WO2012086564A1

WO2012086564A1 - Lubricant for plastic processing of metal material

Info

Publication number: WO2012086564A1
Application number: PCT/JP2011/079283
Authority: WO
Inventors: 敦芹田; 康介幢崎; 小見山　忍; 藤脇　健史; 正人大竹
Original assignee: 日本パーカライジング株式会社
Priority date: 2010-12-20
Filing date: 2011-12-19
Publication date: 2012-06-28
Also published as: JP5718944B2; CN103261384A; CN103261384B; KR20130096301A; KR101497252B1; JPWO2012086564A1

Abstract

[Problem] To provide a lubricant for plastic processing of metal materials which is also applicable in severe plastic deformation applications, does not have a black appearance that significantly stains a working environment, and does not tend to generate lubrication residue that cause molding defects. [Solution] A lubricant for plastic processing of metal materials characterized by comprising in the range of 5-95%, in solid content ratio, an organic modified clay mineral supporting a cationic organic compound between the layers of the layered clay mineral.

Description

Lubricant for plastic working of metal materials

The present invention provides a metal material to be processed such as steel, stainless steel, aluminum and aluminum alloy, titanium and titanium alloy, copper and copper alloy, magnesium and magnesium alloy, such as forging, wire drawing, tube drawing, rolling, and pressing. The present invention relates to a lubricant for reducing seizure and frictional resistance at a frictional interface between a metal material to be processed and a tool such as a die, which is generated when plastic working is performed.

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

More specifically, the present invention relates to a non-black plasticity of a metal material that is interposed between the friction interface between a metal material to be processed and a tool such as a die and exhibits both seizure resistance and friction reduction ability. It relates to a processing lubricant.

In plastic processing of metal materials such as forging, wire drawing, pipe drawing, rolling, and pressing, the use of lubricant is indispensable because the metal material that is the workpiece and tools such as molds rub against each other at the friction interface. It is.

Lubricants in the plastic processing of metal materials intervene in the friction interface and contribute to prevention of seizure (direct contact between metals), reduction of frictional resistance and suppression of wear, etc. This is one of the important factors directly linked to reduction and quality improvement of processed products.

In forging, for example, plastic deformation is caused by applying a force exceeding the yield stress to the metal material that is the work material, so the friction interface is subjected to extremely high contact pressure, and the work material undergoes deformation work. And affected by heat and surface area increase converted from friction work.

Since it is necessary for the lubricant to maintain its performance under such severe conditions as high surface pressure, thermal load, and surface area expansion, it has been devised to have both seizure resistance and friction reducing ability. Lubricants have been used.

As a lubricant for plastic processing, a method of interposing a lubricant such as oils, soaps, waxes, etc., at the friction interface may be used for mild processing, but it is a cooling agent that is forced to slide at a particularly high contact pressure. In inter-forging, etc., direct contact between the workpiece and the mold cannot be prevented, and seizure is likely to occur, so that it is not usually used.

Therefore, in general, a chemical conversion film for plastic working is formed by forming a crystalline chemical conversion film such as phosphate or oxalate on the surface of a metal material that is a workpiece, and then performing a lubricating treatment with soap or the like thereon. Used as a lubricant.

In this chemical conversion coating for plastic working, the inorganic salt film deposited by chemical reaction on the metal surface that is the workpiece is responsible for seizure resistance, and the upper soap film chemically reacts with the lower inorganic salt to produce metal soap. It forms an ideal lubricating film that exhibits excellent friction reducing ability.

However, chemical conversion coatings for plastic working require liquid management because the chemical reaction must be controlled in each processing step, and consume a large amount of energy to keep the processing bath at a high temperature.

Also, a large amount of insoluble salt (sludge) and waste liquid are generated in the treatment process, and waste water treatment and industrial waste treatment are necessary.

Since it is composed of many processes including these effects and water washing and pickling at the time of treatment, a lot of costs are required at the time of introduction and operation, and it is a preferable method in terms of process management and environmental conservation. Therefore, there is a demand for lubricants and processing methods that are simple in process and do not generate waste.

In response to such demands, various lubricants and processing methods have been proposed.

For example, “a lubricant composition in which a water-soluble polymer or an aqueous emulsion thereof is used as a base material and a solid lubricant and a chemical film forming agent are blended” (Patent Document 1), “a lubricant composition for plastic working of a metal material” (Patent Document 2) and the like show a lubricant in which a lubricating film is formed by simple application and drying based on a synthetic resin.

Further, in “Aqueous Lubricant for Cold Plastic Working of Metal Material” (Patent Document 3), a film in which a synthetic resin and a water-soluble inorganic salt are uniformly deposited is formed on the surface of a workpiece, thereby directly It is intended to avoid metal contact, and by adding a lubricating component or the like in the film at an arbitrary ratio, it is shown that performance equal to or higher than that obtained when a lubricating component layer is formed on a phosphate film is shown. ing.

In addition, in “Metallic material for plastic working having an inclined two-layer lubricating film and manufacturing method thereof” (Patent Document 4), phosphate, sulfate, borate, silicate, molybdate, and tungstate. For plastic processing by forming a base layer mainly composed of inorganic compounds such as, and a slanted two-layer lubricating layer composed mainly of metal soap, wax, polytetrafluoroethylene, molybdenum disulfide and graphite. It is shown as a lubricant having the same performance as the chemical conversion film.

In recent plastic working, especially cold forging, in addition to conventional needs such as environmental protection and longer tool life, cutting with loss of material is reduced as much as possible, and it is more smooth with complex shape and high dimensional accuracy. Aiming at net shape forgings that are economical to obtain high-quality processed products with smooth surfaces, the demand for lubricants is increasing.

Therefore, the surface pressure and surface area expansion during processing increase further, and the difficulty of processing increases, and processing that is difficult to cope with with conventional plastic processing lubricants is increasing.

As a lubricant that can cope with such strong processing, a lubricant containing a large amount of a solid lubricant such as molybdenum disulfide, tungsten disulfide, or graphite is generally used.

These solid lubricants have a hexagonal layered crystal structure, and the friction between them is reduced due to the low bonding force between the layers (van der Waals force, π bond). It has characteristics suitable for plastic working, such as being well tolerated.

Examples of the use of these solid lubricants include: (A) water-soluble inorganic salt, (B) molybdenum disulfide, and “water-based lubricant for plastic processing of metal materials and method for treating lubricating film” (Patent Document 5). It contains one or more lubricants selected from graphite and (C) wax, and these components are dissolved or dispersed in water, and the solid content concentration ratio (mass ratio) (B) / (A) is An aqueous lubricant for plastic working of a metal material characterized by 1.0 to 5.0 and (C) / (A) of 0.1 to 1.0 is shown.

However, since the appearance of solid lubricants such as molybdenum disulfide, tungsten disulfide, and graphite is black, significant contamination is seen as a problem in the working environment, and it has a non-black appearance and excellent lubricity. Solid lubricants are highly desired.

In addition, the following are general solid lubricants having a non-black appearance.

Fluorinated graphite is synthesized by fluorinating a carbon material such as graphite with fluorine gas at high temperature (by synthesizing a highly crystalline carbon material at high temperature, a synthetic product with a whiter appearance can be obtained). Although it is a solid lubricant having a layered structure having a slippery layer plane composed of covalent bonds of carbon and carbon, it is a disadvantage that it becomes a very expensive material because it requires raw material costs and high temperature heat treatment.

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

Polytetrafluoroethylene (PTFE), an organic polymer with a white appearance, is a solid lubricant that expresses a low coefficient of friction due to the fact that the molecular chains are slidable with each other because of its smooth and small cohesive molecular structure. However, since it is an organic substance and chemically inert, it is not as good as an inorganic substance in terms of pressure resistance and heat resistance.

In addition, a mica having a lamellar structure with cleavable minerals, and sericite, which belongs to this, is a solid lubricant with a very fine grain and white appearance. However, since the interlayer is a strong ionic bond, the interlayer is difficult to slip and the friction coefficient is also increased.

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

Also, melamine cyanurate, amino acid compounds and the like are organic substances and have a friction reducing ability like polytetrafluoroethylene, but are not as good as inorganic substances due to pressure resistance and heat resistance.

In these general non-black solid lubricants, no material has been found that is comparable to the seizure resistance and friction reducing ability of black molybdenum disulfide, tungsten disulfide, graphite, etc. for plastic processing. Is the current situation.

Also, in the field of hot forging, white non-graphite based forging lubricants have been proposed, but this is not a solid lubricating action, but a mixture of melt and residue due to melting and thermal decomposition of organic substances under high temperature conditions. It is considered that the combination of the quasi-solid lubrication due to the above and the mold release effect due to the gas generated by the thermal decomposition exert the performance, and it is difficult to say that it is suitable in the cold forging field where the processing power is high.

Soaps and waxes, which are lubricant components of general plastic processing lubricants, are vulnerable to shearing, and develop friction reducing ability by receiving heat generated from friction during processing and material deformation. It has almost no seizure resistance.

These molten lubricant components flow in a tool such as a mold, and are deposited locally together with a lubricant film that has fallen off during processing.

This will hinder the flow of the work piece to the detailed shape of the mold, leading to molding defects such as undercutting and defective dimensions.

As described above, this problem is serious for the recent needs to obtain a desired processed product with high accuracy, and improvement is an indispensable problem.

JP-A-52-20967 JP2000-63880 JP-A-10-008085 JP 2002-264252 A International Publication WO2002 / 012419

の通り As described above, the main problems of the current plastic working lubricant are as follows.

(1) Contamination of black solid lubricant-containing lubricant in working environment

(2) Molding failure due to accumulation of lubricating debris caused by lubricant component in mold

Based on the above, the main problem of the present invention is to solve these problems. Specifically, it is not applicable to black-type appearances that can be applied even in strong processing applications and that significantly contaminates the work environment. Another object of the present invention is to provide a lubricant for plastic working of a metal material that is less likely to cause lubrication debris that causes molding defects.

In addition to the main issues, there are further issues. In general, many forged parts manufacturers first perform forging with large plastic deformation, and finally perform precision forging to finish the final part shape. However, in recent years, due to intensifying cost competition, each manufacturer has become active in further reducing production costs. One way to reduce costs is to reduce the number of forging processes.For example, if precision forging, which is the final process, can be omitted, an annealing process before precision forging, a lubrication process for forging, and a forging process can be performed. Since it is omitted, the cost can be greatly reduced. For this purpose, it is necessary to provide a lubricant film that can withstand large deformations and has excellent processing accuracy and workability.

Because precision forging is omitted, it is required to maintain good dimensional accuracy and surface finish even when forging with large plastic deformation. For this purpose, it is necessary to control the generation of film residue adhering to the mold, which is the cause of molding defects and workpiece introduction defects.

Based on the above, a sub-task of the present invention is to provide a lubricant for plastic working of a metal material that can prevent the occurrence of film residue as much as possible in order to omit precision forging.

(Means for solving the main problems)
As a result of intensive studies to solve the above-mentioned main problems, the present inventors have found that an organically modified clay mineral carrying a cationic organic compound between layers (preferably a layered structure having exchangeable cations between layers). It has been found that a lubricant containing a specific ratio of an organically modified clay mineral obtained by ion exchange between a clay mineral and a cationic organic compound) can have both seizure resistance and friction reducing performance. The invention has been completed.

One of the features of the present invention is that the appearance is non-black, and the significant contamination in the working environment possessed by a lubricant containing a black solid lubricant such as molybdenum disulfide and graphite is present in the present invention. It disappears by applying.

In addition, the organic compound that expresses the friction reducing ability is supported between the layers of the layered clay mineral that expresses seizure resistance by chemical bonding. Local deposition due to flow is less likely to occur, leading to the effect of eliminating or minimizing the use of lubricant components such as soaps and waxes.

As a result, the present invention improves the problem of molding defects caused by the accumulation of lubricating debris, which is possessed by general plastic working lubricants that contain a large amount of lubricant components that have been the cause of lubricating debris.

The lubricant according to the present invention is a well-known means of coating with a binder component and the like, and then drying the water contained after application, soaking, etc. It can be interposed at the friction interface of the tool.

Here, the appearances of black and non-black colors in the present invention are defined.

There are roughly three elements for color expression: hue representing hue, lightness representing brightness, and saturation representing vividness.

Among them, the lightness is a high value when it becomes white, and a low value when it becomes black. In the antifouling material evaluation promotion test, the difference in brightness is used as an index of the degree of dirt.

Therefore, it is considered that the material with low lightness is scattered as the material is scattered, and the lightness of each solid lubricant powder was actually measured for molybdenum disulfide and graphite.

The measurement was performed using a color difference meter through a glass plate on a sample in which an appropriate amount of solid lubricant powder was placed in a glass petri dish and compressed vertically to a thickness of 2 mm. (Konica Minolta CR-300, D65 light source, CAE Lab color system L value)

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

For this reason, the value is lower than the lightness value of molybdenum disulfide and graphite, which are considered to be significantly contaminated in practical use, that is, the material is naturally noticeable in the dark color appearance, and conversely, the lightness is high, that is, the light color appearance. Is considered to be a material that makes contamination less noticeable.

Therefore, the hue and saturation are not taken into consideration, and the lightness is used as an index. A dark color with a lightness less than 50 is defined as “black”, and a bright color with a lightness of 50 or more is defined as “non-black”.

(Means for solving sub-tasks)
There are two types of film residue generation: a case where the film softens due to processing heat and adheres to the mold, and a case where the film falls off due to plastic deformation and adheres to the mold. In order to solve the former, it is necessary to control the blending amount of the (C) lubricating component that is easily tackified by processing heat. Moreover, in order to solve the latter, it is necessary to control the blending amount of the (A) organically modified clay mineral that inhibits the adhesion of the lubricating film. Specifically, in the agent composition, (A) the organically modified clay mineral is in the range of 2 to 5% by mass in the solid content ratio, and (C) the lubricant component is in the range of 1 to 10% by mass in the solid content ratio. By configuring as above, the sub-task is achieved.

As described above, as an effect corresponding to the main problem, a non-black system of a metal material characterized by containing an organically modified clay mineral carrying a cationic organic compound between layers in a specific ratio The plastic working lubricant can exhibit both extremely excellent seizure resistance and friction reducing ability. The application of the present invention leads to the solution of problems (contamination problems in the working environment of black solid lubricant-containing lubricants and molding defects due to accumulation of lubricating debris) that had previously been involved in plastic working lubricants. There is an effect.

Furthermore, as an effect corresponding to the sub-problem, since it is possible to prevent generation of film residue as much as possible, there is an effect that precision forging can be omitted.

FIG. 1 shows a hermetic extrusion mold used in a hermetic extrusion test in an example (an example corresponding to the main problem). FIG. 2 shows a principle diagram of a spike test in an example (an example corresponding to a sub-task) and an appearance after forging. FIG. 3 shows a principle diagram of an upsetting-ball ironing test in an example (an example corresponding to a sub-task) and an appearance after the test.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the contents of the present invention will be described in more detail.

≪Lubricant for plastic working≫
(Component A: Organically modified clay mineral)
Layered clay mineral A layered clay mineral that is one raw material of the organically modified clay mineral according to the present invention is a cationic organic compound that acts as a base material that imparts seizure resistance and friction reducing ability, and improves the slipperiness between layers. A material having an exchangeable cation capable of undergoing an ion exchange reaction with is used.

The layered clay mineral is selected from natural products or synthetic products such as smectite (montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite), stevensite, vermiculite, mica group, brittle mica group. Although at least one kind is exemplified, a synthetic clay mineral having a small particle diameter is more preferable, and specific examples thereof include synthetic mica and hectorite type synthetic smectite.

Particularly, hectorite-type synthetic smectite is preferable for the present invention because it has a small particle size and is easily retained in a lubricant that becomes an extremely thin film at the friction interface.

The primary particles of hectorite-type synthetic smectite are two-dimensional platelets with a thickness of about 1 nm, that is, rectangular or disk-like plates. One side or diameter of the plate surface is considered to be 20 to 500 nm, and the thickness is about 1 nm. A synthetic product which is a disk-like particle having a diameter of 20 to 40 nm is on the market.

Examples of the synthesis of hectorite smectite include hydrothermal synthesis as disclosed in, for example, Japanese Patent Publication No. 61-12845, Japanese Patent Application Laid-Open No. 5-279002, and the like. Includes a method of synthesizing talc, a transition metal compound, and an alkali silicofluoride by heat treatment as disclosed in, for example, JP-A-6-298522. Is not important.

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

Clay minerals are the main constituent minerals of clay. Layered silicate minerals (phyllosilicate minerals), calcite (calcite), dolomite, feldspars, quartz, zeolites (zeolites), and other chains Those with a structure (Attapulgite, Sepiolite, etc.) and those without a clear crystal structure (Allophane) are called clay minerals. Generally, layered silicate minerals are called layered clay. It is called a mineral.

Layered clay minerals have two-dimensional layers of positive and negative ions stacked in parallel to form a crystal structure. In this layer structure, there are two structural units, one that surrounds Si ⁴⁺ . The tetrahedral layer is composed of O ^2−, and the other is composed of an octahedral layer composed of Al ³⁺ (or Mg ²⁺ , Fe ^2+, etc.) and (OH) ⁻ surrounding it.

In the tetrahedron layer, O at the four vertices of the tetrahedron and Si located at the center form an Si—O tetrahedron, which is connected to each other at the three vertices to spread two-dimensionally, and Si ₄ O A layer lattice having a composition of ₁₀ is formed. Si ⁴⁺ is often replaced by Al ³⁺ .

In the octahedron layer, the octahedron formed by (OH) or O at the six vertices of the octahedron and Al, Mg, Fe, etc. located at the center of the octahedron is connected at each vertex and spreads two-dimensionally. A layer lattice having a composition of Al ₂ (OH) ₆ or Mg ₃ (OH) ₆ is formed.

In the octahedral layer, a divalent cation (such as Mg ²⁺ ) enters the lattice point of the cation surrounded by 6 anions, and occupies all of the lattice points. There is a 2-octahedron type in which trivalent cations (Al ^3+, etc.) enter the lattice points and occupy 2/3, and the remaining 1/3 is empty.

There are two types of tetrahedron and octahedron combinations, one is a 1: 1 type structure with the unit of one tetrahedron layer and one octahedron layer, and the other is two tetrahedrons. There is a 2: 1 type structure in which a unit is a unit of an octahedral layer sandwiched between layers.

In the tetrahedral layer, one Si ⁴⁺ is usually surrounded by four O atoms and has a stable coordination, but sometimes Al ³⁺ having a slightly larger ion radius than this Si ⁴⁺ replaces Si ⁴⁺ . Exists in the tetrahedral layer.

Since there is no change in the number of coordinated O atoms, every time one Al ³⁺ replaces Si ⁴⁺ , a unit of negative charge is generated in the tetrahedral layer.

Similarly, in the octahedron layer, negative charges are generated with the replacement of Al ³⁺ and Fe ³⁺ by Mg ²⁺ and Fe ²⁺ .

This negatively charged layer is a positive layer such as Li ⁺ , K ⁺ , Na ⁺ , NH ₄ ⁺ , H ₃ O ⁺ , Ca ²⁺ , Mg ²⁺ , Sr ²⁺ , Ba ²⁺ , Co ²⁺ , Fe ²⁺ , Al ^3+. The ions are electrically neutral due to the presence of ions, resulting in a laminated structure in which these exchangeable cations exist between layers.

-Cationic organic compound The cationic organic compound (organic compound inserted and carried between the layers) which is one raw material of the organically modified clay mineral according to the present invention is the interlayer spacing of the layered clay mineral. And an excellent effect as a lubricant for improving the slipperiness between layers.

Examples of the organic compound include at least one cationic organic compound (organic group + cationic group) selected from organic ammonium compounds, organic phosphonium compounds, and organic sulfonium compounds. Here, the organic group of the organic compound is not particularly limited, but is a linear, branched or cyclic (having a cyclic group), saturated hydrocarbon group or unsaturated hydrocarbon group having 1 to 30 carbon atoms. A group is preferred. Moreover, the hydrogen atom couple | bonded with the carbon atom which comprises a carbon chain or a carbocycle may be substituted by the other substituent, and the one part carbon atom which comprises a carbon chain or a carbocycle is another atom ( For example, it may be substituted with O, S, etc., and may further contain another bond (for example, ester bond, ether bond) between the CC chains. Preferable is an organic ammonium compound composed of an aliphatic hydrocarbon group (preferably having 1 to 30 carbon atoms) advantageous for friction reducing ability and an ammonium group advantageous for fixing ability between layers. Here, as the 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 are quaternary ammonium chlorides (capryltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dicapryldimethylammonium chloride, dilauryldimethylammonium chloride which are easy to wash away by-product salts with water. Chloride, distearyldimethylammonium chloride, etc.).

・ Quantity ratio of layered clay mineral / cationic organic compound The amount of cationic organic compound of 0.8 to 1.2 moles of cation exchange capacity (CEC) of each layered clay mineral is ion-exchanged. Is preferred.

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

As described above, the layered clay mineral has a laminated structure in which a cation is present between layers in order to keep the negative charge in the layer structure electrically neutral, and when dispersed in the aqueous phase, the cation between layers is water. As a result, the particles swell and separate into layer platelets.

In this state, an organic exchange agent is carried out in the presence of a cationic organic salt, which is an organic agent, and by-product salt is removed by washing with water, dried and pulverized to insert and carry organic compounds between layers. Clay mineral is obtained as a powder material.

In the present invention, the type of the exchangeable cation between the layers of the layered clay mineral is preferably Li ⁺ or Na ⁺ from the viewpoint of ease of hydration or substitution, but can also be used for other types, for example, Ca ²⁺ is the interlayer. In the case of the layered clay mineral present in, it can be indirectly organized, for example, by pretreatment such as replacement with Na ^{+ in an} aqueous Na ₂ CO ₃ solution.

As for means for producing an organically modified clay mineral in which an organic compound is inserted between layers of layered clay mineral, for example, those means are disclosed in JP-A-2-267113, JP-A-2002-348365, etc. It exists as an off-the-shelf product and the process is not important.

Also, it may be inserted directly or in an organic solvent without using water.

-Mechanism of action The organic compound carried between the layers of the layered clay mineral in the present invention is adsorbed with a cationic group directed to the negatively charged plate surface, and in a state where organic chains are grown between the layers. It seems to exist.

As a specific example, in an organic compound having a structure having an ammonium group and an aliphatic hydrocarbon group, the ammonium group is adsorbed toward the plate surface of the layered clay mineral, and an aliphatic hydrocarbon group is grown between the layers, The aliphatic hydrocarbon group acts as a lubricant component, making the layers very slippery.

Since the lubricant component is carried between the layers, it is possible to express the friction reducing ability without using or reducing the lubricant component such as soaps and waxes as much as possible. Local lubrication debris accumulation due to flow is much less likely to occur than general plastic working lubricants, and the problem of molding defects caused by lubrication debris accumulation is improved.

As for the appearance of the organically modified clay mineral of the present invention, as a specific example, the brightness of the synthetic hectorite powder organically treated with distearyldimethylammonium chloride and the untreated synthetic hectorite powder were measured by the same method as described above. Since both are about 95 and have a non-black appearance, they are suitable for the present invention for the purpose of improving the pollution problem of the work environment.

As an example of a combination of a layered clay mineral and an organic compound, a “molding agent for plastic working” (Japanese Patent Laid-Open No. Sho 56-145994) describes a mixture containing mica powder and wax having an initial boiling point of 230 ° C. or higher as main components ( A brazing / mica ratio = 1.5 to 9) has been proposed for the same purpose as in the present invention, but this is because the brazing steam generated during hot forging exhibits mold release performance and slides between the layers. Since there is no description as a thing and it is a mixture containing a large amount of lubricant components, for example, when this composition is applied by cold forging, lubricating debris is likely to occur.

For materials in which organic compounds are inserted between layers of layered clay minerals, the main characteristics are imparting properties in organic materials, such as swelling in organic solvents, imparting viscosity, or improving mechanical properties by kneading into various organic materials, and barrier effects. Is the purpose.

In the lubrication field, it is generally used as a thickener in paints and greases, but the organic compound between the layers imparts swellability in an organic solvent, and the action of the organic compound is different from that of the present invention. .

Further, in “Organic clay composite and production method thereof” (Japanese Patent Laid-Open No. 2006-52136), a material in which an organic compound is inserted between layers of a layered clay mineral is used for melt kneading or polymerization reaction with a high melting point polymer material. The content provided as a heat-resistant filler that withstands, disperses in an organic solvent, and exhibits a sufficient thickening effect.

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)
In the lubricant of the present invention, (A) used as a film component for introducing and maintaining an organically modified clay mineral and other blending components at the friction interface with the mold (B) Binder components include sulfate, silica Water-soluble inorganic salts such as acid salts, borates, molybdates, vanadates and tungstates, water-soluble organic salts such as malates, succinates, citrates and tartrates, acrylic resins, Organic polymers such as amide resin, epoxy resin, phenol resin, urethane resin, and polymaleic acid resin are exemplified, but are not particularly limited and are selected in consideration of the required items.

(Component C: Lubricant component)
Examples of the (C) lubricant component used in the lubricant of the present invention include soaps (sodium stearate, potassium stearate, sodium oleate, etc.), metal soaps (calcium stearate, magnesium stearate, aluminum stearate, stearin). Barium, lithium stearate, zinc stearate, calcium palmitate, etc.), waxes (polyethylene wax, polypropylene wax, carnauba wax, beeswax, paraffin wax, microcrystalline wax, etc.) Can do.

(Component D: Other components)
The lubricant of the present invention can be appropriately selected and contained as an example of the other components described below.

Note that adding a small amount of a black solid lubricant such as molybdenum disulfide, tungsten disulfide, or graphite does not impair the purpose of the present invention, but depending on the amount to be added, it may cause contamination of the work environment, so it must be considered. .

Solid lubricant Molybdenum disulfide, tungsten disulfide, graphite, fluorinated graphite, hexagonal boron nitride (h-BN), mica, talc, calcium carbonate, basic magnesium carbonate, basic zinc carbonate, water Calcium oxide, magnesium hydroxide, magnesium oxide, calcium phosphate, zinc phosphate, aluminum trihydrogen phosphate, polytetrafluoroethylene (PTFE), melamine cyanurate, amino acid compounds, etc.

Extreme pressure additive Sulfurized olefin, sulfurized ester, sulfite, thiocarbonate, chlorinated fatty acid, phosphate ester, phosphite ester, molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDTP), zinc dithio Sulfur-based extreme pressure additives such as phosphate (ZnDTP), organic molybdenum-based extreme pressure additives, phosphorus-based extreme pressure additives, chlorine-based extreme pressure additives, etc.

・ Corrosion inhibitor <br/> Phosphite, zirconium compound, tungstate, vanadate, tungstate, silicate, borate, carbonate, amine, benzotriazole, chelate compound, etc.

・ Viscosity modifiers Hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylic amide, sodium polyacrylate, polyvinyl pyrrolidone, polyvinyl alcohol, smectite clay mineral, finely divided silica, bentonite, kaolin, etc.

・ Oil <br/> Vegetable oil, mineral oil, synthetic oil, etc.

・ Various surfactants and polymer dispersants for dispersing or emulsifying each component Nonionic surfactant, anionic surfactant, amphoteric surfactant, cationic surfactant, 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, you may contain liquid media other than water as a liquid medium (for example, alcohol), In this case, it is suitable to set it as 10 mass% or less on the basis of the total mass of a liquid medium. The agent may be in a dry form or a concentrated form. In this case, dilute with water on site.

(composition)
Next, the composition of each component contained in the lubricant according to the present invention will be described.

-Content of component A The lubricant of the present invention contains the organically modified clay mineral in a solid content ratio of 5 to 95% by mass, but if it is less than this range, the lubricity and seizure resistance are insufficient. If it exceeds this range, it becomes difficult to retain the organically modified clay mineral in the film, and seizure resistance cannot be exhibited. More preferably, the organically modified clay mineral is in the range of 10 to 40% by mass in terms of solid content.

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

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

-Content ratio of component A / component C (+ content of component C)
The lubricant of the present invention has a mass ratio of (A) an organically modified clay mineral and (C) a lubricant component in the range of (A) / (C) = 25/75 to 100/0, and (C) is a solid content. The ratio is in the range of 0 to 25% by mass.

(C) can be contained for the purpose of supplementing the friction reducing ability, but it causes lubrication residue, so it is preferable to make it as small as possible.

≪Lubricant for plastic working (especially lubricant for forging) ≫
The above is an explanation of plastic processing in general, but it is preferable that the agent has the following composition when assuming the use of forging, in particular, omitting precision forging.

(Component A to Component C)
The forging lubricant may be any combination of component A to component C in the description of plastic processing as a whole. However, when considering the use, as component A, as synthetic smectite and / or synthetic mica, as component B Particularly suitable are combinations of water-soluble inorganic salts (silicates, borates, molybdates, tungstates) and / or polymaleic acid resins, as component C, metal soaps and / or waxes. . Furthermore, as component C, polyethylene wax and / or polypropylene wax are particularly preferred.

(Amount of component A and component C)
The forging lubricant contains (Component A) an organically modified clay mineral in a solid content ratio of 2 to 5% by mass. When it is less than this range, the seizure resistance is insufficient. If it exceeds this range, the lubricating film will fall off due to plastic deformation and will tend to adhere to the mold, resulting in insufficient moldability. More preferably, the organically modified clay mineral component is in the range of 2 to 4% by mass in terms of solid content. The forging lubricant contains (Component C) a lubricant component in the range of 1 to 10% by mass in terms of solid content. If it is less than this range, the friction reducing ability is insufficient. When it exceeds this range, the lubricating film adheres to the mold and the moldability becomes insufficient. More preferably, the lubricant component is in the range of 5 to 7% by mass in terms of solid content.

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

≪Use and application of lubricant for plastic working≫
There is no limitation on the means for interposing the lubricant of the present invention at the frictional interface between a metal material to be processed for plastic working and a tool such as a die.

The lubricant of the present invention is applied to a frictional interface by drying the moisture contained in a tool such as a metal material or a die to be processed after being applied or dipped, which is a well-known means. Thus, seizure resistance and friction reducing ability in cold forging can be imparted.

In addition, before interposing the lubricant of the present invention at the friction interface between the metal material to be processed and a tool such as a mold, the seizure resistance is greatly raised, and various bases are applied to the processed material as necessary. Processing may be performed.

As base treatments here, zinc phosphate treatment, iron zinc phosphate treatment, calcium zinc phosphate treatment, iron phosphate treatment, iron oxalate treatment, zirconium oxide treatment, conversion treatment such as aluminum fluoride treatment, alkali silicate Examples of the coating treatment include salt treatment, alkali sulfate treatment, alkali borate treatment, alkali metal salt treatment of organic acid salts, and organic polymer film treatment, but there is no particular limitation.

The metal material used in the present invention is preferably cleaned by at least one method selected from alkali cleaning, acid cleaning, sand blasting and shot blasting prior to adhering the composition of the present invention.

This is because if the metal surface is dirty, the adhesion of the lubricant is adversely affected and the lubricity is hindered.

In recent years, it has been desired not to generate waste liquid from the viewpoint of environmental conservation, but by applying a blast treatment to this, it is possible to clean the metal surface without generating waste water.

The metal material targeted in the present invention is not particularly limited from the viewpoint of material, but iron, steel, stainless steel, copper, copper alloy, aluminum, aluminum alloy, titanium, titanium alloy, magnesium, magnesium alloy, etc. The metal material which consists of metals is illustrated.

In addition, from the shape aspect, the metal material targeted by the present invention is not particularly limited. For example, not only materials such as wires, pipes, rods, block materials, but also shapes (gears, shafts, etc.) Is also included.

≪Lubrication film formed using plastic working lubricant≫
The adhesion amount of the film formed as described above needs to be 0.1 to 50 g / m ² , preferably 0.5 to 30 g / m ² , and preferably 1 to 25 g / m ^2. More preferred. If it is less than 0.1 g / m ² , the lubricity is insufficient and sufficient performance for plastic working cannot be exhibited. If it exceeds 50 g / m ² , the surplus is increased, and the residue of the lubricating film is likely to be deposited on the mold, which is not preferable in terms of forming defects and cost.

<Example>
Hereinafter, some examples of the present invention will be given, and their usefulness will be shown in comparison with comparative examples. The description will be divided into an example corresponding to the main problem and an example corresponding to the sub problem.

{1. Examples corresponding to main issues}
Table 1 shows the component types (A) to (D), the solid content ratio, and the coating amount for the formulations of Examples and Comparative Examples. Subsequently, the details of the preparation method (A) and the treatment liquid preparation method were described. In addition, the ratio in Table 1 is a mass part.
(A) Organically modified clay mineral (B) Binder component (C) Lubricant component (D) Other components

≪ (Component A) Preparation method of organically modified clay mineral≫
(Synthetic mica (Organic A))
Synthetic mica (manufactured by Coop Chemical Co., Ltd .: Somasif ME-100; exchangeable cation = Na ⁺ ; CEC value = 120 meq / 100 g) was added to 1000 ml of deionized water, and the mixture was stirred for 1 hour with a homogenizer and dispersed in water. Thereafter, the mixture was heated to 90 ° C., and 36 g (corresponding to 1.0 mol amount of CMC value) of distearyldimethylammonium chloride (manufactured by Kao Corporation: Cotamine D86P) was added while stirring with a propeller. Stirring was then continued for 1 hour, the produced insoluble particles were filtered using filter paper (5C), washed with deionized water, dried in a 60 ° C. warm air drying oven for 16 hours, and then pulverized to form synthetic mica. (Organic A) powder was obtained.

(Synthetic smectite (Organic A))
Synthetic smectite (manufactured by Coop Chemical Co., Ltd .: Lucentite SWN; exchangeable cation = Na ⁺ ; CEC value = 101 meq / 100 g) was added to 1000 ml of deionized water, stirred for 1 hour with a homogenizer, dispersed in water and dispersed in water. Dispersed, and then heated to 90 ° C. and stirred with a propeller, distearyldimethylammonium chloride (manufactured by Kao Corp .: Cotamine D86P) was added as an active ingredient in an amount of 32 g (corresponding to 1.0 mol amount of CMC value). . Stirring was then continued for 1 hour, and the resulting insoluble particles were filtered using filter paper (5C), washed with deionized water, dried in a warm air drying oven at 60 ° C. for 16 hours, and then pulverized to synthesize synthetic smectite. (Organic A) powder was obtained.

(Natural montmorillonite (Organic A))
50 ml of natural montmorillonite (Hogel Co., Ltd .: Bengel A; exchangeable cation = Na ⁺ ; CEC value = 115 meq / 100 g) was added to 1000 ml of deionized water, stirred for 1 hour with a homogenizer, dispersed in water and dispersed in water. Thereafter, the mixture was heated to 90 ° C., and 27 g (corresponding to 1.0 mole amount of CMC value) of distearyldimethylammonium chloride (manufactured by Kao Corporation: Cotamine D86P) was added while stirring with a propeller. Stirring was then continued for 1 hour, the produced insoluble particles were filtered using filter paper (5C), washed with deionized water, dried in a 60 ° C. hot air drying oven for 16 hours, and then pulverized to form natural montmorillonite. (Organic A) powder was obtained

(Synthetic smectite (organic B))
Synthetic smectite (manufactured by Coop Chemical Co., Ltd .: Lucentite SWN; exchangeable cation = Na ⁺ ; CEC value = 101 meq / 100 g) was added to 1000 ml of deionized water, stirred for 1 hour with a homogenizer, dispersed in water and dispersed in water. Dispersed, then heated to 90 ° C and stirred with a propeller, added 30 g of dioleyldimethylammonium chloride (Lion Corp .: ARCARD 2O-75I) as an active ingredient (equivalent to 1.0 mol of CMC value) did. Stirring was then continued for 1 hour, and the resulting insoluble particles were filtered using filter paper (5C), washed with deionized water, dried in a warm air drying oven at 60 ° C. for 16 hours, and then pulverized to synthesize synthetic smectite. (Organic B) powder was obtained.

(Synthetic smectite (organic C))
Synthetic smectite (manufactured by Coop Chemical Co., Ltd .: Lucentite SWN; exchangeable cation = Na ⁺ ; CEC value = 101 meq / 100 g) was added to 1000 ml of deionized water, stirred for 1 hour with a homogenizer, dispersed in water and dispersed in water. After dispersion, the mixture was heated to 90 ° C., and stearyltrimethylammonium chloride (manufactured by Kao Corporation: Cotamine 86W) was added as an active ingredient while stirring with a propeller as an active ingredient (17 mol equivalent). Stirring was then continued for 1 hour, and the resulting insoluble particles were filtered using filter paper (5C), washed with deionized water, dried in a warm air drying oven at 60 ° C. for 16 hours, and then pulverized to synthesize synthetic smectite. (Organic C) powder was obtained.

(Natural montmorillonite (organic D))
50 ml of natural montmorillonite (Hogel Co., Ltd .: Bengel A; exchangeable cation = Na ⁺ ; CEC value = 115 meq / 100 g) was added to 1000 ml of deionized water, stirred for 1 hour with a homogenizer, dispersed in water and dispersed in water. Thereafter, the mixture was heated to 90 ° C. and 22 g of benzyltriphenylphosphonium chloride as an active ingredient (corresponding to 1.0 molar amount of CMC value) was added while stirring the propeller. Stirring was then continued for 3 hours, and the resulting insoluble particles were filtered using filter paper (5C), washed with deionized water, dried in a 60 ° C. hot air drying oven for 16 hours, and then pulverized to form natural montmorillonite. A powder of (Organic D) was obtained.

(Synthetic mica (Organic D))
Synthetic mica (manufactured by Coop Chemical Co., Ltd .: Somasif ME-100; exchangeable cation = Na ⁺ ; CEC value = 120 meq / 100 g) was added to 1000 ml of deionized water, and the mixture was stirred for 1 hour with a homogenizer and dispersed in water. Thereafter, the mixture was heated to 90 ° C., and 23 g (corresponding to 1.0 mole amount of CMC value) of benzyltriphenylphosphonium chloride as an active ingredient was added while stirring with a propeller. Stirring was then continued for 3 hours, and the produced insoluble particles were filtered using filter paper (5C), washed with deionized water, dried in a hot air drying oven at 60 ° C. for 16 hours, and then pulverized to form synthetic mica. A powder of (Organic D) was obtained.

≪Method of preparing treatment liquid of example≫
Example 1
17.4 g of potassium tetraborate was added to 77.4 g of deionized water while stirring with a propeller, and dissolved by heating to 60 ° C. Then, 0.2 g of 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 for 1 hour with a homogenizer. And dispersed in the liquid. Thereafter, 4 g of polyethylene wax emulsion (manufactured by Mitsui Chemicals, Inc.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Example 2)
24.2 g of an epoxy resin aqueous solution (Arakawa Chemical Industries, Ltd.) and 0.4 g of a nonionic surfactant (Shin-Etsu Chemical Co., Ltd.) were prepared while 58.1 g of deionized water was stirred with a propeller. 3 g of synthetic smectite (organic C) and 6 g of calcium carbonate were added, and the liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid. Thereafter, 8.3 g of a zinc stearate emulsion (manufactured by Chukyo Yushi Co., Ltd.) was added while stirring with a propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

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

Example 4
179.8 g of potassium tetraborate was added to 79.8 g of deionized water while stirring with a propeller, and heated to 60 ° C. to dissolve. Then, 0.2 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 g of the produced synthetic smectite (Organic C) were added while stirring the propeller at room temperature, and the solution was stirred for 1 hour with a homogenizer. 100 g of a treatment liquid having a concentration of about 20% was obtained by dispersing in the liquid.

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

(Example 6)
Preparation of 60 g of styrene-maleic anhydride resin aqueous solution (manufactured by Nichiyu Solution Co., Ltd.) and 0.2 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) while stirring 28.2 g of deionized water with a propeller 5 g of the synthesized smectite (Organic A) and 1 g of untreated synthetic smectite (Coop Chemical Co., Ltd.) were added, and the liquid was stirred with a homogenizer for 1 hour and dispersed in the liquid. Thereafter, 5.6 g of a zinc stearate emulsion (manufactured by Chukyo Yushi Co., Ltd.) was added while stirring with a propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Example 7)
While stirring the propeller, 7 g of deionized water was added with 5 g of sodium silicate and dissolved by heating to 60 ° C. Then, 0.6 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of the produced synthetic smectite (organic B) and 4 g of calcium carbonate were added while stirring the propeller at room temperature, and the liquid was mixed with a homogenizer. The mixture was stirred for 1 hour and dispersed in the liquid. Thereafter, 10 g of paraffin wax emulsion (Nippon Seiki Co., Ltd.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Example 8)
97.6 g of potassium tetraborate was added to 77.6 g of deionized water while stirring with a propeller, and dissolved by heating to 60 ° C. Then, 0.4 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of the produced synthetic smectite (organic B) and 2 g of magnesium hydroxide were added while stirring the propeller at room temperature, and the liquid was homogenized. The mixture was stirred for 1 hour and dispersed in the liquid. Thereafter, 4 g of calcium stearate emulsion (manufactured by Modern Chemical Industry Co., Ltd.) was added while stirring with a propeller to obtain 100 g of a treatment liquid having a concentration of about 20%.

Example 9
4 g of sodium vanadate was added to 74.9 g of deionized water while stirring with a propeller, and dissolved by heating to 60 ° C. Then, 0.6 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 9 g of the prepared synthetic mica (organic A), and 4 g of talc (manufactured by Nippon Talc Co., Ltd.) were added while stirring the propeller at room temperature. The liquid was stirred with a homogenizer for 1 hour and dispersed in the liquid. Thereafter, 7.5 g of polyethylene wax emulsion (Mitsui Chemicals, Inc.) was added while stirring with a propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Example 10)
79.4 g of sodium succinate was added to 79.4 g of deionized water while stirring with a propeller, and heated to 60 ° C. to dissolve. Then, while stirring the propeller at room temperature, 0.6 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 9 g of the prepared synthetic mica (Organic A), untreated synthetic mica (manufactured by Coop Chemical Co., Ltd.) 2 g) and 2 g of lithium stearate were added, and the liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid to obtain 100 g of a processing liquid having a concentration of about 20%.

(Example 11)
While propylene stirring 35.6 g of deionized water, 55 g of isobutylene-maleic anhydride resin aqueous solution (manufactured by Kuraray Co., Ltd.) and 0.4 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) were prepared. 9 g of synthetic mica (Organic A) was added, and the liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid to obtain 100 g of a processing liquid having a concentration of about 20%.

(Example 12)
While propylene stirring 76.6 g of deionized water, 5 g of polyamide resin (manufactured by Toray Industries, Inc.) was added and heated to 60 ° C. to dissolve. Then, 0.4 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 11 g of the prepared natural montmorillonite (organic A), and 2 g of calcium carbonate were added while stirring the propeller at room temperature, and the liquid was mixed with a homogenizer. The mixture was stirred for 1 hour and dispersed in the liquid. Thereafter, 5 g of a polypropylene wax emulsion (Mitsui Chemicals, Inc.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Example 13)
79.4 g of sodium tartrate was added to 79.4 g of deionized water while stirring with a propeller and heated to 60 ° C. to dissolve. Then, 0.6 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 11 g of the produced synthetic smectite (organic B), and a layered structure amino acid compound (manufactured by Ajinomoto Co., Inc.) while stirring the propeller at room temperature. 2 g was added, and the liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid to obtain 100 g of a processing liquid having a concentration of about 20%.

(Example 14)
59.4 g of ammonium molybdate was added to 79.4 g of deionized water while stirring with a propeller, and heated to 60 ° C. to dissolve. Then, 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 while stirring the propeller at room temperature, and the liquid was homogenized. The mixture was stirred for 1 hour and dispersed in the liquid to obtain 100 g of a treatment liquid having a concentration of about 20%.

(Example 15)
While 18.6 g of polyurethane resin aqueous solution (manufactured by Adeka Co., Ltd.) was added to 68.6 g of deionized water with propeller stirring, the mixture was heated to 60 ° C. and dissolved. Then, 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 while stirring the propeller at room temperature, and the liquid was stirred with a homogenizer for 1 hour. Dispersed in the liquid. Thereafter, 2.5 g of microcrystalline wax emulsion (manufactured by Nippon Seiki Co., Ltd.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Example 16)
While propeller stirring 88.2 g of deionized water, 3.5 g of potassium tetraborate was added and heated to 60 ° C. to dissolve. Then, 0.3 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 3.5 g of the produced synthetic smectite (Organic A) and 1.5 g of magnesium hydroxide were added while stirring the propeller at room temperature. The liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid. Thereafter, 3 g of calcium stearate emulsion (manufactured by Modern Chemical Industry Co., Ltd.) was added while stirring the propeller to obtain 100 g of a treatment liquid having a concentration of about 10%.

(Example 17)
While stirring the propeller, 5 g of deionized water was added with 14 g of sodium succinate and heated to 60 ° C. to dissolve. 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 are added while stirring the propeller at room temperature, and the liquid is homogenized. The mixture was stirred for 1 hour and dispersed in the liquid. Thereafter, 10 g of polyethylene wax emulsion (manufactured by Mitsui Chemicals, Inc.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 40%.

(Example 18)
While propeller stirring 35.8 g of deionized water, 6.7 g of an aqueous phenol resin solution (manufactured by Konishi Chemical Industry Co., Ltd.) and 0.4 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) were prepared. 18 g of synthetic mica (Organic A) was added, and the liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid to obtain 100 g of a treatment liquid having a concentration of about 20%.

(Example 19)
97.8 g of potassium tetraborate was added to 77.8 g of deionized water with propeller stirring, and the mixture was heated to 60 ° C. to dissolve. Then, 0.4 g of a nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 9 g of the produced natural montmorillonite (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 liquid. Thereafter, 3.8 g of calcium stearate emulsion (manufactured by Modern Chemical Industry Co., Ltd.) was added while stirring with a propeller to obtain 100 g of a processing solution having a concentration of about 20%.

(Example 20)
11 g of sodium silicate was added to 76.6 g of deionized water while stirring with a propeller, and heated to 60 ° C. to dissolve. Then, while stirring the propeller at room temperature, 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, and the liquid was stirred with a homogenizer for 1 hour. Dispersed in the liquid. Thereafter, 5 g of polyethylene wax emulsion (Mitsui Chemicals, Inc.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

≪Method for preparing treatment liquid of comparative example≫
(Comparative Example 1)
Preparation of 80 g of styrene-maleic anhydride resin aqueous solution (manufactured by Nichiyu Solution Co., Ltd.) and 0.2 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) while stirring 12.4 g of deionized water with a propeller 0.6 g of the synthesized mica (organic A) was added, and the liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid. Thereafter, 6.8 g of calcium stearate emulsion (manufactured by Modern Chemical Industry Co., Ltd.) was added while stirring the propeller to obtain 100 g of a treatment liquid having a concentration of about 20%.

(Comparative Example 2)
While stirring the propeller, 79.6 g of deionized water was added with 0.6 g of potassium tetraborate and heated to 60 ° C. to dissolve. Then, 0.4 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 19.4 g of the produced synthetic smectite (Organic B) were added while stirring the propeller at room temperature, and the solution was stirred for 1 hour with a homogenizer. Then, it was dispersed in the liquid to obtain 100 g of a processing liquid having a concentration of about 20%.

(Comparative Example 3)
While stirring propeller with 35.6 g of deionized water, 55 g of isobutylene-maleic anhydride resin aqueous solution (manufactured by Kuraray Co., Ltd.), 0.4 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), untreated 9 g of a synthetic mica (manufactured by Coop Chemical Co., Ltd.) was added, and the liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid to obtain 100 g of a treatment liquid having a concentration of about 20%.

(Comparative Example 4)
30 g of isobutylene-maleic anhydride resin aqueous solution (manufactured by Kuraray Co., Ltd.), 0.2 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), untreated while stirring 48.8 g of deionized water with a propeller 6 g of a synthetic mica (manufactured by Coop Chemical Co., Ltd.) was added, and the liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid. Thereafter, 15 g of a polyethylene wax emulsion (manufactured by Mitsui Chemicals, Inc.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Comparative Example 5)
69.4 g of sodium citrate was added to 79.4 g of deionized water while stirring with a propeller, and heated to 60 ° C. to dissolve. Then, 0.6 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of melamine cyanurate (manufactured by Sakai Chemical Industry Co., Ltd.) and 7 g of barium stearate were added while stirring the propeller at room temperature. The liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid to obtain 100 g of a processing liquid having a concentration of about 20%.

(Comparative Example 6)
While propylene stirring 42.3 g of deionized water, 30 g of isobutylene-maleic anhydride resin aqueous solution (manufactured by Kuraray Co., Ltd.), 0.2 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.), phosphoric acid 5 g of zinc was added, and the 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 Chemicals, Inc.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Comparative Example 7)
8 g of sodium tartrate was added to 75.6 g of deionized water while stirring with a propeller, and dissolved by heating to 60 ° C. Then, 0.4 g of 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. And dispersed in the liquid. Thereafter, 8 g of calcium stearate emulsion (manufactured by Modern Chemical Industry Co., Ltd.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Comparative Example 8)
5 g of sodium silicate was added to 72.1 g of deionized water while stirring with a propeller, and heated to 60 ° C. to dissolve. Then, 0.4 g of nonionic surfactant (manufactured by Shin-Etsu Chemical Co., Ltd.) and 10 g of molybdenum disulfide are added while stirring the propeller at room temperature, and the liquid is stirred for 1 hour with a homogenizer and dispersed in the liquid. It was. Thereafter, 12.5 g of paraffin wax emulsion (manufactured by Nippon Seiki Co., Ltd.) was added while stirring the propeller to obtain 100 g of a treatment solution having a concentration of about 20%.

(Comparative Example 9)
30 g of a polyurethane resin aqueous solution (manufactured by Adeka Co., Ltd.) was added to 47.7 g of deionized water while propeller stirring, and the mixture was heated to 60 ° C. and dissolved. Thereafter, 0.6 g of 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 liquid was stirred for 1 hour with a homogenizer and dispersed in the liquid. Thereafter, 16.7 g of zinc stearate emulsion (manufactured by Chukyo Yushi Co., Ltd.) was added with propeller stirring to obtain 100 g of a processing solution having a concentration of about 20%.

≪Test method≫
(Sealed extrusion test)
<Specimen material>
SAE1008 (tensile strength 488MPa) cylindrical shape (diameter 11.8mmφ × 20mm)
<Processing process>
(3) Cleaning: Alkaline degreasing Commercially available alkaline degreasing agent (Fine Cleaner 4360, manufactured by Nihon Parkerizing Co., Ltd.) concentration 20 g / L, temperature 60 ° C., immersion 10 minutes.
(3) Washing with water: tap water, room temperature and immersion for 1 minute.
(1) Surface treatment: A test piece was dip-coated on each level of drug and dried under conditions of 100 ° C. for 30 minutes.
<Processing conditions>
Using the hermetic extrusion mold shown in FIG. 1, the test piece is extruded with a servo press, and the processing load at that time is subjected to a chemical conversion treatment for plastic working (soap lubrication treatment on the zinc phosphate chemical conversion coating). The lubricity was evaluated by comparison with what was referred to as a bond.
<Evaluation criteria>
・ Lubricity ◎: Average processing load is less than bondage ○: Average processing load is equal to or less than 10% increase of bondage △: Average processing load is greater than 10% to less than 20% increase ×: Average processing load is 20% of bondage Super

≪Spike test≫
<Specimen material>
Cylindrical shape of S45C spheroidizing material (diameter 25mmφ, height 30mm)
<Processing process>
(3) Cleaning: Alkaline degreasing Commercially available alkaline degreasing agent (Fine Cleaner 4360, manufactured by Nihon Parkerizing Co., Ltd.) concentration 20 g / L, temperature 60 ° C., immersion 10 minutes.
(3) Washing with water: tap water, room temperature and immersion for 1 minute.
(1) Surface treatment: A test piece was dip-coated on each level of drug and dried under conditions of 100 ° C. for 30 minutes.
<Processing conditions>
According to the invention of JP-A-5-7969, a 200-ton crank press is used, a constrained finish flat die (SKD11) is set on the top, and a mirror finish funnel-like die (SKD11) is set on the bottom. A test piece was placed in the center of the plate and struck from above (processing speed was 30 strokes / min). The seizure resistance was evaluated by observing the degree of seizure at the spike tip of the test piece after processing.
<Evaluation criteria>
・ Evaluate the presence or absence of seizure by observing the spike tip of the specimen after seizure resistance processing.
○: No seizure △: Micro seizure ×: Severe seizure

≪Upset processing test≫
<Specimen material>
Cylindrical shape of S45C spheroidizing material (diameter 25mmφ, height 30mm)
<Processing process>
(3) Cleaning: Alkaline degreasing Commercially available alkaline degreasing agent (Fine Cleaner 4360, manufactured by Nihon Parkerizing Co., Ltd.) concentration 20 g / L, temperature 60 ° C., immersion 10 minutes.
(3) Washing with water: tap water, room temperature and immersion for 1 minute.
(2) Surface treatment: A test piece was dip-coated on each level of chemical and dried in a hot air electric furnace set at 100 ° C. for 1 hour. (The surface treatment of Comparative Example 2 was performed by the method described in the level item.)
<Processing conditions>
Using a 200-ton crank press, a flat mold (SKD11) with a mirror finish on both the upper and lower parts was set, and a test piece was placed in the center of the lower mold, and was struck from above so that the compression ratio was about 50% (processing speed) Is 30 strokes / minute). Three test pieces were continuously processed and evaluated by observing the degree of lubrication residue accumulated in the lower mold.
<Evaluation criteria>
・ Lubrication residue accumulated on the lower mold after machining of lubrication residue is observed and evaluated.
○: Almost no deposit or easy removal with little accumulation Δ: Slightly deposited but easy to remove ×: Many deposits, slightly fused

≪Work environment evaluation≫
In each of the above processing tests, the state of contamination around the mold during operation was observed.
<Evaluation criteria>
・ Work environment ○: There is almost no noticeable contamination, or it is mild ×: Conspicuous dirt such as black is generated

Table 2 shows the results of the above tests.

It can be seen that Examples 1 to 20 using the present invention exhibit a practical level of lubricity and seizure resistance, and there are few lubrication residues generated during processing.

For comparison, Comparative Example 1 with a small amount of the organically modified clay mineral is inferior in lubricity and seizure resistance, and in Comparative Example 2 in which the amount is too large, seizure resistance and lubrication residue resistance are inferior due to the removal of the components.

In Comparative Example 3 containing a layered clay mineral in which no organic compound is inserted, the lubricity is inferior, and in Comparative Example 4 containing a lubricant component to compensate for it, the lubrication residue resistance is inferior.

In Comparative Examples 5 to 7, which are a combination of a general solid lubricant and a lubricant component, there was a tendency that the evaluation of lubricity and seizure resistance and the evaluation of lubrication resistance were contradictory.

Comparative Examples 7 to 8 using a black solid lubricant had good lubricity and seizure resistance, but of course, the mold periphery was contaminated black.

{2. Examples corresponding to sub-tasks}
Table 3 shows an example of the determination result (friction reduction ability) in the spike test when the combination of components A to C is changed. The adhesion amount of the lubricating film was 10 g / m ² (the same applies to other tests). Here, FIG. 2 shows the principle diagram of the spike test in this example and the appearance after forging. In addition, the matters not specifically mentioned, such as the production method of the agent, were carried out according to “1. Examples corresponding to main problems”. As can be seen from this table, regarding the friction reducing ability, a 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 is particularly good. It was confirmed that. Moreover, it can be seen from this result that the friction reducing ability is secured if the wax is contained in an amount of 1% by mass as the lower limit. In addition, below, the test result about synthetic mica as A component, potassium tetraborate as B component, and polyethylene wax as C component is described as an example among these favorable combinations. In the following tables, “%” means “% by mass” unless otherwise specified.

Table 4 shows the result of verifying the amount of residue transferred to the mold when the solid content ratio of the polyethylene wax was changed after fixing the synthetic mica at 3 mass% (upsetting test). . From this result, it can be seen that if the upper limit value is up to 10% by mass, reduction of the amount of residue transferred to the mold can be ensured even if wax is contained.

Table 5 shows the result of verifying the difficulty of falling off the film residue when the solid content ratio of the synthetic mica is changed after fixing the polyethylene wax at 5% by mass. Test (upset-ball ironing test)}. Here, FIG. 3 shows the principle diagram of the upsetting-ball ironing test in this example and the appearance after the test. From this result, it can be seen that if the upper limit value is up to 5% by mass, it is possible to ensure that the coating residue does not easily fall off even if an organically modified clay mineral is contained.

Table 6 shows the determination result (anti-seizure ability) in the upsetting-ball ironing test when the content of the organically modified clay mineral was changed after fixing polyethylene wax at 5% by mass. From this result, it is understood that the seizure resistance can be secured if the organic modified clay mineral is contained in an amount of 2% by mass as the lower limit.

Claims

A lubricant for plastic working of a metal material, characterized by containing an organically modified clay mineral carrying a cationic organic compound between layers of a layered clay mineral in a solid content ratio of 5 to 95% by mass.
The layered clay mineral is at least one selected from smectite (montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, saconite), stevensite, vermiculite, mica group, brittle mica group natural product or synthetic product. The lubricant for plastic working of a metal material according to claim 1, wherein the lubricant is provided.
3. 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 metal material according to any one of claims 1 to 3, wherein the organic compound carried between the layers is at least one selected from organic ammonium salts, organic phosphonium salts, and organic sulfonium salts. Lubricant for plastic working.
The metal processing lubricant according to claim 4, wherein the organic compound carried between the layers is at least one selected from aliphatic quaternary ammonium salts.
The total of (A) the organically modified clay mineral and (B) the binder component is in the range of 30 to 100% by mass in terms of solid content, and the mass ratio of (A) and (B) is (A) / (B) = 5 The lubricant for plastic working of a metal material according to any one of claims 1 to 5, wherein the lubricant is in a range of / 95 to 95/5.
(B) The binder component is a sulfate, silicate, borate, molybdate, vanadate, tungstate, water-soluble inorganic salt, malate, succinate, citrate, tartrate The water-soluble organic salt, acrylic resin, amide resin, epoxy resin, phenolic resin, urethane resin, and polymaleic acid resin are at least one selected from organic polymers. The lubricant for plastic working of a metal material according to any one of claims 6 to 10.
(C) The lubricant component is in the range of 0 to 25% by mass in terms of solid content, and the mass ratio of (A) to (C) is in the range of (A) / (C) = 25/75 to 100/0. The lubricant for plastic working of a metal material according to any one of claims 1 to 7, wherein the lubricant is a plastic working lubricant.
(C) The lubricant component for plastic processing of a metal material according to claim 8, wherein the lubricant component is at least one selected from soaps, metal soaps, and waxes.
10. The plasticity of the metal material according to claim 1, wherein the metal material to be processed is steel, stainless steel, aluminum and aluminum alloy, titanium and titanium alloy, copper and copper alloy, magnesium and magnesium alloy. Processing lubricant.
The lubricant for plastic working of a metal material according to any one of claims 1 to 10, wherein the applied processing method is cold forging.
Contains an organically modified clay mineral carrying a cationic organic compound between layers of layered clay mineral in a solid content ratio of 2 to 5% by mass, and a lubricant component in a solid content ratio of 1 to 10% by mass. A forging lubricant characterized by comprising: