150 minutes per minute by a header punch of tool steel, and the number of tool surfaces and cracks. The presence or absence of defect generation, etc. was observed.

The test result was favorable, and the lubricating film of this example was able to obtain 15000 tool lifespan over the oxalate film of a comparative example. Moreover, the header process was possible without problems, such as a process crack and burn. This process score evaluates the process life of pressure-form workability, and it was recognized that the film of this Example is lubricity equivalent or more than the oxalate film which is a comparative lubricant. Although an example of the surface state of the obtained pressure vessel product (sample No. A-2) is shown in FIG. 5, the trace of burning was not seen.

Example  2

About the solid solution heat treatment material of the said XM7 stainless steel wire (wire diameter: 3.65 mm), the following processability evaluation was performed together by changing the level of the said structural material (A) inorganic salt, (B) lubricating material, and (C) water-soluble resin. The evaluation is confirmed by the tool life by header processing as above, and the result is shown in Table 2.

From each of these examples, it has been confirmed that the lubricating film according to the present invention can be employed for the steel processing film of a hard-working material, especially for header pressing of stainless steel, similarly to the conventional lubricant.

Example  3

[Application Example to Titanium-Nickel Alloy Band Material]

The lubricant composition of the following composition was prepared.

(A) sodium silicate

(B) molybdenum disulfide (average particle diameter 2 mu m)

10% by weight of acrylic acid resin (D)

(Anionic alkyl acrylate ester copolymer / dielectric constant of 2.7 with charge and polarity)

Solid content weight ratio (A) :( B) :( C) = 5: 4: 2

Solid content concentration 22 wt%

Ni-Ti alloy is an intermetallic compound and is known as a hard-working material, and it is easy to generate | occur | produce the flaw and disconnection by drawing die also in drawing. As a countermeasure, for example, descaling is performed by an oxide film, but descaling is unlikely to cause scratches or disconnection, but must be descaled in the final product. There is a drawback to it.

Then, in order to evaluate the adaptability of the present lubricating film to the Ni-Ti alloy wire, the lubricant composition was coated with 2 to 6 g / m 2 to 100 kg of the alloy annealing material having a wire diameter of 1.8 mm, and drawn to a wire diameter of 1.6 mm. Was performed. There was no scratch or disconnection in the fresh wire, and good workability was obtained. As the final product, the entire lubricating film could be removed only by alkaline cleaning and hot water cleaning required for removing the upper metal soap. As a result, the acid washing step can be omitted, the workability is improved while reducing the environmental load, and the quality has been succeeded in narrowing the range of the linear diameter tolerance.

Example  4

[Draw processing of stainless steel wire for spring]

The lubricant composition of the following composition was prepared.

(A) potassium sulfate

(B) Graphite (average particle diameter 3 μm)

(C) carboxylate-based water-soluble resin (ammonium salt / charge, polarity)

Solid content weight ratio (A) :( B) :( C) = 1: 15: 2

Solid content 18 wt%

0.3-2 g / m <2> of said lubricant compositions were apply | coated to 200 kg of annealed materials of the SUS304N1 stainless steel wire of 1.5 mm of wire diameters, and the wire diameter was wired to 0.7 mm of wire diameters. Although the material after drawing was confirmed whether or not there was a flaw, surface state was favorable and surface defects, such as peeling of a film and a scratch, were not seen. Then, the coiling property of the spring was confirmed. Conventionally, since nickel plating material is the mainstream in the coiling process of a spring material, the comparative test was done using the nickel plating material as a comparative material.

The test evaluated the compression spring which conforms to the following specification by the fluctuation | variation (3σ) of the spring free length in the coiling shaping | molding, and is a result nearly equivalent to the comparative example 0.24 with respect to 0.25 of an example material, and also nickel plating In the ash, for example, in addition to the health effects such as biological allergies, there is a problem that it is difficult to avoid environmental loads such as waste liquid treatment and lowering of the surface state after removal, even when removing this. It was possible.

Spring specifications

Compression spring D / d = 20.0

Free length 15.5 mm

Free length tolerance ± 0.3 mm

Total Take 10

50 speeds / min

As explained above, the lubricating film which concerns on this invention can be used for various uses for which lubricity is calculated | required. In particular, as a lubricating means for harsh plastic working, such as pressing, pressing, bending, rolling, spring processing, etc., of hard-working metal materials such as stainless steel, titanium or titanium alloys, nickel or nickel alloys, niobium, or niobium alloys. It can be used to solve the problem of excellent lubricity and global environmental issues to provide inline technology.

1 clad metal material
2 metal wire
3 lubrication film
K decision part

Claims (16)

(A) at least one inorganic salt selected from the group consisting of sulfates, borates, silicates, phosphates, molybdates and tungstates,
(B) a lubricating substance having an average particle diameter of 20 μm or less,
(C) a water-soluble resin material having an average molecular weight of 5000 to 100000, and
(D) water
And the weight ratio of said component (A) :( B) :( C) is 1: 0.01-20: 0.01-20, The lubricant composition for plastic working of metal materials characterized by the above-mentioned. The water-soluble resin according to claim 1, wherein the resin material (C) is at least one electrical property selected from the group consisting of acrylic acid resins and other carboxylic acid group-containing resins, sulfonic acid resins, and polyvinyl alcohols. And an average molecular weight of 8000 to 50000 lubricant composition for plastic working of metal materials. The lubricant composition for metal material plastic working according to claim 1, wherein the resin material (C) is an anionic group-containing alkyl acrylate ester copolymer containing alkyl acrylate as a main component. (A) at least one inorganic salt selected from the group consisting of sulfates, borates, silicates, phosphates, molybdates and tungstates,
(B) a lubricating substance having an average particle diameter of 20 μm or less, and
(C) Water-soluble resin material with an average molecular weight of 5000-100000 for fixing and holding the inorganic salt (A) and the lubricating substance (B)
It is a solid containing and the lubricating film characterized by the crystal part which at least one part of the said inorganic salt (A) crystallized in the said solidified material. The lubricating film of Claim 4 whose weight ratio of the said structural raw material (A) :( B) :( C) is 1: 0.01-20: 0.01-20. The lubricating film according to claim 4 or 5, wherein the crystal part is formed as a protrusion having a shape of any one or more of granular, monofiber, and leaf veins, and formed convexly on the outer surface of the lubricating film. The lubricating film of any one of Claims 4-6 whose area ratio of the said crystal | crystallization part is 20 to 80% when seen from the surface. The lubricating film in any one of Claims 4-7 whose structural dimension of the said crystal | crystallization part is 0.5 mm or less. The said resin material (C) is 1 type in any one of Claims 4-8 selected from the group which consists of acrylic acid resin and other carboxylic acid group containing resin, sulfonic acid resin, and polyvinyl alcohol. It is a water-soluble resin which has the above electrical property, and is a lubricating film whose average molecular weight is 8000-50000. The coated metal material in which the lubricating film in any one of Claims 4-9 is formed in the adhesion amount of 0.3-12 g / m <2> on the surface of the metal material to be processed. The metal material for work according to claim 10, wherein the metal material to be processed has any one of linear, rod, strip, sheet, and lump shapes according to end use for cold or warm rolling, pressing, rolling or spring. Clad metal materials. The coating according to claim 10 or 11, wherein the metal material to be processed is any one kind of hard-working metal wire selected from the group consisting of stainless steel, titanium, titanium alloys, nickel, nickel alloys, niobium, and niobium alloys. Metal materials. (1) the raw metal material for work to be preformed according to the form of the final product;
(2) at least one inorganic salt (A) selected from the group consisting of sulfates, borates, silicates, phosphates, molybdates and tungstates, lubricating substances (B) having a particle diameter of 20 µm or less, and water-soluble molecular weights of 5000 to 100,000 A preparation step of preparing a lubricant composition containing a resin material (C) and water (D),
(3) immersing the raw material metal material in the lubricant composition heated to a predetermined temperature to warm the raw material metal material;
(4) a film forming step of crystallizing or filmifying the inorganic salt (A), the lubricating material (B) and the resin material (C) on the material metal material;
(5) Drying step of solidifying the lubricating film obtained with the crystal part and fixing the crystal part
The manufacturing method of the coating metal material characterized by the above-mentioned. The method of claim 13,
After the drying step, further comprising an intermediate processing step of performing plastic working of the raw material metal material,
In the intermediate processing step, a method of producing a coated metal material, in which a second lubricating substance different from the lubricating film is applied to the material metal material and processed. The manufacturing method of the coating metal material of Claim 14 whose said coating metal material is a coating metal wire for pressure rolling, and the said intermediate | middle processing is the drawing or rolling process of hardness of 30% or less of the processing rate. The method for producing a coated metal material according to claim 14, wherein the coated metal material is a coated metal wire for spring processing, and the intermediate work is drawn or rolled with a strength of 60% or more.

Images