WO2019004328A1

WO2019004328A1 - Lubricant, metal material, method for plastically forming metal material, and method for producing formed metal material

Info

Publication number: WO2019004328A1
Application number: PCT/JP2018/024478
Authority: WO
Inventors: 睦柳; 小見山　忍
Original assignee: 日本パーカライジング株式会社
Priority date: 2017-06-29
Filing date: 2018-06-28
Publication date: 2019-01-03
Also published as: EP3647396A1; JP2019011416A; CN110662823A

Abstract

[Problem] To provide a novel lubricant which is capable of suppressing seizing of metal materials due to friction between the metal materials. [Solution] The above-mentioned problem is able to be solved by a lubricant which contains a smectite clay mineral and ammonium ions obtained by cationizing a primary amine, a secondary amine or a tertiary amine, and wherein: the ammonium ions are intercalated between layers of the smectite clay mineral; the primary amine, the secondary amine or the tertiary amine contains one or more long-chain alkyl groups, each of which has 8 or more carbon atoms in the main chain; and the total number of carbon atoms in the main chains of the long-chain alkyl groups is 16 or more.

Description

Lubricant, metal material, plastic working method of metal material and manufacturing method of shaped metal material

The present invention relates to a lubricant useful for plastic processing of a metal material, a metal material having a film of the lubricant, a metal material to which the lubricant adheres, and a method of plastically working a metal material using the lubricant The present invention relates to a method of manufacturing a shaped and processed metal material.

The friction between metal materials (for example, machine parts, molds and metal materials for forming process) occurs during plastic working and friction movement, and the friction adversely affects the metal materials, so the friction is reduced. Various lubricants have been developed. For example, in Patent Document 1, for plastic processing of a metal material containing an organically modified clay mineral carrying a cationic organic compound between layers of a layered clay mineral in a solid content ratio in a range of 5 to 95% by mass Lubricants are disclosed.

International Publication No. 2012/086564

The present invention uses a novel lubricant capable of suppressing seizing due to friction between metal materials, a metal material having a film of the lubricant, a metal material to which the lubricant adheres, and the lubricant. An object of the present invention is to provide a method of plastically working a metal material and a method of manufacturing a shaped metal material.

As a result of intensive studies to solve the above problems, the present inventors have included smectite clay minerals in which predetermined cationized primary, secondary or tertiary amines are inserted between layers. A lubricant is brought into contact with a metal material (plastic working material to be worked) before plastic working to form a lubricating film on the surface of the metal material, and then plastic working is performed using a die, It has been found that seizure due to friction between a metal material and a mold can be suppressed, and the present invention has been completed.

The present invention (1) comprises a smectite clay mineral and an ammonium ion cationized with a primary amine or a secondary amine or a tertiary amine, and the ammonium ion is inserted between the layers of the smectite clay mineral. The primary amine or secondary amine or tertiary amine has at least one long chain alkyl group having 8 or more carbon atoms in the main chain, and the carbon number in the main chain of the long chain alkyl group Is a lubricant (excluding those containing lithium borate), the total of which is 16 or more.
The present invention (2) is a smectite clay mineral, an ammonium ion cationized with a primary amine or a secondary amine or a tertiary amine, graphite, graphene, graphene oxide, fullerene, carbon nanotube, diamond like carbon At least the ammonium ion is inserted between the layers of the smectite clay mineral, and includes at least one inorganic solid particle selected from (DLC), onion like carbon, molybdenum disulfide, and tungsten disulfide; The amine or secondary amine or tertiary amine has one or more long chain alkyl groups having 8 or more carbon atoms in the main chain, and the total number of carbon atoms in the main chain of the long chain alkyl group is 16 or more There is a lubricant.
The invention (3) is the lubricant according to the invention (1) or (2), which is solid.
The present invention (4) is a metal material having a film of the lubricant according to the invention (1) or (2).
The present invention (5) is a metal material to which the lubricant according to the invention (3) is attached.
The present invention (6) comprises the step of bringing the lubricant according to the invention (1) or (2) into contact with at least one of the two metal materials causing friction to form a lubricating film. It is a plastic working method of metal material.
The present invention (7) is a method for plastically working a metal material, comprising the step of adhering the lubricant according to the invention (3) onto at least one of the two metal materials causing friction.
The present invention (8) comprises the steps of bringing the lubricant according to the invention (1) or (2) into contact with at least one surface of two metal materials causing friction to form a lubricating film; And a step of contacting two metal members to perform plastic working, and a method of producing a formed metal member.
The present invention (9) comprises the steps of adhering the lubricant of the invention (3) onto at least one of the two metal materials causing friction, and contacting the two metal materials for plastic working. It is a manufacturing method of forming processing metal material including the process to perform.

According to the present invention, a novel lubricant capable of suppressing seizure due to friction between metal materials, a metal material having a film of the lubricant, a metal material to which the lubricant adheres, and the lubricant are used. It is possible to provide a method of plastically working a metal material and a method of manufacturing a shaped metal material.

It is a figure which shows the evaluation criteria of a burning degree of the test piece which did the processing performance evaluation test.

Hereinafter, the contents of the present invention will be described in detail, but the present invention is not limited thereto.

<<< Lubricant >>>
In an embodiment of the present invention, the lubricant contains a smectite clay mineral, and an ammonium ion cationized with a primary amine or a secondary amine or a tertiary amine, and the above ammonium in the interlayer of the smectite clay mineral Including those in which ions are inserted. The lubricant does not contain lithium borate. This lubricant may be composed only of smectite clay mineral and the above ammonium ion, or may contain smectite clay mineral and other components in addition to the above ammonium ion.
In the embodiment of the present invention, the lubricant contains a smectite clay mineral, an ammonium ion cationized with a primary amine or a secondary amine or a tertiary amine, and inorganic solid particles, and is a smectite-based lubricant. The thing containing at least the said ammonium ion inserted between the layers of a clay mineral is included. The lubricant may or may not further contain lithium borate. This lubricant may be composed only of smectite clay mineral and the above ammonium ion and inorganic solid particle, or contains smectite clay mineral and other components in addition to the above ammonium ion and inorganic solid particle. May be
These lubricants may be solid lubricants or may be liquid lubricants containing a liquid medium.
The friction between the metal materials is caused by depositing such a lubricant on at least one surface of two metal materials causing the friction or forming a film of the lubricant on the surface. It is possible to suppress burn-in due to

<< ingredients >>
<Smectite clay mineral>
The smectite clay mineral is not particularly limited. Specifically, natural products such as montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, sauconite and synthetic products thereof can be mentioned. These smectite clay minerals may be used alone or in combination of two or more.

Among layers of smectite clay minerals, which are raw materials, usually, Li ⁺ , K ⁺ , Na ⁺ , NH ₄ ⁺ , H ₃ O ⁺ , Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , Fe ²⁺ , Al ^3+, etc. Although ions are present, cations other than these (except for the ammonium ion described later) may be present.

<Ammonium ion>
The ammonium ion is obtained by cationizing a primary amine or a secondary amine or a tertiary amine. As the primary amine or secondary amine or tertiary amine, an alkyl group having 8 or more carbon atoms in its main chain (hereinafter such alkyl group may be referred to as a long chain alkyl group) may be used. It is not particularly limited as long as it has one or more and the total number of carbon atoms contained in the main chain of all long chain alkyl groups is 16 or more. That is, a compound represented by the following formula (1) [hereinafter referred to as a compound (1). In the above, at least R ₁ is a long chain alkyl group, R ₂ is a hydrogen atom or an alkyl group, and R ₃ is a hydrogen atom or an alkyl group. The alkyl groups of R ₂ and R ₃ may be, independently and independently, an alkyl group having 1 to 22 carbon atoms in the main chain, or an alkyl group having 8 to 22 carbon atoms in the main chain. Good. In the compound (1), the total number of carbons contained in the main chain of all long chain alkyl groups bonded to N is 16 or more.

Specifically, in the case of a primary amine, in the compound (1), R ₁ is a long chain alkyl group having 16 or more carbon atoms in the main chain, and R ₂ and R ₃ are hydrogen atoms. In the case of a primary amine, the carbon number of the main chain of the long chain alkyl group is not particularly limited as long as it is 16 or more, but is preferably 22 or less.

Examples of primary amines include, but are not limited to, compounds such as n-palmitylamine and n-stearylamine.

In the case of the secondary amine, in the compound (1), R ₁ is a long chain alkyl group having 16 or more carbon atoms in the main chain, R ₂ is an alkyl group having 1 or more carbon atoms in the main chain, ₃ is a hydrogen atom; or R ₁ is a long chain alkyl group having 8 or more carbon atoms in the main chain, R ₂ is a long chain alkyl group having 8 or more carbon atoms in the main chain, and R ₃ is It is a hydrogen atom. In the case of a secondary amine, the total carbon number of the main chain of the long chain alkyl group is not particularly limited as long as it is 16 or more, but preferably 36 or less.

Examples of secondary amines include, but are not limited to, compounds such as N, N-di-n-stearylamine and Nn-stearyl-N-methylamine.

In the case of a tertiary amine, in compound (1), R ₁ is a long chain alkyl group having 16 or more carbon atoms in the main chain, and R ₂ and R ₃ are alkyl groups having 1 or more carbon atoms in the main chain. Or R ₁ is a long chain alkyl group having 8 or more carbon atoms in the main chain, and R ₂ and / or R ₃ is a long chain alkyl group having 8 or more carbon atoms in the main chain. In the case of a tertiary amine, the total carbon number of the main chain of the long chain alkyl group is not particularly limited as long as it is 16 or more, but preferably 36 or less.

Examples of tertiary amines include N, N-di-n-octyl-N-methylamine, N, N-di-n-decyl-N-methylamine, N, N-di-n-lauryl-N -Methylamine, N, N-di-n-myristyl-N-methylamine, N, N-di-n-stearyl-N-methylamine, N, N-dimethyl-Nn-palmitylamine, N, N-Dimethyl-Nn-stearylamine, N, N-Dimethyl-Nn-behenylamine, N, N, N-tri-n-octylamine, N, N, N-tri-n-decylamine, N Examples include, but are not limited to, compounds such as N, N-tri-n-dodecylamine.

Here, the long-chain alkyl group in the compound (1) is not limited to linear and may be branched as long as the carbon number of the main chain is 8 or more. Examples of compounds having one or more branched long-chain alkyl groups and having a total of 16 or more carbon atoms in the main chain of the long-chain alkyl group include, for example, diisononylamine, tris (7-methyloctyl) Examples include, but are not limited to, amines, bis (2,4-diethyloctyl) amines, bis (10-methylundecyl) amines and the like.

In addition, the ammonium ion which cationized said various amines may be used individually by 1 type, and may be used combining 2 or more types.

<Inorganic solid particles>
Examples of the inorganic solid particles include graphite, graphene, graphene oxide, fullerene, carbon nanotube, onion like carbon, diamond like carbon (DLC), molybdenum disulfide, tungsten disulfide and the like. These inorganic solid particles may be used alone or in combination of two or more. A metal material to which the lubricant adheres, or a lubricating film formed by contacting the lubricant on the surface, which is obtained by bringing the lubricant of the present embodiment containing inorganic solid particles into contact with the surface of the metal material Even if plastic working or friction movement is performed on the metal material having the high temperature (200 ° C. or more; temperature of the metal material), it is possible to further suppress baking on the surface of the metal material.

<Liquid medium>
Examples of the liquid medium include water or a mixed solvent of water and a water-miscible solvent (the proportion of water is, for example, 60% by mass or more based on the total mass of the mixed solvent). The water-miscible solvent is not particularly limited as long as it does not separate after mixing with water, and examples thereof include alcohols such as methanol and ethanol.

<Other ingredients>
Examples of the other components include organic polymers (for example, acrylic resins, amide resins, epoxy resins, epoxy resins, phenol resins, urethane resins and polymaleic acid resins), water-soluble inorganic salts (for example, sulfuric acid) Coatings such as salts, silicates, borates, molybdates, vanadates, tungstates, etc., water-soluble organic salts (eg, malate, succinate, citrate, tartrate, etc.) Forming components: Antirust additives such as phosphites, zirconium compounds, tungstates, vanadates, silicates, borates, carbonates, amines, benzotriazoles, chelate compounds, etc .; hydroxyethyl cellulose, carboxy Methyl cellulose, polyacrylamide, sodium polyacrylate, polyvinyl pyrrolidone, polyvinyl alcohol, mica and talc Clay minerals, viscosity modifiers such as finely divided silica; nonionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants, dispersants such as water-soluble polymers, etc .; Sodium acid, potassium stearate, sodium oleate), metal soaps (calcium stearate, magnesium stearate, aluminum stearate, barium stearate, lithium stearate, zinc stearate, calcium palmitate), waxes (polyethylene wax, Polypropylene wax, carnauba wax, beeswax, paraffin wax, microcrystalline wax), fatty acid amide (ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, N, N'- disteari Lubricating components such as adipic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipate amide); oils such as vegetable oil, mineral oil, synthetic oil And the like. One of these components may be contained in the lubricant of the present invention, or two or more thereof may be contained in combination.
In addition, water solubility means the property to melt | dissolve 1 g or more in 25 degreeC and 100 g of water.

<< Contents >>
The ratio (B _M ) of the mass (A _M ) of the smectite clay mineral to the amine equivalent mass of the above ammonium ion (total mass of the compound (1) which is a raw material of ammonium ion: B _M ) contained in the lubricant There is no particular limitation on / A _M ), which is preferably in the range of 0.1 to 1.0, and more preferably in the range of 0.25 to 0.65. Moreover, when the inorganic solid particles are contained in the lubricant of the present invention, the content of the inorganic solid particles is not particularly limited, but the solid content ratio of the inorganic solid particles in the entire lubricant is preferably 0.01 to It is in the range of 10% by mass, more preferably in the range of 0.05 to 5% by mass.

When the lubricant of the present invention is a liquid lubricant, the content of the liquid medium contained in the liquid lubricant is not particularly limited, and a method of bringing a lubricant into contact with the surface of a metal material, a lubricant film to be formed It is set appropriately in consideration of the film thickness of the

<< Method of producing lubricants >>
The lubricant can be produced, for example, as follows. The compound (1) is dispersed in deionized water heated to a temperature above the melting point of the compound (1), and then an acid for cationizing the compound (1) is added and mixed to adjust the pH to a predetermined range. Adjust to prepare an aqueous solution of a cationized amine. Next, this aqueous solution and a dispersion in which the smectite clay mineral is dispersed in the above liquid medium are mixed while maintaining the pH in a predetermined range. By this mixing, the cation present in the interlayer of the smectite clay mineral is ion-exchanged with the cationized compound (1), and the smectite clay mineral in which the cationized compound (1) is inserted between the layers is included. Liquid lubricants can be produced. When two or more amines are used in combination, the two or more amines are dispersed in deionized water heated to a temperature higher than the melting point of the amine having a high melting point temperature, and then the liquid lubricant is used as described above. Can be manufactured. The pH is not particularly limited as long as it is 6.0 or less, and is preferably 4.5 or less. The value of pH is a value measured using the existing pH meter or pH test paper at the above-mentioned temperature at which deionized water is heated. The acid used to cationize the compound (1) is not particularly limited, and, for example, inorganic acids such as nitric acid and phosphoric acid; such as maleic acid, succinic acid, malic acid, tartaric acid, and citric acid Organic acids and the like can be mentioned, but non-halogen acids are preferable.

In addition, when the ion exchange with the cation which exists in the interlayer of a smectite clay mineral and the ammonium ion which cationized compound (1) is performed, the space | interval of the interlayer of a smectite clay mineral will increase. Therefore, the fact that the ammonium ion is inserted between the layers of the smectite clay mineral can be easily confirmed by measuring the distance between the layers of the smectite clay mineral before and after the insertion of the ammonium ion. As for the distance between layers, for example, the diffraction pattern is measured by X-ray diffraction according to the orientation method using a Cu tube, the diffraction angle of the bottom reflection (d001) plane is determined from the diffraction pattern, and Bragg's equation ( The interlayer spacing of the smectite clay mineral can be determined from 2d · sin θ = λ). In the Bragg's equation, “d” means the distance between layers of the smectite clay mineral, “θ” means the determined diffraction angle, and “λ” means the wavelength of the Kα ray.

When manufacturing a lubricant containing inorganic solid particles and other components, the addition timing of the inorganic solid particles and other components is not particularly limited, and, for example, an aqueous solution of the above amine or the above smectite clay mineral is dispersed It may be added to the dispersion liquid, or it may be added to a mixture obtained by mixing the aqueous solution of the amine and the dispersion liquid in which the smectite clay mineral is dispersed. It is preferable to add it.

Also, a solid lubricant can be produced by evaporating or distilling off the liquid medium contained in the above-mentioned liquid lubricant. The liquid lubricant and solid lubricant may be pulverized using a pulverizer. Alternatively, a liquid medium may be added to the produced solid lubricant to produce a liquid lubricant.

<< Usage of Lubricant >>
The friction between metal materials caused by sliding movement, rotational movement, movement such as piston movement or plastic working of wire, tube, bar, block etc. causes seizing of metal material, so seizing of metal material The lubricant of the present invention which can suppress the above is useful for metal materials where friction occurs.

<<< Metal material with coating of lubricant, metal material with lubricant attached >>>
A metal material having a lubricant film (hereinafter sometimes referred to as a lubricant film) comprises a contacting step of bringing the liquid lubricant into contact with the surface of the metal material, and a drying step of drying the contacted liquid lubricant. It can be manufactured by carrying out. Examples of the method of contacting the liquid lubricant include known methods such as immersion method, flow coating method, and spray method. The contact conditions in the contact step, that is, the contact time and the contact temperature are not particularly limited as long as they can produce a lubricating film. Drying of the liquid lubricant is carried out by evaporating the liquid medium in the lubricant to 15 wt% or less, preferably 3 wt% or less. Examples of the drying method include known methods such as natural drying, heat drying and air drying.

The adhesion amount of the lubricant film thus formed is preferably in the range of 0.5 to 40 g / m ² , more preferably in the range of 0.5 to 30 g / m ² , and 2 It is particularly preferable to be in the range of ̃20 g / m ² . By setting the adhesion amount of the lubricant film in the range of 0.5 to 40 g / m ² , not only excellent lubricity but also performances such as seizure resistance and clogging resistance can be improved.

The metal material to which the solid lubricant adheres can be manufactured by performing a deposition step of depositing the solid lubricant on the surface of the metal material. Examples of the method of depositing the solid lubricant include known methods such as electrostatic application, fluid immersion, and spraying. The deposition conditions in the deposition step, ie, the deposition temperature, are not particularly limited.

The adhesion amount of the solid lubricant is preferably in the range of 0.5 to 40 g / m ² , more preferably in the range of 0.5 to 30 g / m ² , and more preferably 2 to 20 g / m ² It is particularly preferred to be within the range. By setting the adhesion amount of the solid lubricant in the range of 0.5 to 40 g / m ² , it is possible to improve not only the excellent lubricity but also the performances such as seizure resistance and debris clogging resistance. .

In the method of manufacturing a metal material having a lubricant film or the method of manufacturing a metal material to which a solid lubricant adheres, shot blasting, sand blasting, wet blasting, peeling on the metal material before the contact step or the adhesion step. At least one cleaning treatment selected from the group consisting of alkaline degreasing and acid washing may be performed. Here, the purpose of the cleaning is to remove oxide scale and various stains (such as oil) grown by annealing or the like. Before and / or after these treatments, water washing may or may not be performed.

In addition, before the contacting step or the attaching step, if necessary, the metal material may be subjected to chemical conversion treatment, base treatment, and the like. Examples of the chemical conversion treatment include iron phosphate conversion treatment, zinc phosphate conversion treatment, zinc calcium phosphate conversion treatment, iron oxalate conversion treatment, aluminum fluoride conversion treatment, zircon oxide conversion treatment, and the like. As the surface treatment, for example, a method of bringing a surface treatment agent containing an alkali metal salt such as boric acid, silicic acid, sulfuric acid, phosphoric acid, tungstic acid or the like into contact on the surface of a metal material and drying; Other than the lubricants of the present invention (eg, zinc phosphate, zinc oxide, titanium dioxide, mica, molybdenum disulfide, tungsten disulfide, tin disulfide, graphite fluoride, graphite, boron nitride) A method of mechanically coating calcium hydroxide, calcium carbonate, lime, calcium sulfate, barium sulfate etc .; and the like.

The metal material is not particularly limited, and examples thereof include iron, iron alloys (eg, steel, stainless steel), copper, copper alloys, aluminum, aluminum alloys, titanium, titanium alloys and the like. The metal material is a sliding member, a member in contact with the sliding member, a rotary motion member, a cylinder, a piston, a workpiece for plastic working, a mold member for plastic working, and the like.

<<< The plastic working method of the metal material and the manufacturing method of the forming metal material >>>
By using the above-mentioned lubricant, plastic processing of the metal material can be efficiently performed. In the plastic working method of the metal material, a liquid lubricant is brought into contact with at least one surface of two metal materials (work material for plastic working and mold member for plastic working) which generate friction, and a lubricating film is formed. Including the steps of The formation of the lubricating coating can be carried out by carrying out the above-mentioned contacting step and drying step. The formation of the lubricating coating may be performed on the surface on which the two metal materials (the workpiece for plastic working and the surface of the plastic working mold member) come in contact with each other.

Further, the plastic working method of the metal material is a step of adhering a solid lubricant on the surface of at least one of two metal materials (work material for plastic working and mold member for plastic working) causing friction. including. The deposition of the solid lubricant can be carried out by carrying out the above-mentioned deposition step. The adhesion of the solid lubricant may be performed on the surface with which two metal materials (workpiece for plastic working and mold member for plastic working) come in contact with each other.

In addition, before formation of a lubricating film or adhesion of a solid lubricant, processing such as the above-mentioned cleaning treatment, chemical conversion treatment, or surface treatment may be performed.

As described above, after forming a lubricating film or depositing a solid lubricant, the step of plastically working by bringing two metal materials into contact with each other produces a metal material molded into a desired shape. can do. The plastic working method is not particularly limited, and examples thereof include known methods such as extrusion, wire drawing, drawing, drawing, bending, bonding, shearing, and sizing.

Hereinafter, the present invention will be more specifically described along with the effects thereof by listing examples of the present invention together with comparative examples. The present invention is not limited by these examples.

I. Production of Lubricant An example of production of a lubricant is shown below.
(Production Example 1)
To 950 g of deionized water was added 50 g of montmorillonite (exchangeable cation = Na +, CEC (Cation Exchange Capacity) value = 115 meq / 100 g), and the mixture was stirred for 1 hour with a homogenizer to prepare a dispersion. Next, n-palmitylamine [number of long-chain alkyl groups (hereinafter simply referred to as "Num"): 1, total number of carbon atoms in the main chain of long-chain alkyl groups (hereinafter simply referred to as "tot") : 16] 13.9 g (1.0 molar equivalent of CEC) is dispersed in 200 g of deionized water heated above the melting point temperature of the amine, and then brought to a pH of 3.3 using 10 wt% tartaric acid An aqueous solution of cationized amine was prepared by adjustment. The dispersion was added while the pH of the prepared aqueous solution was maintained at 3.3, and further stirred for 1 hour. Subsequently, the stirred mixture was suction filtered using 5 C filter paper, and then the solid content was recovered. The collected matter was dried at 60 ° C. overnight and then ground in an agate mortar to produce a solid lubricant. The CEC value was measured based on the Schollenberger method.

(Production Example 2)
The pH was adjusted to 4.1 by replacing n-palmitylamine (1.0 molar equivalent of CEC) with n-stearylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 18) In the same manner as in Production Example 1, a solid lubricant was produced.

(Production Example 3)
replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N-dimethyl-Nn-palmitylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 16), A solid lubricant was produced in the same manner as in Production Example 1 except that the pH was adjusted to 3.2.

(Production Example 4)
The pH of n-palmitylamine (1.0 molar equivalent of CEC) is replaced with N, N-dimethyl-Nn-stearylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 18), Was adjusted to 3.2, a solid lubricant was produced in the same manner as in Production Example 1.

(Production Example 5)
A solid lubricant was produced in the same manner as in Production Example 4, except that 1.0 molar equivalent of CEC was replaced with 0.8 molar equivalent of CEC, and the pH was adjusted to 3.2.

(Production Example 6)
A solid lubricant was produced in the same manner as in Production Example 4 except that 1.0 molar equivalent of CEC was replaced with 1.2 molar equivalent of CEC and the pH was adjusted to 3.8.

(Production Example 7)
A solid lubricant was produced in the same manner as in Production Example 4, except that 1.0 molar equivalent of CEC was replaced with 1.4 molar equivalent of CEC, and the pH was adjusted to 4.0.

Production Example 8
A solid lubricant was produced in the same manner as in Production Example 4, except that 1.0 molar equivalent of CEC was replaced with 1.6 molar equivalent of CEC, and the pH was adjusted to 3.6.

Production Example 9
n-Palmitylamine (1.0 molar equivalent of CEC) is replaced with N, N-dimethyl-Nn-behenylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 22), pH Was adjusted to 3.7, a solid lubricant was produced in the same manner as in Production Example 1.

Production Example 10
Replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N-di-n-octyl-N-methylamine (1.0 molar equivalent of CEC, Num = 2, Tot = 16) A solid lubricant was produced in the same manner as in Production Example 1 except that the pH was adjusted to 3.7.

(Production Example 11)
Replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N-di-n-lauryl-N-methylamine (1.0 molar equivalent of CEC, Num = 2, Tot = 24), A solid lubricant was produced in the same manner as in Production Example 1 except that the pH was adjusted to 3.9.

Production Example 12
replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N-di-n-stearyl-N-methylamine (1.0 molar equivalent of CEC, Num = 2, Tot = 36), A solid lubricant was produced in the same manner as in Production Example 1 except that the pH was adjusted to 3.5.

Production Example 13
Replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N, N-tri-n-octylamine (1.0 molar equivalent of CEC, Num = 3, Tot = 24), and adjust the pH to A solid lubricant was produced in the same manner as in Production Example 1 except that it was adjusted to 4.0.

Production Example 14
n-Palmitylamine (1.0 molar equivalent of CEC) was replaced with N, N, N-tri-n-decylamine (1.0 molar equivalent of CEC, Num = 3, Tot = 30), pH 3 A solid lubricant was produced in the same manner as in Production Example 1 except that the preparation was adjusted to .8.

Production Example 15
Replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N, N-tri-n-dodecylamine (1.0 molar equivalent of CEC, Num = 3, Tot = 36), and adjust the pH to A solid lubricant was produced in the same manner as in Production Example 1 except that the ratio was adjusted to 3.7.

Production Example 16
4. Change the pH of the n-palmitylamine (1.0 molar equivalent of CEC) to N, N-di-n-stearylamine (1.0 molar equivalent of CEC, Num = 2, Tot = 36); A solid lubricant was produced in the same manner as in Production Example 1 except that the concentration was adjusted to 0.

Production Example 17
To 950 g of deionized water was added 50 g of montmorillonite (exchangeable cation = Na +, CEC value = 115 meq / 100 g), and the mixture was stirred for 1 hour with a homogenizer to prepare a dispersion. Then, after dispersing N, N-di-n-stearylamine (1.0 molar equivalent of CEC, Num = 2, Tot = 36) in 200 g of deionized water heated above the melting point temperature of the amine An aqueous solution of a cationized amine was prepared by adjusting the pH to 3.3 with 10 wt% tartaric acid. Then, a mixed solution was prepared by mixing 0.5 g of graphene (1 wt% of montmorillonite) as inorganic solid particles in this aqueous solution for 30 minutes. While maintaining the pH of the prepared mixture, the dispersion was added and further stirred for 1 hour. Subsequently, the stirred mixture was suction filtered using 5 C filter paper, and then the solid content was recovered. The collected matter was dried at 60 ° C. overnight and then ground in an agate mortar to produce a solid lubricant.

Production Example 18
An aqueous solution of a cationized amine was prepared in the same manner as in Production Example 17 except that the pH was adjusted to 3.7. The dispersion was added while maintaining the pH of the prepared aqueous solution, and after further stirring for 1 hour, 0.5 g of graphene as inorganic solid particles was mixed for 30 minutes to prepare a mixed solution. Subsequently, the mixture was suction filtered using a 5 C filter paper, and then the solid content was recovered. The collected matter was dried at 60 ° C. overnight and then ground in an agate mortar to produce a solid lubricant.

Production Example 19
A solid lubricant was produced in the same manner as in Production Example 17 except that graphene was replaced with carbon nanotubes and the pH was adjusted to 4.0.

Production Example 20
A solid lubricant was produced in the same manner as in Production Example 18 except that graphene was replaced with carbon nanotubes and the pH was adjusted to 4.1.

Production Example 21
A solid lubricant was produced in the same manner as in Production Example 17 except that graphene was replaced by molybdenum disulfide and the pH was adjusted to 3.7.

Production Example 22
A solid lubricant was produced in the same manner as in Production Example 18 except that graphene was replaced by molybdenum disulfide and the pH was adjusted to 4.0.

Production Example 23
Montmorillonite to natural hectorite (exchangeable cation = Na +, CEC value = 97 meq / 100 g), n-palmitylamine to 24. 1 g of N, N-di-n-stearylamine (1.0 molar equivalent of CEC) A solid lubricant was produced in the same manner as in Production Example 1 except that the pH was adjusted to 2.8, respectively.

(Production Example 24)
Synthesis of montmorillonite to hectorite (exchangeable cation = Na +; CEC value = 79 meq / 100 g), N-palmitylamine 29.9 g of N, N-di-n-stearylamine (1.0 molar equivalent of CEC) A solid lubricant was produced in the same manner as in Production Example 1 except that the pH was adjusted to 2.9.

Production Example 25
n-Palmitylamine (1.0 molar equivalent of CEC) was replaced with n-octylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 8), and the pH was adjusted to 3.0 except Then, a solid lubricant was produced in the same manner as in Production Example 1.

Production Example 26
n-Palmitylamine (1.0 molar equivalent of CEC) was replaced with n-laurylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 12), and the pH was adjusted to 3.4 Then, a solid lubricant was produced in the same manner as in Production Example 1.

Production Example 27
Except that n-palmitylamine (1.0 molar equivalent of CEC) was replaced with n-myristylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 14) to adjust the pH to 4.0 Then, a solid lubricant was produced in the same manner as in Production Example 1.

Production Example 28
Replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N-dimethyl-Nn-octylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 8), A solid lubricant was produced in the same manner as in Production Example 1 except that the preparation was adjusted to 3.6.

Production Example 29
Replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N-dimethyl-Nn-laurylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 12), and adjust the pH to A solid lubricant was produced in the same manner as in Production Example 1 except that the preparation was adjusted to 3.8.

(Production Example 30)
Replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N-dimethyl-Nn-myristylamine (1.0 molar equivalent of CEC, Num = 1, Tot = 14), and adjust the pH to A solid lubricant was produced in the same manner as in Production Example 1 except that the preparation was adjusted to 3.9.

Production Example 31
replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N-di-n-hexyl-N-methylamine (1.0 molar equivalent of CEC, Num = 0, Tot = 0), A solid lubricant was produced in the same manner as in Production Example 1 except that the pH was adjusted to 3.6.

Production Example 32
Replace n-palmitylamine (1.0 molar equivalent of CEC) with N, N, N-tri-n-hexylamine (1.0 molar equivalent of CEC, Num = 0, Tot = 0), and adjust the pH to A solid lubricant was produced in the same manner as in Production Example 1 except that the ratio was adjusted to 3.7.

Production Example 33
50 g of montmorillonite was added to 950 g of deionized water, and the mixture was stirred for 1 hour with a homogenizer to prepare a dispersion. Next, N, N-di-n-stearylamine (1.0 molar equivalent of CEC) is dispersed in 200 g of deionized water heated to a temperature above the melting point temperature of the amine, and then 10 wt% of tartaric acid is used. An aqueous solution of cationized amine was prepared by adjusting the pH to 4.0. The dispersion was added while maintaining the pH of the prepared aqueous solution, and the mixture was further stirred for 1 hour to produce a slurry. To 91.0 parts by weight of the slurry, 1.6 parts by weight of potassium tetraborate as a binder, 0.5 parts by weight of carboxymethylcellulose as a dispersant, and 6.9 parts by weight of deionized water A lubricant was produced.

II. Preparation Method of Liquid Lubricant Each liquid lubricant was prepared using each solid lubricant of Production Examples 1 to 32 with the following composition.
(Composition composition)
7.5% by weight organically modified smectite clay mineral (powder)
Binder: potassium tetraborate 2.0% by weight
Dispersing agent: carboxymethylcellulose 0.5% by weight
90.0% by weight of deionized water

III. Machining performance evaluation
<Manufacture of a test piece on which a lubricating film is formed>
The following processing steps were performed using a cylindrical steel material (S10C) having a diameter of 14 mm and a height of 32 mm as a test piece.
(Processing process)
The test piece was immersed for 10 minutes at 60 ° C. in an alkaline degreaser [an aqueous solution prepared by mixing Fine Cleaner E 6400 (manufactured by Nippon Parkerizing Co., Ltd.) in water to a concentration of 20 g / L] for alkaline degreasing. Next, the test piece was immersed in tap water for 1 minute, and then immersed in deionized water for 1 minute. Subsequently, the test piece was immersed in the liquid lubricant prepared using the solid lubricant of Production Examples 1 to 32 or the liquid lubricant of Production Example 33 at 60 ° C. for 1 minute. After immersion, it was dried at 100 ° C. for 30 minutes to prepare test pieces (Examples 1 to 18 and 20 to 28 and Comparative Examples 1 to 8) on which a lubricating coating was formed. With respect to the liquid lubricant prepared using the solid lubricant of Production Example 16, a test piece (Example 19) on which a lubricating film was formed was the same as above except that the above-mentioned drying temperature was changed to 25 ° C. Made.
The adhesion amount of each lubricating film on the test pieces of Examples 1 to 28 and Comparative Examples 1 to 8 is shown in Table 1. The adhesion amount of the lubricant film was determined by the weight difference before and after film formation. In addition, the adhesion amount of the lubricating film was adjusted by changing the solid content ratio in the liquid lubricant.

<Processing performance evaluation test>
Machining performance evaluation can be found in the reference (Akishi Takahashi, Hitoshi Hirose, Shinobu Omiyama, Shigo Wang: 62nd Proceedings of the Japan Joint Conference on Plastic Processing, (2011), 89-90). It carried out based on the friction test method. Upsetting was performed at an upsetting rate of 45%, and the test pieces of Examples 1 to 28 and Comparative Examples 1 to 8 were processed into a barrel shape. An ironing process (strong processing) was performed using three ball molds (SUJ-2 bearing balls with a diameter of 10 mm) on the side portions of the barrel-shaped test pieces that were overhanging.
The processing performance of each test piece was evaluated according to the evaluation standard shown in FIG. The results are shown in Table 1. In addition, "とした" or more was taken as a pass.

IV. Lubrication performance evaluation <Manufacturing of test pieces having a lubricating film formed>
Using the cold-rolled steel plate (SPCC) of 70 mm × 150 mm (thickness 0.8 mm) instead of the cylindrical steel material (S10C) of 14 mmφ in diameter and 32 mm in height as a test piece, The test pieces (Examples 29 to 54 and Comparative Examples 9 to 16) on which a lubricant film was formed were produced. The test piece of Example 44 was dried at 100 ° C., and the test piece of Example 45 was dried at 25 ° C. Moreover, the adhesion amount of the lubricating film was 4 g / m ² respectively.

<Lubrication performance evaluation test>
The sliding test by the friction and wear tester was performed on the test pieces of Examples 29 to 54 and Comparative Examples 9 to 16. The sliding test was performed by the Bowden test. More specifically, a load of 1 kg was applied to a SUJ2 steel ball (10 mmφ) against the surface on which the lubricating coating was formed, and the test piece was reciprocated at a speed of 10 mm / s. In addition, the reciprocating motion was implemented at 1 cm intervals. Moreover, this test was implemented on 25 degreeC conditions. The lubricating performance evaluation of each test piece measured the dynamic friction coefficient value of the 5th reciprocation, and evaluated it according to the following evaluation criteria. In addition, "とした" or more was taken as a pass.
(Evaluation criteria)
○: Dynamic coefficient of friction is less than 0.15 Δ: Dynamic coefficient of friction is 0.15 or more and less than 0.2 ×: Dynamic coefficient of friction is 0.2 or more

V. Corrosion resistance evaluation <Manufacturing of test pieces having a lubricant film formed>
Using the cylindrical steel material (S45C) having a diameter of 25 mmφ and a height of 30 mm instead of the cylindrical steel material (S10C) having a diameter of 14 mmφ and a height of 32 mm as the test piece, the treatment process described in the processing performance evaluation is performed. Test pieces (Examples 55 to 80 and Comparative Examples 17 to 24) on which a lubricant film was formed were produced. The test piece of Example 70 was dried at 100 ° C., and the test piece of Example 71 was dried at 25 ° C. Moreover, the adhesion amount of the lubricating film was 4 g / m ² respectively.

<Corrosion resistance evaluation test>
Upset processing was performed on the test pieces of Examples 55 to 80 and Comparative Examples 17 to 24. Upset processing was carried out using a 200 ton crank press, sandwiching each test piece with a mirror-finished flat mold (SKD11) and applying pressure so that the compression ratio was about 50% (processing speed is 30) Strokes per minute).
The corrosion resistance evaluation of the upset processed test piece was carried out by leaving the upset processed test piece in the room for 10 days and observing the processed surface to confirm the presence or absence of rusting. Those with no rusting were evaluated as ○, and those with rusting were evaluated as x. The results are shown in Table 3.

Claims

The smectite clay mineral and an ammonium ion cationized with a primary amine or a secondary amine or a tertiary amine, wherein the ammonium ion is inserted between layers of the smectite clay mineral, and the primary amine Alternatively, the secondary amine or tertiary amine has one or more long chain alkyl groups having 8 or more carbon atoms in the main chain, and the total number of carbon atoms in the main chain of the long chain alkyl group is 16 or more. , Lubricants (except those containing lithium borate).
Smectite clay mineral, ammonium ion cationized with primary amine or secondary amine or tertiary amine, graphite, graphene, graphene oxide, fullerene, carbon nanotube, diamond like carbon (DLC), onion like carbon And at least the ammonium ion is inserted between the layers of the smectite clay mineral, and at least the primary amine or the secondary amine or the inorganic solid particles selected from the group consisting of molybdenum disulfide, and tungsten disulfide. The tertiary amine is a lubricant having one or more long chain alkyl groups whose main chain carbon number is 8 or more, and the total carbon number of the main chain long chain alkyl group is 16 or more.
The lubricant according to claim 1 or 2, which is solid.
A metal material having a coating of the lubricant according to claim 1 or 2.
A metal material to which the lubricant according to claim 3 is attached.
A method of plastic working a metal material, comprising the step of bringing a lubricant according to claim 1 into contact with at least one of two metal materials causing friction to form a lubricating film.
A method of plastic working a metal material, comprising the step of depositing the lubricant according to claim 3 on at least one surface of the two metal materials causing friction.
A process of causing a lubricant according to claim 1 or 2 to contact on at least one surface of two metal materials causing friction to form a lubricating film, and contacting two metal materials to perform plastic processing And B. a method of producing a formed and processed metal material.
4. A step of depositing the lubricant according to claim 3 on at least one surface of two metal materials causing friction, and a step of contacting two metal materials to perform plastic working. Method of manufacturing formed metal material.