KR20130096301A - Lubricant for plastic processing of metal material - Google Patents

Abstract

The present invention provides a lubricant for plastic working of a metal material which is applicable to steel processing applications, which is not a black appearance that significantly contaminates the working environment, and which is less likely to generate lubrication dregs, which is a cause of poor molding.
The solution of the present invention is a lubricant for plastic working of a metal material, comprising an organically modified clay mineral carrying a cationic organic compound in a range of 5 to 95 mass% between layers of layered clay minerals.

Description

LUBRICANT FOR PLASTIC PROCESSING OF METAL MATERIAL}

Industrial Applicability The present invention relates to the plastic working of metal materials, such as steel, stainless steel, aluminum and aluminum alloys, titanium and titanium alloys, copper and copper alloys, magnesium and magnesium alloys, forging, wire drawing, pipe drawing, rolling, and pressing. The present invention relates to a lubricant for reducing baking and frictional resistance at the friction interface between a metal material, such as a workpiece, and a tool, such as a work piece, which is generated during the process.

The technical field in which the present invention is useful is in the general field of cold plastic working of the metal material, and the most suitable is the field of cold forging which is susceptible to high contact pressure at the friction interface.

In more detail, the present invention relates to a lubricant for non-black plastic processing of metal materials interposed at the friction interface between a metal material to be processed and a tool such as a mold, and exhibiting performances of both plastic resistance and friction reducing ability. .

In the plastic working of metal materials represented by forging, wire drawing, pipe drawing, rolling, pressing, and the like, the use of a lubricant is indispensable because the metal material, which is a workpiece, and tools such as a mold rub against each other violently at the friction interface.

Lubricants in the plastic working of metal materials are interposed at their friction interfaces to contribute to the prevention of quenching (direct contact between metals), to lower frictional resistance and to suppress wear, and to improve tool life and reduce processing energy. It is one of the important factors directly related to the improvement of product quality.

For example, in forging, since the plastic deformation is caused by applying a force exceeding the yield stress to the metal material as the workpiece, its frictional interface is subjected to very high contact pressure, and the workpiece is subjected to deformation and frictional operations. It is influenced by the heat to be converted and the increase of the surface area.

Since the lubricant needs to maintain its performance under such severe conditions as high surface pressure, heat load, and surface area expansion, a lubricant designed to have both a plastic resistance and a friction reducing ability has been used.

As a lubricant for plastic working, a method of interposing a lubricant such as oils, soaps, waxes, etc. on the friction interface may be used for light processing. Especially, in cold forging or the like where sliding at a high contact pressure is forced, It is not usually used because it does not prevent direct contact of the mold and is likely to cause baking.

Therefore, generally, the chemical conversion film for plastic processing which produced the crystalline chemical conversion film, such as a phosphate and an oxalate, on the surface of the metal material which is a to-be-processed material, and performed the lubricating process, such as soap, is used as a lubricant.

In the plastic film for plastic working, the inorganic salt film deposited by the chemical reaction on the metal surface, which is the work material, is responsible for the corrosion resistance, and the upper soap film chemically reacts with the inorganic salt in the lower layer to produce metal soap, thereby providing excellent friction reducing ability. An ideal lubricating film is formed.

However, the chemical conversion coating for plastic processing requires liquid management because it requires control of the chemical reaction in each treatment step, and consumes a large amount of energy to keep the treatment tank at a high temperature.

In addition, a large amount of insoluble salts (sludge) and waste liquid are generated in the treatment process, and waste water treatment or industrial waste treatment is required.

Since it is composed of many processes including the influence of these and washing with water and acid washing at the time of treatment, a large amount of cost is required both at the time of introduction and operation, and it is a preferable method in terms of process control and environmental conservation. There is a need for a lubricant and a method for treating the process which are simple but do not generate waste.

From such a request, various lubricants and treatment methods have been proposed.

For example, "the lubricant composition which made water-soluble polymer or its aqueous emulsion the base material, and mix | blended the solid lubricant and the chemical conversion film forming agent" (patent document 1), "lubricating composition for plastic working of metal materials" (patent document 2), etc. Discloses a lubricant in which a lubricating film is formed by simple application and drying based on synthetic resins.

In addition, in the "water-based lubricant for cold plastic working of metal materials" (Patent Document 3), a direct metal contact with the tool is avoided by forming a film in which the synthetic resin and the water-soluble inorganic salt are uniformly deposited on the surface of the workpiece. By containing a lubricating component etc. in a film by the ratio of, it is disclosed that performance equivalent to or more than when the lubricating component layer is formed on a phosphate film is obtained.

In addition, in "the metal material for plastic working which has an inclined two-layer lubricating film, and its manufacturing method" (patent document 4), the base layer which has inorganic compounds, such as a phosphate, a sulfate, a borate, a silicate, a molybdate, and a tungstate, as a main component And a lubricant having a performance equivalent to that of a chemical conversion coating for plastic working is formed by forming an inclined two-layer lubricating layer of a lubricant layer mainly composed of metal soap, wax, polytetrafluoroethylene, molybdenum disulfide, graphite, and the like.

In the recent plastic processing, especially cold forging, not only the conventional necessity such as environmental preservation and the long life of the mold, but also the cutting processing with material loss as much as possible, the complex shape, high dimensional accuracy, smoother surface quality With the aim of precision net shape forgings that want to obtain processed products economically, the demand for lubricants is increasing.

Therefore, the surface pressure and surface area enlargement at the time of processing increase, and the difficulty of a process increases, and the process which becomes difficult to cope with the conventional plastic working lubricant is increasing.

As a lubricant which can respond to such steel processing, the lubricant which contains a large amount of solid lubricants, such as molybdenum disulfide, tungsten disulfide, and graphite, is common.

These solid lubricants have a hexagonal crystal lattice structure and exhibit friction reducing ability due to the small interlayer bonding force (van der Waals force,? Bonding), followed by increase in surface area, plastic working with high pressure and high heat resistance .

As a usage example of these solid lubricants, in "the processing method of the water-based lubricant for lubricating metal materials, and a lubricating film" (patent document 5), (A) water-soluble inorganic salt, (B) molybdenum disulfide and at least 1 type selected from graphite It contains a lubricant and (C) wax, and these components are melt | dissolved or disperse | distributed in water, solid content ratio (mass ratio) (B) / (A) is 1.0-5.0, (C) / (A) is 0.1- An aqueous lubricant for metal material plastic working is characterized by being 1.0.

However, since the external appearance of solid lubricants such as molybdenum disulfide, tungsten disulfide, and graphite is black, remarkable contamination is a problem in its working environment, and a solid lubricant excellent in non-black appearance and excellent in lubricity is strongly desired.

In addition, as a general solid lubricant which has a non-black appearance, there are the following.

Graphite fluoride is synthesized by fluorination of a carbon material such as graphite at high temperature with fluorine gas (synthesis of a high crystalline carbon material at high temperature results in a whiter synthetic product), and lubrication composed of covalent bonds of fluorine and carbon Although it is a solid lubricant of the layered structure which has a layer plane which is easy to become, it is a drawback that it becomes a very expensive material because it requires raw material cost and high temperature heat processing.

In addition, hexagonal boron nitride (h-BN) has a yellowish white or white appearance, has a hexagonal layered structure, and has excellent heat resistance, but has high bonding strength between layers, and has a high coefficient of friction compared to molybdenum disulfide and graphite having a similar structure. Is high.

In addition, polytetrafluoroethylene (PTFE), which is an organic polymer having a white appearance, has a smooth and small cohesive molecular structure, and is a solid lubricant that exhibits a low coefficient of friction due to slippage between molecular chains, but is an organic substance. Moreover, since it is chemically inert, it was less than inorganic in pressure resistance, heat resistance, etc.

In addition, flake mineral having a cleavage property and layered mica, and mica (serite) belonging to it are very fine solid and white solid solid lubricants, and have a function of inhibiting pressure resistance and oxidation of metal surfaces, but between layers. Because of this strong ionic bond, the interlayer is difficult to lubricate and the friction coefficient is high.

In addition, the friction reducing ability is also low for inorganic materials having a layered structure or cleaved crystal structure such as talc, hard calcium carbonate, magnesium hydroxide, and magnesium oxide.

In addition, melamine cyanurate, amino acid compounds and the like are organic substances, and similar to polytetrafluoroethylene, they have a friction reducing ability, but have not reached inorganic substances in pressure resistance and heat resistance.

In these general non-black solid lubricants, it has been found that no material comparable to the plasticity resistance and friction reducing ability of black molybdenum disulfide, tungsten disulfide, graphite, and the like for plastic working has been found.

In addition, in the field of hot forging, a white non-graphite forging lubricant has been proposed, but this is not a solid lubrication action, but rather a pseudo solid lubrication by a mixture of a melt and a residue by melting and thermal decomposition of an organic substance under high temperature conditions, and It is considered that performance is exhibited by the combination of the release effect by the gas which arises by thermal decomposition, and it is hard to say that it is suitable in the field of cold forging with high processing power.

Soaps, waxes, and the like, which are lubricant components of general plastic working lubricants, are weak in shear and exhibit a friction reducing ability by being subjected to heat generated from friction during processing and material deformation to melt, and hardly exhibit any seizure resistance. .

These melted lubricant components flow in tools such as molds, and the lubricating film dropped during processing is also locally deposited.

As a result, the flow of the workpiece to the detailed shape of the mold is hindered and develops into molding defects such as underfill and dimensional defects.

As mentioned above, from the recent necessity of obtaining the desired workpiece with high accuracy, this problem is serious and an improvement is indispensable.

Japanese Patent Laid-Open No. 52-20967 Japanese Patent Laid-Open No. 2000-63880 Japanese Patent Publication No. 10-008085 Japanese Patent Laid-Open No. 2002-264252 International publication WO2002 / 012419

As mentioned above, the main problem with the current plastic processing lubricant is as follows.

(1) Contamination in the Working Environment of Black Solid Lubricant-containing Lubricants in Steel Processing Applications

(2) Molding defect due to the accumulation of lubrication residues caused by lubricant components in the mold

Based on the above, the main subject of the present invention is to solve these problems, and in particular, it is applicable to steel processing applications, and it is a cause of poor molding without the appearance of a black system that significantly contaminates the working environment. It is to provide a lubricating agent for plastic working of a metal material which is hard to generate lubrication dregs.

In addition to the main tasks, there are more tasks. In general, many forged parts manufacturers first forge with large plastic deformations, and then precisely forge and finish to the final part shape. However, as the cost competition intensifies in recent years, the movement toward further reduction of production cost is becoming active in each manufacturer. As a means of reducing cost, the number of forging processes can be shortened. For example, if the final forging can be omitted, the annealing process before precision forging, the lubrication treatment for forging, and the forging process can be omitted. Therefore, the cost can be greatly reduced. For that purpose, it is necessary to provide a lubricating coating agent that withstands large deformation and is excellent in processing accuracy and workability.

In order to omit precision forging, even if forging with large plastic deformation is performed, it is required to maintain good dimensional accuracy and surface finish. For that purpose, it is necessary to control the generation of the coating dregs adhering to the mold, which is a cause of molding failure or work introduction failure.

Based on the above, in order to omit the precision forging, the impregnation agent of this invention provides the lubricant for plastic working of a metal material which can prevent generation | occurrence | production of a film waste to the maximum.

(Measures to solve the subject)

The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result, organic modified clay minerals carrying cationic organic compounds between layers (preferably, layered clay minerals and cationic organic compounds having exchangeable cations between layers) The inventors have found that a lubricant containing an organic modified clay mineral obtained by ion exchange in a specific ratio can have both performance of both plastic resistance and friction reducing ability, and has completed the present invention.

As one of the features of the present invention, remarkable contamination in a working environment possessed by a lubricant containing a black solid lubricant such as molybdenum disulfide or graphite, due to its non-black appearance, is eliminated by applying the present invention.

In addition, because organic compounds expressing friction reducing ability between layers of layered clay minerals expressing fire resistance are supported by chemical bonding, local deposition due to flow in the mold caused by general lubricant components occurs. It is difficult to do so, which leads to the effect of not having to use lubricant components such as soaps and waxes or reducing them as much as possible.

As a result, the problem of the shaping | molding defect by the deposition of lubrication waste which the lubricating agent for general plastic processing which contains a large amount of the lubrication waste which became the cause of lubrication waste is improved by this invention.

The lubricant of the present invention is coated with a binder component or the like, and then coated, immersed, or the like as a well-known means, followed by drying the moisture contained therein, thereby interposing the friction material between the metal material to be processed and the tool such as a mold. Can be.

In addition, the external appearance like a black system and a non-black system in this invention is defined here.

There are three main components of the expression of color: hue indicating hue, brightness indicating brightness, and saturation indicating sharpness.

Among them, brightness is high when it is white and low when it is black, and the sensory degree of contamination is easy to be expressed.For example, an antifouling material evaluation promoting test of a structure performed by (Re) Uses the difference in brightness as an indicator of pollution.

Therefore, it is considered that as the material having low brightness is scattered, it becomes a significant contamination, and the brightness of each solid lubricant powder is actually measured for molybdenum disulfide and graphite.

The measurement was carried out using a color chrominometer after penetrating a glass plate to a sample having a proper amount of solid lubricant powder placed in a glass chalet and vertically compressed to a thickness of 2 mm (Konica Minolta CR-300, D65 light source, CAE Lab colorimeter). L value).

As a result, molybdenum disulfide was about 45 and graphite was about 40.

From this, contamination lower than the brightness value of molybdenum disulfide and graphite, which is a significant contamination in practical use, that is, in the appearance of a dark color, of course, becomes a prominent material. It is thought that this material becomes hard to be outstanding.

Therefore, without considering hue and saturation, the lightness is used as an index, and the dark color below brightness 50 is set to "black system", and the light color of brightness 50 or more is set to "non-black system".

(Measures to solve the task)

There are two types of film dregs: when the film is softened by the processing heat and adheres to the mold, and when the film is dropped due to plastic deformation and adhered to the mold. In order to solve the former, it is necessary to control the compounding quantity of the lubricating component (C) which is easy to stick with process heat. Moreover, in order to solve the latter, it is necessary to control the compounding quantity of (A) organic modified clay mineral which inhibits the adhesiveness of a lubricating film. Specifically, in the composition of the formulation, the imposition is made by (A) organo-modified clay mineral in the range of 2 to 5% by mass in solid content, and (C) the lubricant component in the range of 1 to 10% by mass in solid content. The first is achieved.

As described above, as a corresponding effect with the main subject, the non-black-based plastic working lubricant of the metallic material, characterized in that it contains an organic modified clay mineral carrying a cationic organic compound in the interlayer at a specific ratio. Both the negative and friction reducing ability can be exhibited. By the application of the present invention, it is possible to achieve the effect of solving the problems of the plastic working lubricants (contamination problems in the working environment of the black solid lubricant-containing lubricant and the problem of poor molding due to the deposition of lubrication residues). .

Moreover, since the generation | occurrence | production of a film dreg can be prevented as much as an effect corresponding to the said emulsifier, it exhibits the effect that it becomes possible to omit precision forging.

1 shows a hermetically sealed extrusion mold used in hermetically closed extrusion testing in Examples (Examples corresponding to subjects).
Fig. 2 is a principle diagram of the spike test in the embodiment (the embodiment corresponding to the subsidiary) and the appearance after forging.
FIG. 3 is a schematic of the upset forging-ball ironing test in the examples (the examples corresponding to the sub-view) and the appearance after the test.

The content of the present invention is described in more detail below.

≪Lubricant for plastic working≫

(Component A: organic modified clay mineral)

ㆍ Layered Clay Minerals

The layered clay mineral, which is a raw material of the organic modified clay mineral according to the present invention, acts as a base material to impart plasticity resistance and friction reducing ability and is capable of ion exchange reaction with a cationic organic compound which improves lubricity between layers. One having a cation between layers is used.

Examples of the layered clay minerals include natural products such as smectite (montmorillonite, baydelite, nontronite, saponite, iron saponite, hectorite, and soconite), stevensite, vermiculite, mica, and mica group. Or although at least 1 sort (s) chosen from a synthetic product is illustrated, More preferably, it is a synthetic clay mineral of a small particle size, As a specific example, it is synthetic mica and hectorite type synthetic smectite.

In particular, hectorite-type synthetic smectite has a small particle diameter and is easily retained in a lubricant that becomes an extremely thin film at the friction interface, which is preferable for the present invention.

The primary particles of the hectorite-type synthetic smectite are secondary elemental plates having a thickness of about 1 nm, that is, rectangular or disc shaped plates, and one side or diameter of the plate surface is considered to be 20 to 500 nm, and has a thickness of about 1 nm and 20 to Synthetic products that are discotic particles having a diameter of 40 nm are sold.

In addition, about the synthesis | combination of hectorite type smectite, hydrothermal synthesis etc. which are disclosed by Unexamined-Japanese-Patent No. 61-12845, Unexamined-Japanese-Patent No. 5-279012, etc. are mentioned, for example. Examples of the synthesis of mica include, for example, a method of synthesizing by heat treatment of talc, a transition metal compound, and silicicated alkali disclosed in JP-A-6-298522. Each exists as a ready-made product and the process is not important.

Here, a general layered clay mineral and its structure will be described.

Clay minerals are the main constituent minerals that make up the clay, and are layered silicate minerals (phyllosilicate minerals), calcite (calcite), high lime (dollomite), feldspars, quartz, fluorite (zeolites), and others with a chain structure ( Attapulgite, Sepiolite, etc.) and those which do not have a definite crystal structure (alpine) are called clay minerals, but in general, layered silicate minerals are called layered clay minerals.

Layered clay minerals are formed by stacking two-dimensional layers of positive ions in parallel to form a crystalline structure, in which two structural units, one with Si ⁴⁺ and an O ^{2 −} surrounding it, are formed. consisting of tetrahedral layers, except that ^{3 +} Al (OH) (or Mg ^{2 +,} Fe ^{2 +,} etc.) and surrounding it ^- is composed of an octahedral layer comprising a.

In the tetrahedral layer, tetrahedrons of Si-O are formed by O at four vertices of tetrahedron and Si located at the center, which are connected to each other at three vertices and enlarged two-dimensionally, and have a composition of Si ₄ O ₁₀ . The layered grid is formed. Si ^{4 +} are often substituted by Al ^{+ 3.}

In the octahedral layer, octahedrons formed by (OH) or O at six apexes of the octahedron and Al, Mg, Fe, etc., located at the center thereof are connected at each apex and expanded two-dimensionally, thereby Al ₂ (OH) ₆ Or layer lattice having a composition of Mg ₃ (OH) ₆ .

In the octahedral layer, and a divalent cation in the lattice points of the cation surrounded by six negative ions (Mg ^{+ 2,} and so on) into the 3-octahedral, which accounts for all of the lattice points body, the lattice points of the cation trivalent cations (Al ^{+ 3,} etc. ) Occupy two thirds, and the third one is empty, octahedral.

There are two types of tetrahedral layers and octahedral layers, one of which is a 1: 1 type structure based on the combination of one tetrahedral layer and one octahedral layer, and the other two tetrahedral layers and one sandwiched therebetween. There is a 2: 1 type structure based on the bond of the octahedra layer of the hawk.

In the tetrahedron layer is usually 1 Si ^{+ 4} is taking four O atoms surrounded by a stable coordination, but sometimes present in the tetrahedral layer, instead of the slightly larger ionic radius than Al ^{3 +} a Si ^{+ 4} Si ^{4 +.}

The number of coordinating atoms and O, the tetrahedral layer, generating a negative charge of one unit each time one of the Al ^{3 +} are substituted to the Si ^{+ 4} since there is no change.

Similarly, in the octahedral layer generates a negative electric charges depending on the Al ^{+ 3,} Fe ^{3 +} substitutions by Mg ^{2 +,} Fe ^{2 +.}

Layer caused the negative charges ^{is, Li +, K +, Na} +, NH 4 +, H 3 O +, Ca 2 +, Mg 2 +, Sr 2 +, Ba 2+, Co 2 +, Fe 2 +, Al ^{+ 3} by sandwiching a cation of being electrically neutral, is a layered structure of these exchangeable cations present in the interlayer.

ㆍ cationic organic compounds

The cationic organic compound (an organic compound inserted and supported between layers), which is a raw material of the organic modified clay mineral according to the present invention, has an excellent effect as a lubricant that increases the layer spacing of the layered clay mineral and improves lubricity between the layers. Indicates.

As said organic compound, at least 1 type of cationic organic compound (organic + cationic group) chosen from an organic ammonium compound, an organic phosphonium compound, and an organic sulfonium compound is mentioned. Here, although the organic group which the said organic compound has is not specifically limited, A C1-C30 linear, branched, or cyclic (having a cyclic group) saturated hydrocarbon group or unsaturated hydrocarbon group is preferable. Moreover, the hydrogen atom couple | bonded with the carbon atom which comprises a carbon chain or a carbocyclic ring may be substituted by another substituent, and some carbon atoms which comprise a carbon chain or carbocyclic ring are another atom (for example, O, S, etc.). ), And may further contain other bonds (eg, ester bonds, ether bonds) between the CC chains. Preferred are organic ammonium compounds composed of aliphatic hydrocarbon groups (preferably having from 1 to 30 carbon atoms) which are advantageous for friction reducing ability and ammonium groups which are advantageous in fixing ability between layers. Here, as organic salts used when introducing the organic compound between the layers, chloride, bromide, iodide, nitride, fluoride, hydroxide and the like are preferable. Particularly preferred organic salts include quaternary ammonium chlorides (capryltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dicapryldimethylammonium chloride, dilauryldimethylammonium chloride, dise) which are easy to flush off byproduct salts. Tearyldimethylammonium chloride, etc.).

ㆍ The ratio of layered clay mineral / cationic organic compound

It is preferable to ion exchange 0.8-1.2 molar amount of cationic organic compound of the cation exchange capacity (CEC) which each layered clay mineral has.

ㆍ Method of producing organic modified clay mineral

As a manufacturing method (means for inserting and supporting an organic compound between layers of layered clay minerals) as an organic modified clay mineral, it is performed by organicization of the clay mineral which is a well-known technique.

As described above, the layered clay mineral has a laminated structure in which cations exist between layers in order to maintain the negative charge in the layer structure as electrical neutral, and when dispersed in an aqueous phase, the cations are hydrated and the particles swell to form a layered plate (層 小 板) is separated.

In this state, a cationic organic salt as an organic agent is coexisted to perform an ion exchange reaction, and a by-produced salt is washed, removed, dried and pulverized to obtain an organic modified clay mineral as a powder material in which an organic compound is inserted and supported between the layers.

The type of exchangeable cation in the layered layered clay mineral in the present invention is preferably Li ⁺ and Na ⁺ from the ease of hydration or substitution, but other than that can be used, for example, Ca ^{2 +} is present between the layers. In the case of the layered clay mineral to be mentioned, it can be indirectly organicized by performing pretreatment such as substitution with Na ⁺ in an aqueous Na ₂ CO ₃ solution.

Moreover, about the means of producing the organic modified clay mineral which inserted the organic compound between the layered clay mineral layers, For example, Unexamined-Japanese-Patent No. 2-267113, 2002-348365, etc. He has the means, exists as ready-made, and the process is not important.

Moreover, the method of inserting directly or in an organic solvent, without passing through water may be sufficient.

ㆍ action mechanism

The organic compound supported between the layers of the layered clay mineral in the present invention is considered to exist in a state in which organic chains are grown between layers in a state in which a cationic group is adsorbed to a plate surface charged with a negative charge.

As an example, as an organic compound of the structure which has an ammonium group and an aliphatic hydrocarbon group, an ammonium group is adsorbed toward the plate surface of a layered clay mineral, and the aliphatic hydrocarbon group was made to grow between layers, and an aliphatic hydrocarbon group acts as a lubricant component, and it is an interlayer This is very easy to lubricate.

Since the lubricant component is supported between the layers, it can eliminate the need for lubricant components such as soaps and waxes, or exhibit friction reducing ability in a form that minimizes the friction. Local lubrication by flow in the mold during processing Since depositing of dregs becomes very difficult to occur compared with general plastic processing lubricants, the problem of molding failure caused by the deposition of lubricated dregs is improved.

Regarding the appearance of the organic modified clay mineral of the present invention, the brightness of the synthetic hectorite powder and the untreated synthetic hectorite powder which were organically treated with distearyldimethylammonium chloride as an example were measured in the same manner as above. Since all were about 95 and are non-black in appearance, they are suitable for the present invention for the purpose of improving the pollution problem of the working environment.

As a case of combining a layered clay mineral and an organic compound, in the "release agent for plastic processing" (Japanese Patent Laid-Open No. 56-145994), a mixture containing mica powder and lead having an initial point of 230 ° C or higher (lead / mica ratio) = 1.5 to 9) is proposed for the same purpose as the present invention, but this is not described as the lead vapor generated during hot forging exhibits a releasing performance, so as to lubricate the interlayers, and a large amount of lubricant components Because of the mixture contained, lubrication dregs are liable to occur, for example, when the composition is applied in cold forging.

For materials in which organic compounds are intercalated between layers of layered clay minerals, the main purpose is to impart properties in organic materials, for example, to swell in organic solvents, to impart viscosity, or to improve mechanical properties due to kneading with various organic materials and a barrier effect. to be.

Although generally used as a viscous agent in coatings and greases in the field of lubrication, the organic compound between layers provides swelling property in an organic solvent, and the action of an organic compound differs from this invention.

In addition, in "Organic clay composite and its manufacturing method" (Japanese Patent Laid-Open No. 2006-52136), melt kneading with a high melting point polymer material or polymerization reaction with a material in which an organic compound is inserted between layers of layered clay minerals The contents provided as a heat-resistant filler which endures and disperse | distributes with respect to an organic solvent, or exhibits sufficient thickening effect are mentioned.

The organic compound here is also selected for the purpose of affinity with a polymer material or an organic solvent, and is different from the action of the organic compound of the present invention.

(Component B: Binder Component)

As the lubricant of the present invention, (A) a binder component which is used as a coating component for introducing and retaining (A) an organic modified clay mineral or other compounding components at a friction interface with a mold, includes sulfate, silicate, borate, molybdate and vanadium. Water-soluble inorganic salts such as acid and tungstate salts, water-soluble organic salts such as malate, succinate, citrate and tartarate salts, acrylic resins, amide resins, epoxy resins, phenolic resins, urethane resins and polymaleic acid resins Although the organic polymer of is illustrated, there is no restriction | limiting in particular and it selects in consideration of a requirement item.

(Component C: lubricant component)

As the lubricant component (C) used in the lubricant of the present invention, soaps (sodium stearate, potassium stearate, sodium oleate, etc.), metal soaps (calcium stearate, magnesium stearate, aluminum stearate, barium stearate, At least one selected from lithium stearate, zinc stearate, calcium palmitate and the like) and waxes (polyethylene wax, polypropylene wax, carnauba wax, beeswax, paraffin wax, microcrystalline wax, etc.) It may contain.

(Component D: Other Ingredients)

The lubricant of the present invention can be appropriately selected and contained as examples by way of example, as the other components.

In addition, the addition of a small amount of black solid lubricants such as molybdenum disulfide, tungsten disulfide, graphite, etc. does not impair the object of the present invention, but depending on the amount of the compounding, it is necessary to consider it because of contamination of the working environment.

Solid lubricant

Molybdenum disulfide, tungsten disulfide, graphite, graphite fluoride, hexagonal boron nitride (h-BN), mica, talc, calcium carbonate, basic magnesium carbonate, basic zinc carbonate, calcium hydroxide, magnesium hydroxide, magnesium oxide, calcium phosphate, zinc phosphate, Tripolyphosphate aluminum dihydrogen, polytetrafluoroethylene (PTFE), melamine cyanurate, amino acid compound, etc.

ㆍ Extreme Pressure Additives

Sulfide olefins, sulfide esters, sulfites, thiocarbonates, chlorinated fatty acids, phosphate esters, phosphite esters, molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), zinc dithiophosphate (ZnDTP) Sulfur extreme pressure additives, organic molybdenum extreme pressure additives, phosphorus extreme pressure additives and chlorine extreme pressure additives, etc.

Corrosion Inhibitor

Phosphates, zirconium compounds, tungstates, vanadium salts, tungstates, silicates, borates, carbonates, amines, benzotriazoles, chelate compounds, etc.

ㆍ viscosity adjuster

Hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylic amide, sodium polyacrylate, polyvinylpyrrolidone, polyvinyl alcohol, smectite clay mineral, finely divided silica, bentonite, kaolin and the like

ㆍ Oils

Vegetable oil, mineral oil, synthetic oil, etc.

ㆍ Various surfactants or polymer dispersants for dispersing or emulsifying each component

Nonionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants, water-soluble polymer dispersants, etc.

(Liquid medium)

The liquid medium of the lubricant according to the present invention is preferably water (for example, deionized water or pure water). In addition, the liquid medium may contain other liquid medium other than water (for example, alcohol). In this case, the total mass of the liquid medium is preferably 10% by mass or less. In addition, the formulations may be in dry or concentrated form. In this case, dilute with water in the field.

(Furtherance)

Next, the composition of each component contained in the lubricant concerning this invention is demonstrated.

ㆍ Content of component A

The lubricant of the present invention contains the organic modified clay mineral in the range of 5 to 95% by mass in solid content, but if less than this range, the lubricity and plasticity resistance are insufficient, and if more than this range, the organic modified clay mineral is contained in the film. It becomes difficult to hold | maintain, and it becomes impossible to express baking resistance. More preferably, the said organic modified clay mineral is 10-40 mass% in solid content ratio.

ㆍ Content of component A / component B

The lubricant of the present invention has a total content of (A) organic modified clay mineral and (B) binder component in the range of 30 to 100 mass% in solid content ratio, and the mass ratio of (A) and (B) is (A) / (B) = 5/95 to 95/5.

More preferably, the sum total of (A) and (B) is 50-90 mass% in solid content ratio, and the mass ratio of (A) and (B) is (A) / (B) = 15 / 85-65 / It is in the range of 35.

ㆍ Content of component A / component C (content of + component C)

The lubricant of the present invention has a mass ratio of (A) organic modified clay mineral and (C) lubricant component in the range of (A) / (C) = 25/75 to 100/0, and (C) to 0 to 25 in solid content It consists of the range of mass%.

Although (C) may be included for the purpose of supplementing the friction reducing ability, it is preferable to make it as small as possible because it causes lubrication residue.

`` Lubricant for firing (particularly forging lubricant) ''

Although the above is description in the whole plastic working, when it is assumed that the use of forging, especially the forging of precision, is abbreviate | omitted, it is preferable that a agent is the following composition.

(Component A to Component C)

The forging lubricant may be a combination of any of components A to C in the description of the overall plastic working. However, in view of the above uses, synthetic smectite and / or synthetic mica as component A and water-soluble inorganic salts as component B ( Particular preference is given to combinations of silicates, borates, molybdates, tungstates) and / or polymaleic acid-based resins, as component C, with metal soaps and / or waxes. As component C, polyethylene wax and / or polypropylene wax are particularly preferred.

(Amount of component A and component C)

The forging lubricant contains the (component A) organic modified clay mineral in the range of 2 to 5% by mass in solid content. If it is less than this range, sinter resistance is insufficient. When it exceeds this range, a lubricating film will fall out by plastic deformation and will adhere to a metal mold | die, and moldability will become inadequate. More preferably, the said organic modified clay mineral component is 2-4 mass% in solid content ratio. In addition, the forging lubricant contains the (component C) lubricant component in 1 to 10 mass% of solid content ratio. If it is less than this range, the friction reducing ability is insufficient. When more than this range, a lubricating film will adhere to a metal mold | die, and moldability will become inadequate. More preferably, the said lubricant component is 5-7 mass% in solid content ratio.

(Ratio of components A and C)

The ratio {(A) / (C)} of the component (A) and the component (C) in the forging lubricant is preferably 2/10 to 5/1, more preferably 2/7 to 4/5 to be.

`` How to Use and Use Lubricants for Plastic Processing ''

The lubricant of the present invention may be a means for interposing a friction material between a metal material, which is to be processed, and a tool such as a mold for plastic working.

The lubricant of the present invention is applied to a tool such as a metal material or a mold to be a workpiece, and the moisture contained therein after drying is applied to a tool such as a metal material or a mold, which is a well-known means, and interposed at the frictional interface to prevent the sintering resistance in cold forging. The friction reducing ability can be provided.

In addition, before the lubricant of the present invention is interposed on the frictional interface between a metal material serving as the work material and a tool such as a mold, various ground treatments may be performed on the work material as necessary, such as significantly increasing the plastic resistance.

As the ground treatment here, zinc oxide phosphate treatment, iron phosphate zinc treatment, calcium phosphate treatment, iron phosphate treatment, iron oxalate treatment, zirconium oxide treatment, aluminum fluoride treatment, etc., chemical film treatment, alkali silicate treatment, alkali sulfate treatment, alkali Coating type coating treatments such as borate treatment, alkali metal salt treatment of organic acid salts and organic polymer coating treatment are exemplified, but there is no particular limitation.

Prior to depositing the composition of the present invention, the metal material used in the present invention is preferably cleaned by at least one or more methods selected from alkali washing, acid washing, sand blast and shot blast.

This is because when the metal surface is dirty, it adversely affects the adhesion of the lubricant and causes a problem in lubricity.

In recent years, it is desired not to generate waste liquid in terms of environmental conservation. In this case, the blast treatment can be used to clean the metal surface without generating waste water.

The metal material targeted in the present invention is not particularly limited in terms of material, but is made of metal such as iron, steel, stainless steel, copper, copper alloy, aluminum, aluminum alloy, titanium, titanium alloy, magnesium, magnesium alloy, or the like. Material is illustrated.

In addition, the metal material targeted by this invention in a shape is not specifically limited, For example, not only raw materials, such as a wire rod, a pipe | tube material, a rod material, and a block material, but also shaped objects (gears, a shaft, etc.).

`` Lubrication film formed using lubricant for plastic working ''

Adhesion amount of film formed by the above is in the range of 0.1 to 50 g / m ² which is necessary and, preferably of 0.5 to 30 g / m ^2, more preferably 1 to 25 g / m ^2. If it is less than 0.1 g / m <^2> , lubricity is inadequate and sufficient performance cannot be exhibited with respect to plastic working. When it exceeds 50 g / m < ² >, excess amount will become large, and the residue of a lubricating film will become easy to accumulate in a metal mold | die, and it is unpreferable also in terms of a cause of a molding defect, and a cost.

&Lt; Embodiment &gt;

Several examples are given below about this invention, and their usefulness is compared with a comparative example. In addition, the present invention will be described by dividing the example corresponding to the main subject and the example corresponding to the levy.

{One. Example corresponding to main subject}

About the prescription of an Example and a comparative example, the component type, solid content ratio, and coating amount of (A)-(D) were described in Table 1. Subsequently, the detail of the manufacturing method of (A) and the processing liquid preparation method was described. In addition, the ratio in Table 1 is a mass part.

(A) organic modified clay mineral

(B) binder component

(C) lubricant components

(D) other components

≪ (Component A) Production Method of Organic Modified Clay Minerals≫

(Synthetic mica (organic A))

50 g of synthetic mica (manufactured by Cope Chemical Co., Ltd .: Somasif ME-100; exchange cation = Na ⁺ ; CEC value = 120 meq / 100 g) was added to 1000 ml of deionized water, and stirred in a homogenizer for 1 hour in water. It disperse | distributed and it warmed at 90 degreeC, Then, 36 g (1.0 molar amount of CMC value) of distearyl dimethylammonium chloride (Kao Co., Ltd. product: Cotamine D86P) was added as an active ingredient, stirring with propeller. After that, stirring was continued for 1 hour, and the produced insoluble particles were filtered using filter paper (5 C), washed with deionized water, dried in a 60 DEG C warm air drying furnace for 16 hours, and then pulverized and synthesized. A powder of mica (organic A) was obtained.

(Synthetic smectite (organic A))

To 1000 ml of deionized water, 50 g of synthetic smectite (manufactured by Cope Chemical Co., Ltd .: Lucentite SWN; exchange cation = Na ⁺ ; CEC value = 101 meq / 100 g) was added and stirred in a homogenizer for 1 hour and dispersed in water. Then, 32 g (corresponding to 1.0 molar amount of CMC value) of distearyldimethylammonium chloride (manufactured by Kao Co., Ltd .: Cotamine D86P) was added while heating to 90 ° C. and stirring the propeller. After that, stirring was continued for 1 hour, and the produced insoluble particles were filtered using filter paper (5 C), washed with deionized water, dried in a 60 DEG C warm air drying furnace for 16 hours, and then pulverized and synthesized. A powder of smectite (organic A) was obtained.

(Natural montmorillonite (organic A))

50 g of natural montmorillonite (manufactured by Hojun Co., Ltd .: exchange gel cation = Na ⁺ ; CEC value = 115 meq / 100 g) was added to 1000 ml of deionized water, and stirred in a homogenizer for 1 hour and dispersed in water. Then, heated to 90 ° C., distearyldimethylammonium chloride (manufactured by Kao Co., Ltd .: Cotamine D86P) was added as an active ingredient with a propeller stirring to 27 g (corresponding to 1.0 molar amount of CMC value). After that, stirring was continued for 1 hour, and the produced insoluble particles were filtered using filter paper (5 C), washed with deionized water, dried in a 60 DEG C warm air drying furnace for 16 hours, and then ground to natural A powder of montmorillonite (organic A) was obtained.

(Synthetic smectite (organic B))

To 1000 ml of deionized water, 50 g of synthetic smectite (manufactured by Cope Chemical Co., Ltd .: Lucentite SWN; exchange cation = Na ⁺ ; CEC value = 101 meq / 100 g) was added and stirred in a homogenizer for 1 hour and dispersed in water. Then, 30 g (corresponding to 1.0 molar amount of CMC value) of dioleyldimethylammonium chloride (manufactured by Lion Co., Ltd .: Acad 2O-75I) was added as an active ingredient with warming to 90 ° C and propeller stirring. After that, stirring was continued for 1 hour, and the produced insoluble particles were filtered using filter paper (5 C), washed with deionized water, dried in a 60 DEG C warm air drying furnace for 16 hours, and then pulverized and synthesized. A powder of smectite (organic B) was obtained.

(Synthetic smectite (organic C))

To 1000 ml of deionized water, 50 g of synthetic smectite (manufactured by Cope Chemical Co., Ltd .: Lucentite SWN; exchange cation = Na ⁺ ; CEC value = 101 meq / 100 g) was added and stirred in a homogenizer for 1 hour and dispersed in water. Then, 17 g (corresponding to 1.0 molar amount of CMC value) of stearyltrimethylammonium chloride (manufactured by Kao Co., Ltd .: 86W) was added as an active ingredient while heating to 90 ° C. and stirring the propeller. After that, stirring was continued for 1 hour, and the produced insoluble particles were filtered using filter paper (5 C), washed with deionized water, dried in a 60 DEG C warm air drying furnace for 16 hours, and then pulverized and synthesized. A powder of smectite (organic C) was obtained.

(Natural Montmorillonite (Organic D))

50 g of natural montmorillonite (manufactured by Hojun Co., Ltd .: exchange gel cation = Na ⁺ ; CEC value = 115 meq / 100 g) was added to 1000 ml of deionized water, and stirred in a homogenizer for 1 hour and dispersed in water. Then, benzyl triphenylphosphonium chloride was added 22 g (1.0 molar amount of CMC value) as an active ingredient while heating to 90 degreeC and stirring propeller. After that, stirring was continued for 3 hours, and the produced insoluble particles were filtered using filter paper (5 C), washed with deionized water, dried in a 60 DEG C warm air drying furnace for 16 hours, and then ground to natural A powder of montmorillonite (organic D) was obtained.

(Synthetic mica (organic D))

50 g of synthetic mica (manufactured by Cope Chemical Co., Ltd .: Somasif ME-100; exchange cation = Na ⁺ ; CEC value = 120 meq / 100 g) was added to 1000 ml of deionized water, and stirred in a homogenizer for 1 hour in water. It disperse | distributed, after that, it heated at 90 degreeC and added the benzyl triphenyl phosphonium chloride as an active ingredient 23g (1.0 molar amount of CMC value), stirring propeller. After that, stirring was continued for 3 hours, and the produced insoluble particles were filtered using filter paper (5 C), washed with deionized water, dried in a 60 DEG C warm air drying furnace for 16 hours, and then pulverized and synthesized. A powder of mica (organic D) was obtained.

`` Processing solution preparation method of Examples ''

(Example 1)

77.4 g of deionized water was added with 16.8 g of potassium tetraborate while stirring with propeller, and it heated and dissolved at 60 degreeC. Thereafter, 0.2 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.6 g of the prepared synthetic mica (organic A) were added while stirring the propeller at room temperature, and the solution was stirred with a homogenizer for 1 hour. Dispersed in the middle. Thereafter, 4 g of a polyethylene wax emulsion (manufactured by Mitsui Chemical Industries, Ltd.) was added while stirring the propeller, and 100 g of a treatment liquid having a concentration of about 20% was obtained.

(Example 2)

Synthetic smectite (organic) made with 24.2 g of an epoxy resin aqueous solution (manufactured by Arakawa Chemical Industries, Ltd.), 0.4 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) while propeller stirring 58.1 g of deionized water (organic) 3 g of C) and 6 g of calcium carbonate were added, and this liquid was stirred with a homogenizer for 1 hour to disperse in the liquid. Thereafter, 8.3 g of a zinc stearate emulsion (produced by Chukyo Co., Ltd.) was added while stirring the propeller, thereby obtaining 100 g of a treatment liquid having a concentration of about 20%.

(Example 3)

76.2 g of deionized water was added with 13 g of sodium citrate while stirring with propeller, and it heated and dissolved at 60 degreeC. Thereafter, 0.2 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 3 g of the prepared synthetic smectite (organic C) and 2 g of zinc phosphate were added while stirring the propeller at room temperature, and the solution was homogeneous. The mixture was stirred for 1 hour with air and dispersed in the liquid. Thereafter, 5.6 g of a zinc stearate emulsion (produced by Chukyo Yushi Co., Ltd.) was added while stirring the propeller, thereby obtaining 100 g of a treatment liquid having a concentration of about 20%.

(Example 4)

179.8 g of potassium tetraborate was added while propeller stirring 79.8 g of deionized water, and the mixture was heated to 60 ° C to dissolve. Thereafter, 0.2 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 g of the prepared synthetic smectite (organic C) were added while stirring the propeller at room temperature, and the liquid was stirred with a homogenizer for 1 hour. It disperse | distributed in the inside and 100 g of process liquids of concentration about 20% were obtained.

(Example 5)

75.1 g of deionized water was added with 8 g of sodium silicate with propeller stirring, and the mixture was heated to 60 deg. C to dissolve. Then, while stirring the propeller at room temperature, 0.4 g of nonionic surfactant (made by Shin-Etsu Chemical Co., Ltd.), 5 g of produced synthetic smectite (organic A), and melamine cyanurate (Sakai Chemical Co., Ltd.) 4g) was added, and the liquid was stirred with a homogenizer for 1 hour to disperse in the liquid. Thereafter, 7.5 g of a polypropylene wax emulsion (manufactured by Mitsui Chemical Industries, Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

(Example 6)

Synthesis which produced 60 g of styrene-maleic anhydride aqueous solution (made by Nichiyu Solutions Co., Ltd.), 0.2 g of nonionic surfactants (made by Shin-Etsu Chemical Co., Ltd.), while stirring 28.2 g of deionized water. 5 g of smectite (organic A) and 1 g of untreated synthetic smectite (manufactured by Cope Chemical Co., Ltd.) were added, and the liquid was stirred with a homogenizer for 1 hour to disperse in the liquid. Thereafter, 5.6 g of a zinc stearate emulsion (produced by Chukyo Yushi Co., Ltd.) was added while stirring the propeller, and 100 g of a treatment liquid having a concentration of about 20% was obtained.

(Example 7)

73.4 g of deionized water was added with 5 g of sodium silicate while propeller stirring, and the mixture was heated and dissolved at 60 deg. Subsequently, while stirring the propeller at room temperature, 0.6 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of the prepared synthetic smectite (organic B), and 4 g of calcium carbonate were added, and the solution was homogeneous. The mixture was stirred for 1 hour with air and dispersed in the liquid. Thereafter, 10 g of a paraffin wax emulsion (manufactured by Nippon Siro Co., Ltd.) was added while stirring the propeller to obtain 100 g of the treatment liquid having a concentration of about 20%.

(Example 8)

77.6 g of deionized water was added with 9 g of potassium tetraborate while stirring with propeller, and it heated and dissolved at 60 degreeC. Then, 0.4 g of nonionic surfactants (manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of the prepared synthetic smectite (organic B) and 2 g of magnesium hydroxide were added while stirring the propeller at room temperature, and the solution was homogeneous. The mixture was stirred for 1 hour with air and dispersed in the liquid. Thereafter, 4 g of a calcium stearate emulsion (manufactured by Kindai Chemical Co., Ltd.) was added while stirring the propeller, thereby obtaining 100 g of a treatment liquid having a concentration of about 20%.

(Example 9)

4 g of sodium vanadate was added while propeller stirring 74.9 g of deionized water was heated, and it melt | dissolved at 60 degreeC. Thereafter, while stirring the propeller at room temperature, 0.6 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 9 g of the produced synthetic mica (organic A), and 4 g of talc (made by Nippon Talc Co., Ltd.) It was added, and this liquid was stirred with a homogenizer for 1 hour and dispersed in the liquid. Thereafter, 7.5 g of a polyethylene wax emulsion (manufactured by Mitsui Chemical Industries, Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

(Example 10)

79.4 g of deionized water was stirred with propeller, and 7 g of sodium succinate was added and dissolved by heating to 60 캜. Subsequently, while stirring the propeller at room temperature, 0.6 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 9 g of the produced synthetic mica (organic A), and untreated synthetic mica (manufactured by Kope Chemical Co., Ltd.) 2 g and 2 g of lithium stearate were added, the solution was stirred with a homogenizer for 1 hour and dispersed in the liquid to obtain 100 g of a treatment liquid having a concentration of about 20%.

(Example 11)

55 g of isobutylene-maleic anhydride aqueous solution (manufactured by Kuraray Co., Ltd.) and 0.4 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) were produced while propeller stirring with 35.6 g of deionized water. 9 g of synthetic mica (organic A) was added, and the liquid was stirred with a homogenizer for 1 hour to disperse in the liquid, thereby obtaining 100 g of a treatment liquid having a concentration of about 20%.

(Example 12)

76.6 g of deionized water was added with 5 g of polyamide resin (manufactured by Toray Co., Ltd.) while stirring the propeller, and the mixture was heated to 60 ° C and dissolved. Thereafter, 0.4 g of a nonionic surfactant (produced by Shin-Etsu Chemical Co., Ltd.), 11 g of produced natural montmorillonite (organic A) and 2 g of calcium carbonate were added while stirring the propeller at room temperature, and the solution was homogeneous. The mixture was stirred for 1 hour with air and dispersed in the liquid. Thereafter, 5 g of a polypropylene wax emulsion (manufactured by Mitsui Chemical Industries, Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

(Example 13)

79.4 g of deionized water was added with 7 g of sodium tartrate while propeller stirring, and the mixture was warmed to 60 deg. C to dissolve. Thereafter, while stirring the propeller at room temperature, 0.6 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 11 g of the produced synthetic smectite (organic B), and a layered amino acid compound (manufactured by Ajinomoto Co., Ltd.) ) 2g) was added, and this liquid was stirred with a homogenizer for 1 hour and dispersed in the liquid to obtain 100 g of a treatment liquid having a concentration of about 20%.

(Example 14)

 79.4 g of deionized water was added with 5 g of ammonium molybdate while propeller stirring, and the mixture was heated and dissolved at 60 ° C. Thereafter, 0.6 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 13 g of the prepared synthetic smectite (organic A), and 2 g of barium stearate were added thereto while stirring the propeller at room temperature. It stirred for 1 hour with the homogenizer, and disperse | distributed in liquid, and obtained 100 g of process liquids with a density | concentration of about 20%.

(Example 15)

13.3g of polyurethane resin aqueous solution (made by Adeka Co., Ltd.) was added, stirring 68.6g of deionized waters, and it melt | dissolved by heating at 60 degreeC. Thereafter, while stirring the propeller at room temperature, 0.6 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 15 g of the prepared synthetic smectite (organic C) were added, and the solution was stirred with a homogenizer for 1 hour. Dispersed in the middle. Thereafter, 2.5 g of a microcrystalline wax emulsion (manufactured by Nippon Siro Co., Ltd.) was added while stirring the propeller to obtain 100 g of the treatment liquid having a concentration of about 20%.

(Example 16)

88.2 g of deionized water was stirred with propeller, and 3.5 g of potassium tetraborate was added and dissolved by heating to 60 캜. Thereafter, 0.3 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 3.5 g of the prepared synthetic smectite (organic A) and 1.5 g of magnesium hydroxide were added while stirring the propeller at room temperature, and the solution was homogeneous. The mixture was stirred for 1 hour with air and dispersed in the liquid. Thereafter, 3 g of a calcium stearate emulsion (manufactured by Kindai Chemical Co., Ltd.) was added while stirring the propeller, thereby obtaining 100 g of a treatment liquid having a concentration of about 10%.

(Example 17)

14 g of sodium succinate was added with 53.2 g of deionized water with propeller stirring, and it heated and dissolved at 60 degreeC. Thereafter, 0.8 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 18 g of the prepared synthetic smectite (organic B) and 4 g of zinc phosphate were added thereto while stirring the propeller at room temperature. The mixture was stirred for 1 hour with air and dispersed in the liquid. Thereafter, 10 g of a polyethylene wax emulsion (manufactured by Mitsui Chemical Industries, Ltd.) was added while stirring the propeller, and 100 g of a treatment liquid having a concentration of about 40% was obtained.

(Example 18)

Synthetic mica (organic mica) produced with 6.7 g of a non-ionic surfactant (produced by Shin-Etsu Chemical Co., Ltd.) and 6.7 g of an aqueous phenol resin solution (manufactured by Konishi Kagaku Kogyo Co., Ltd.) while propeller stirring 35.8 g of deionized water. 18 g of A) was added, and the liquid was stirred with a homogenizer for 1 hour to disperse in the liquid, thereby obtaining 100 g of a treatment liquid having a concentration of about 20%.

(Example 19)

77.8 g of deionized water was added with 9 g of potassium tetraborate while stirring with propeller, and it heated and melt | dissolved at 60 degreeC. Then, 0.4 g of nonionic surfactants (manufactured by Shin-Etsu Chemical Co., Ltd.) and 9 g of natural montmorillonite (organic D) produced were added while stirring the propeller at room temperature, and the liquid was stirred with a homogenizer for 1 hour. Dispersed in the middle. Thereafter, 3.8 g of calcium stearate emulsion (manufactured by Kindai Chemical Co., Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

(Example 20)

76.6 g of deionized water was added with 11 g of sodium silicate while propeller stirring, and the mixture was heated and dissolved at 60 deg. Thereafter, 0.4 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 7 g of the prepared synthetic mica (organic D) were added while stirring the propeller at room temperature, and the liquid was stirred with a homogenizer for 1 hour. Dispersed in the middle. Thereafter, 5 g of a polyethylene wax emulsion (manufactured by Mitsui Chemical Industries, Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

≪Processing liquid production method of the comparative example≫

(Comparative Example 1)

80 g of styrene-maleic anhydride aqueous solution (manufactured by Nichiyu Solution Co., Ltd.), 0.2 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) while producing 12.4 g of deionized water with propeller stirring 0.6 g of mica (organic A) was added, and the liquid was stirred with a homogenizer for 1 hour to disperse in the liquid. Thereafter, 6.8 g of calcium stearate emulsion (manufactured by Kindai Chemical Co., Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

(Comparative Example 2)

79.6 g of deionized water was added with 0.6 g of potassium tetraborate while stirring with propeller, and it heated and dissolved at 60 degreeC. Thereafter, 0.4 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 19.4 g of the prepared synthetic smectite (organic B) were added while stirring the propeller at room temperature, and the liquid was stirred with a homogenizer for 1 hour. It disperse | distributed in the inside and 100 g of process liquids of concentration about 20% were obtained.

(Comparative Example 3)

55 g of isobutylene-maleic anhydride aqueous solution (manufactured by Kuraray Co., Ltd.), 0.4 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), untreated with 35.6 g of deionized water and propeller stirring 9 g of synthetic mica (manufactured by Cope Chemical Co., Ltd.) was added, and the liquid was stirred with a homogenizer for 1 hour to disperse in the liquid, thereby obtaining 100 g of a treatment liquid having a concentration of about 20%.

(Comparative Example 4)

While stirring 48.8 g of deionized water, 30 g of an isobutylene-maleic anhydride aqueous solution (manufactured by Kuraray Co., Ltd.), 0.2 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), untreated 6 g of synthetic mica (manufactured by Cope Chemical Co., Ltd.) was added, and the liquid was stirred with a homogenizer for 1 hour to disperse in the liquid. Thereafter, 15 g of a polyethylene wax emulsion (manufactured by Mitsui Chemical Industries, Ltd.) was added while stirring the propeller, thereby obtaining 100 g of a treatment liquid having a concentration of about 20%.

(Comparative Example 5)

79.4 g of deionized water was added to 6 g of sodium citrate while stirring the propeller, and the mixture was heated to 60 DEG C to dissolve. Then, while stirring the propeller at room temperature, 0.6 g of nonionic surfactants (manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of melamine cyanurate (manufactured by Sakai Chemical Industries, Ltd.), and 7 g of barium stearate The solution was stirred for 1 hour with a homogenizer and dispersed in the solution to obtain 100 g of a treatment liquid having a concentration of about 20%.

(Comparative Example 6)

30 g of isobutylene-maleic anhydride aqueous solution (made by Kuraray Co., Ltd.), 0.2 g of nonionic surfactants (made by Shin-Etsu Chemical Co., Ltd.), zinc phosphate, stirring 42.3 g of deionized waters with a propeller 5 g was added, and this liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid. Thereafter, 22.5 g of a polyethylene wax emulsion (manufactured by Mitsui Chemical Industries, Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

(Comparative Example 7)

75.6 g of deionized water was added with 8 g of sodium tartrate while propeller stirring, and the mixture was heated and dissolved at 60 ° C. Thereafter, 0.4 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 8 g of PTFE (manufactured by Sumitomo 3M Co., Ltd.) were added while stirring the propeller at room temperature, and the solution was stirred with a homogenizer for 1 hour. It was dispersed in the liquid. Thereafter, 8 g of a calcium stearate emulsion (manufactured by Kindai Chemical Co., Ltd.) was added while stirring the propeller, and 100 g of a treatment liquid having a concentration of about 20% was obtained.

(Comparative Example 8)

72.1 g of deionized water was added with 5 g of sodium silicate with propeller stirring, and the mixture was heated to 60 deg. C to dissolve. Thereafter, 0.4 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 10 g of molybdenum disulfide were added while stirring the propeller at room temperature, and the liquid was stirred with a homogenizer for 1 hour and dispersed in the liquid. Thereafter, 12.5 g of a paraffin wax emulsion (manufactured by Nippon Siro Co., Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

(Comparative Example 9)

30 g of polyurethane resin aqueous solution (made by Adeka Co., Ltd.) was added, stirring 47.7 g of deionized water, and it heated and melt | dissolved at 60 degreeC. Thereafter, 0.6 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of graphite were added while stirring the propeller at room temperature, and the solution was stirred with a homogenizer for 1 hour and dispersed in the liquid. Thereafter, 16.7 g of a zinc stearate emulsion (produced by Chukyo Yushi Co., Ltd.) was added while stirring the propeller, and 100 g of the treatment liquid having a concentration of about 20% was obtained.

≪Test method≫

(Closed extrusion test)

<Test piece material>

Cylindrical shape (diameter 11.8mm φ * 20mm) of SAE1008 (tensile strength 488MPa)

<Treatment process>

■ Purification: Alkali degreasing and commercial alkali degreasing agent (Fine Cleaner 4360, Nippon Parkering Co., Ltd.) concentration were 20 g / L, temperature 60 degreeC, and immersion for 10 minutes.

■ washing with water: 1 minute of tap water, room temperature, immersion.

■ Surface treatment: The test piece was immersed and applied to each level of chemical | medical agent, and it dried on the conditions of 100 degreeC and 30 minutes.

<Processing Conditions>

Extrusion of the test piece is performed by a servo press using the closed extrusion die shown in Fig. 1, and chemical conversion treatment (soap lubrication treatment on zinc phosphate chemical conversion coating) is performed on the processing load at this time. Lubricity) was evaluated by comparison with.

<Evaluation Criteria>

ㆍ lubrication

◎: average processing load is less than

○: average machining load is equal to or less than 10% increase

(Triangle | delta): The average processing load is more than 10%-20% increase or less of this bond

X: average processing load exceeds 20% of bond

≪Spike test≫

<Test piece material>

Cylindrical shape (25mm diameter, 30mm in height) of S45C spheroidizing annealing material

<Treatment process>

■ Purification: Alkali degreasing and commercial alkali degreasing agent (Fine Cleaner 4360, Nippon Parkering Co., Ltd.) concentration were 20 g / L, temperature 60 degreeC, and immersion for 10 minutes.

■ washing with water: 1 minute of tap water, room temperature, immersion.

■ Surface treatment: The test piece was immersed and applied to each level of chemical | medical agent, and it dried on the conditions of 100 degreeC and 30 minutes.

<Processing Conditions>

According to the invention of Japanese Patent Laid-Open No. 5-7969, a flat mold (SKD11) constrained and finished on the upper side using a 200-ton crank press, and a funnel-shaped mold (SKD11) mirror-finished on the bottom, were set The test piece was placed in the center of the mold and hit from the upper side (machining speed was 30 strokes / minute). The degree of burning of the spike tip portion of the test piece after processing was observed to evaluate the fire resistance.

<Evaluation Criteria>

ㆍ Spark resistance

The spike tip of the test piece after processing is observed to evaluate the presence or absence of quench.

○: no baking

△: small baking

X: Severe firing

≪Upset forging processing test≫

<Test piece material>

Cylindrical shape (25mm diameter, 30mm in height) of S45C spheroidizing annealing material

<Treatment process>

■ Purification: Alkali degreasing and commercial alkali degreasing agent (Fine Cleaner 4360, Nippon Parkering Co., Ltd.) concentration were 20 g / L, temperature 60 degreeC, and immersion for 10 minutes.

■ washing with water: 1 minute of tap water, room temperature, immersion.

■ Surface treatment: The test piece was immersed in each level of chemical | medical agent, and it dried in the warm air electric furnace of 100 degreeC setting for 1 hour (surface treatment of the comparative example 2 was performed by the method of the item of a level).

<Processing Conditions>

Using a 200-ton crank press, a flat mold (SKD11) with both top and bottom mirrors was set, the test piece was placed in the center of the bottom mold and hit from the upper side so that the compression ratio was about 50% (processing speed is 30 strokes / min). ). Three test pieces were processed continuously, and the grade of the lubrication waste deposited on the lower metal mold | die was observed and evaluated.

<Evaluation Criteria>

ㆍ lubrication residue

Lubrication residue deposited on the lower mold after processing is observed and evaluated.

(Circle): There is little deposition or there is little and is easily eliminated.

(Triangle | delta): It is easy to remove although there are some depositions a little

X: There are many deposits and there are signs of fusion

≪Work environmental assessment≫

In each of the above processing tests, the contamination situation around the mold during operation was observed.

<Evaluation Criteria>

ㆍ Work Environment

○: little or no visible contamination

×: noticeable contamination such as blackness occurs

Table 2 shows the results of the above test.

Examples 1 to 20 using the present invention express a practical level of lubricity and fire resistance, and it can be seen that lubrication residues generated during processing are small.

As a comparison, in Comparative Example 1 where the organically modified clay minerals are few, the lubricity and seizure resistance are inferior, and in Comparative Example 2 which is too much, the seizure resistance and lubrication residue are inferior due to the dropping of components.

In Comparative Example 3 containing a layered clay mineral containing no organic compound, the lubricity is poor, and in Comparative Example 4 containing the lubricant component to replenish it, the lubrication residue is inferior.

Comparative Examples 5 to 7, which are a combination of a general solid lubricant and a lubricant component, tended to have a contradictory evaluation of lubricity, baking resistance and evaluation of lubrication residue.

Comparative Examples 7 and 8 using a black solid lubricant had good lubricity and fire resistance, but naturally had a black stain around the mold.

{2. Example corresponding to imposition agent}

Table 3 shows an example of the determination result (friction reduction ability) in the spike test at the time of changing the combination of components A-C. Moreover, the adhesion amount of the lubricating film was 10 g / m <^2> (other test is also the same). 2 is a schematic diagram of the spike test in this example and an appearance after forging. In addition, matters which are not specially mentioned, such as a manufacturing method of an agent, "1. Example corresponding to the main subject ". As can be seen from this table, it was confirmed that the combination of synthetic mica or montmorillonite as component A, potassium tetraborate, sodium tungstate or sodium molybdate as component B, and polyethylene wax as component C was particularly good with respect to the friction reducing ability. . Moreover, it turned out that friction reducing ability is ensured when 1 mass% of wax is contained as a lower limit from this result. In addition, below, among these preferable combinations, the test result about synthetic mica as an A component, potassium tetraborate as a B component, and polyethylene wax as a C component is described as an example. In addition, in the following table, "%" shows the "mass%" unless it mentions specially.

Table 4 shows the results of verifying the amount of deposit electrodeposited to the mold when the solid content of polyethylene wax was changed after fixing the synthetic mica at 3 mass% (upset forging test). From this result, it turned out that even if it contains up to 10 mass% as an upper limit, even if it contains wax, the deposit amount of residue to a metal mold | die can be ensured.

In addition, Table 5 shows the result of verifying that the film residue is difficult to fall off when the solid content of the synthetic mica is fixed after fixing the polyethylene wax to 5% by mass (restraint upset forging test (upset forging-ball ironing test). )). 3 is a principle diagram of the upset forging-ball ironing test in the present example and an appearance after the test. From this result, it turned out that when it is an upper limit to 5 mass%, even if it contains an organic modified clay mineral, it is hard to fall off the film dregs.

Table 6 shows the determination results (resistance to fire) in the upset forging-ball ironing test when the content of organic modified clay mineral was changed after fixing the polyethylene wax to 5% by mass. From this result, it turned out that sedimentation resistance can be ensured when 2 mass% of organic modified clay minerals are contained as a lower limit.

Claims (12)

An organic modified clay mineral carrying a cationic organic compound between layers of a layered clay mineral, in a solid content, in the range of 5 to 95 mass%, a lubricant for plastic working of a metal material. 2. The layered clay mineral according to claim 1, wherein the layered clay mineral is smectite (montmorillonite, baydelite, nontronite, saponite, iron saponite, hectorite, soconite), stevensite, vermiculite, mica, brood It is at least 1 sort (s) chosen from natural or synthetic | combination goods, The lubricant for plastic working of a metal material characterized by the above-mentioned. The lubricant for plastic working of a metal material according to claim 2, wherein the layered clay mineral is at least one selected from synthetic smectite and synthetic mica. The plastic working according to any one of claims 1 to 3, wherein the organic compound supported between the layers is at least one selected from organic ammonium salts, organic phosphonium salts, and organic sulfonium salts. slush. The lubricant for plastic working of a metal material according to claim 4, wherein the organic compound supported between the layers is at least one selected from aliphatic quaternary ammonium salts. The sum total of (A) organic modified clay mineral and (B) binder component is 30-100 mass% in solid content ratio, The mass ratio of (A) and (B) in any one of Claims 1-5. Lubricant for plastic working of metal materials whose value is (A) / (B) = 5 / 95-95 / 5. The water-soluble inorganic salt of sulfate, silicate, borate, molybdate, vanadium salt, tungstate salt, malate, succinate salt, citrate salt, tartarate salt according to any one of claims 1 to 6 A lubricant for plastic working of metal materials, characterized in that it is at least one selected from organic polymers of water-soluble organic salts, acrylic resins, amide resins, epoxy resins, phenol resins, urethane resins, and polymaleic acid resins. The (C) lubricant component is in the range of 0-25 mass% in solid content ratio, The mass ratio of (A) and (C) is (A) / (C) = 25 in any one of Claims 1-7. A lubricant for plastic working of metal materials, which is in the range of / 75 to 100/0. The lubricant for plastic working of a metal material according to claim 8, wherein (C) the lubricant component is at least one selected from soaps, metal soaps, and waxes. 10. The plastic working according to any one of claims 1 to 9, wherein the metal material to be processed is steel, stainless steel, aluminum and aluminum alloys, titanium and titanium alloys, copper and copper alloys, magnesium and magnesium alloys. slush. The lubricant for plastic working of a metal material according to any one of claims 1 to 10, wherein the processing method applied is cold forging. An organic modified clay mineral carrying a cationic organic compound between layers of the layered clay mineral is contained in the range of 2 to 5% by mass in solid content, and the lubricant component is contained in the range of 1 to 10% by mass in solid content. Forging lubricant.

Images