CN105899650B

CN105899650B - Aqueous lubricating coating treatment agent having excellent corrosion resistance and workability, and metal material

Info

Publication number: CN105899650B
Application number: CN201580004211.5A
Authority: CN
Inventors: 畠山豪; 小见山忍
Original assignee: Nihon Parkerizing Co Ltd
Current assignee: Nihon Parkerizing Co Ltd
Priority date: 2014-03-28
Filing date: 2015-03-20
Publication date: 2020-02-21
Anticipated expiration: 2035-03-20
Also published as: EP3124582A1; EP3124582A4; US20170137741A1; JP6243515B2; CN105899650A; EP3124582B1; MX2016012566A; ES2928160T3; WO2015146818A1; JPWO2015146818A1

Abstract

The invention provides a water-based lubricating coating treatment agent which can obtain a lubricating coating with excellent practical corrosion resistance, processability and stripping performance. The aqueous lubricating coating agent is characterized in that a water-soluble silicate (A) and at least 1 water-soluble inorganic salt (B) selected from tungstate, phosphate and borate are blended so that the solid mass ratio (B)/(A) is in the range of 0.7 to 25.

Description

Aqueous lubricating coating treatment agent having excellent corrosion resistance and workability, and metal material

Technical Field

The present invention relates to an aqueous lubricating coating treatment agent used for plastic working of various metal materials, and a metal material having a coating formed by applying the treatment agent to the surface of a metal material and drying the coating.

Background

As the lubricant for plastic working, a so-called chemical conversion coating, which is a composite coating using a phosphate coating and a soap, is generally used. However, the chemical conversion coating has problems such as a by-product resulting from a reaction with a metal material, a water discharge treatment such as washing water, and a large treatment space, and in recent years, an aqueous coating type 1-liquid lubricant which is environmentally friendly has been developed.

Patent document 1 discloses a water-based lubricating coating treatment agent for plastic working of a metal material, which is characterized by: the composition is obtained by dissolving or dispersing (A) a water-soluble inorganic salt and (B) a wax in water, wherein the mass ratio of the solid components (B)/(A) is in the range of 0.3-1.5.

Patent document 2 discloses a water-based lubricating coating treatment agent for plastic working of a metal material, which is characterized in that: the aqueous lubricating coating treatment agent contains an alkali metal borate (A), wherein the alkali metal borate (A) contains lithium borate, the molar ratio of lithium in the alkali metal borate (A) to all alkali metals is 0.1-1.0, and the molar ratio (B/M) of boric acid B to alkali metal M in the alkali metal borate (A) is 1.5-4.0. This technique can form a coating film having not only high workability but also high corrosion resistance by suppressing crystallization of the coating film caused by moisture absorption of the coating film.

Patent document 3 discloses a water-soluble lubricant for non-phosphorus plastic working, which contains component a: inorganic solid lubricant, component B: wax, and component C: the water-soluble inorganic metal salt has a solid content mass ratio of component A to component B (component A/component B) of 0.1 to 5, and a solid content mass ratio of component C to the total amount of components A, B and C (component C/(component A + component B + component C)) of 1 to 30%. This technique is a lubricant containing no phosphorus and can achieve corrosion resistance equivalent to that of a chemical conversion coating film.

Patent document 4 discloses an aqueous lubricating coating treatment agent containing a water-soluble inorganic salt (a), a lubricant (B) selected from molybdenum disulfide and graphite, and a wax (C), and these substances and the like are dissolved or dispersed in water, and the ratio of (B)/(a) is 1.0 to 5.0 in terms of the weight ratio of solid components, and the ratio of (C)/(a) is 0.1 to 1.0 in terms of the weight ratio of solid components, and a method for forming a coating film thereof. This technique can achieve high workability at the same level as that of a chemical conversion coating by blending molybdenum disulfide and graphite with a conventional aqueous lubricating coating treatment agent.

Patent document 5 describes a skin membrane forming agent containing a silicate (a), a polycarboxylate (B), a water-compatible polymer and/or a water-compatible organic flake (lamelae) structure (C), and a molybdate and/or tungstate (D), wherein the mass ratio of the components is B/a of 0.02 to 0.6, C/a of 0.05 to 0.6, and D/a of 0.05 to 0.6.

Documents of the prior art

Patent document

Patent document 1: international publication WO02/012420

Patent document 2: japanese patent laid-open publication 2011-246684

Patent document 3: japanese patent laid-open No. 2013-209625

Patent document 4: international publication WO02/012419

Patent document 5: japanese laid-open patent publication No. 2002-

Disclosure of Invention

Technical problem to be solved by the invention

However, even when the aqueous lubricating coating treatment agents of patent documents 1 to 5 are used, there is a problem that it is impossible to form a coating film in a practical environment which combines high corrosion resistance (particularly long-term rust resistance) comparable to a chemical conversion treated coating film and workability at the time of imposing man-hours. In addition, when an aqueous lubricating coating treatment agent containing a silicate is used, the agent may cause a film release failure, a plating failure, an oxide film peeling failure, and the like.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that a coating film obtained by compounding a water-soluble silicate and a specific water-soluble inorganic salt at a specific ratio can provide high corrosion resistance (particularly long-term rust resistance) and workability, which cannot be achieved by these components alone, and sufficient film release properties, and have completed the present invention.

The present invention (1): an aqueous lubricating coating treatment agent characterized by being prepared by mixing a water-soluble silicate (A) and at least 1 water-soluble inorganic salt (B) selected from tungstate, phosphate and borate so that the solid mass ratio (B)/(A) is in the range of 0.7 to 25.

Invention (2): the aqueous lubricating coating treatment agent according to the invention (1) is characterized by containing a resin component (C) in which the solid content mass ratio (C)/{ (a) + (B) } is 0.01 to 3.

Invention (3): the aqueous lubricating coating agent according to the invention (2) above, characterized in that the resin component (C) is at least 1 selected from the group consisting of vinyl resins, acrylic resins, epoxy resins, urethane resins, phenolic resins, cellulose derivatives, polymaleic acids, polyolefins and polyesters.

Invention (4): the aqueous lubricating coating treatment agent according to any one of the above inventions (1) to (3), characterized by comprising a lubricant (D) having a solid content mass ratio (D)/{ (a) + (B) } of 0.01 to 6.

The present invention (5): the aqueous lubricating coating agent according to the invention (4) above, characterized in that the lubricant (D) is at least 1 selected from the group consisting of wax, polytetrafluoroethylene, fatty acid soap, fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, melamine cyanurate, amino acid compounds having a layered structure, and layered clay minerals.

Invention (6): a metal material having excellent plastic workability, wherein an adhesion amount of 0.5 to 40g/m is formed on a surface of the metal material²The lubricating coating according to (1) to (5) above, which is formed by applying the aqueous lubricating coating treatment agent for plastic working according to (1) to (5) above and drying the coating.

Effects of the invention

When the aqueous lubricating coating treatment agent of the present invention is used, a lubricating coating excellent in practical corrosion resistance, workability, and release properties is obtained. These properties are at levels equal to or higher than those of the chemical conversion coating, and are very superior to those of conventional aqueous lubricating coatings. The aqueous lubricating coating agent of the present invention is applied and dried to obtain a metal material having a coating film having the above-described excellent properties formed on the surface of the metal material.

Drawings

Fig. 1 shows the criteria for evaluation in the upset-ball reduction test (evaluation of burning resistance).

Detailed Description

The present invention will be described in detail below in the following order.

Aqueous lubricating coating agent (component, raw material, composition, etc.)

Method for producing aqueous lubricating coating treatment agent

Use of aqueous lubricating coating treatment agent

Method of using aqueous lubricating coating treatment agent

Aqueous lubricating coating treatment agent

The aqueous lubricating coating agent of the present invention is prepared by blending a water-soluble silicate (a) (hereinafter, referred to as silicate (a)) and at least 1 water-soluble inorganic salt (B) (hereinafter, referred to as inorganic salt (B)) selected from tungstate, phosphate and borate so that the solid content mass ratio (B)/(a) is in the range of 0.7 to 25. By blending in this range, a coating film having high corrosion resistance, processability and sufficient releasability, which cannot be obtained by the silicate (a) or the inorganic salt (B) alone, can be formed. The term "water-soluble" as used in the claims and the specification means that the solubility in water at room temperature (25 ℃) { mass (g) of solute dissolved in 100g of water } is at least 1g, preferably 10g or more.

When the silicate (a) and the inorganic salt (B) are combined to form a coating film, the inorganic salt (B) is finely and uniformly incorporated into the network structure formed by the silicate (a). As a result, the brittle film of the silicate (a) becomes soft and the processability is improved. Further, the inorganic salt (B) is incorporated into the network structure of the silicate (a), whereby the coating film is made denser, the barrier property is improved, and the corrosion resistance (particularly, long-term rust resistance) is also improved. In addition, the network structure of the silicate (a) is moderately hindered by the inorganic salt (B), thereby improving the releasability.

To achieve the above properties, the ratio of silicate (A) to inorganic salt (B) is important. The performance is exhibited in the range of the solid content mass ratio (B)/(A) of 0.7 to 25, preferably 0.9 to 10.0, and more preferably 1.1 to 3.0. If (B)/(a) is less than 0.7, a film having insufficient corrosion resistance and workability and poor film release properties cannot be obtained. This is due to: the amount of silicate is relatively increased, resulting in the formation of a strong network structure. If (B)/(a) is higher than 25, sufficient corrosion resistance cannot be obtained, and a film having poor adhesion and uniformity of the film is formed. This is due to: the amount of silicate is relatively too small, so that a sufficient network structure cannot be constructed, and the barrier property is reduced; the adhesion and uniformity of the film are reduced.

In particular, when a silicate and a tungstate are combined, corrosion resistance is remarkably improved by forming a passive film having a self-repairing function peculiar to tungsten. Further, since the steel material has a self-repairing function, stable corrosion resistance can be obtained even when a defect occurs in the coating film due to contact between the steel materials or the like. Therefore, even when a large amount of materials are processed at the same time, such as a large amount of processing using a barrel (barrel) used for the lubricating agent for cold forging and a coil processing of a wire rod, stable corrosion resistance is easily exhibited.

Examples of the silicate (a) used in the film-treating agent of the present invention include lithium silicate, sodium silicate and potassium silicate. These may be used alone, or 2 or more of them may be used in combination. Lithium silicate and/or sodium silicate are particularly preferably used.

The type of the inorganic salt (B) used in the coating agent of the present invention is specifically listed below. Examples of the tungstate include lithium tungstate, sodium tungstate, potassium tungstate, and ammonium tungstate. Examples of the phosphate include ammonium phosphate, lithium phosphate, sodium phosphate, and potassium phosphate. The phosphate also includes salts of condensed phosphoric acids such as tripolyphosphoric acid, metaphosphoric acid, and pyrophosphoric acid. Examples of the borate include sodium borate (sodium tetraborate, etc.), potassium borate (potassium tetraborate, etc.), and ammonium borate (ammonium tetraborate, etc.). These may be used alone or in combination of two or more.

Next, the resin component (C) will be explained. The resin component (C) is blended for the purpose of a pressure-sensitive adhesive action, improvement of adhesion between a substrate and a film, leveling by a thickening action, stabilization of a dispersed component, and improvement of barrier properties. Examples of the resin component (C) having such functions and properties include vinyl resins, acrylic resins, epoxy resins, urethane resins, phenolic resins, cellulose derivatives, polymaleic acids, polyolefins, and polyesters. The resin component (C) used herein is not particularly limited as long as it has film-forming properties, and is usually supplied in a water-soluble or water-dispersed state. These may be used alone or in combination of two or more.

The solid content mass ratio (C)/{ (A) + (B) } of the silicate (A), the inorganic salt (B) and the resin component (C) in the aqueous lubricating film-treating agent is preferably 0.01 to 3, and (C)/{ (A) + (B) } is more preferably 0.1 to 1.5. If (C)/{ (a) + (B) } is less than 0.01, the binder action expected for the resin component (C) may not be sufficiently exhibited, the adhesion between the substrate and the film may not be improved, leveling may be imparted by the thickening action, the dispersion component may be stabilized, the barrier property may not be improved, and if (C)/{ (a) + (B) } exceeds 3, the amount of silicate or inorganic salt may be relatively reduced, and thus high corrosion resistance and high processability may not be sufficiently exhibited.

Next, lubricant (D) will be described. The lubricant (D) has lubricity and slidability, and has a function of reducing the frictional force between the die and the workpiece during machining. In general, when the frictional force is increased during plastic working, an increase in working energy, heat generation, burning, and the like occur, but when the aqueous lubricating coating treatment agent of the present invention contains the lubricant (D), an increase in frictional force can be suppressed. Examples of the lubricant (D) having such functions and properties include wax, polytetrafluoroethylene, fatty acid soap, fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, melamine cyanurate, amino acid compounds having a layered structure, and layered clay minerals. Among them, from the viewpoint of corrosion resistance and liquid stability, it is more preferable to blend wax, polytetrafluoroethylene, fatty acid soap, fatty acid metal soap, fatty acid amide, melamine cyanurate, amino acid compound having a layered structure, and layered clay mineral. These may be used alone or in combination of two or more. Specific examples of the wax include polyethylene wax, paraffin wax, microcrystalline wax, polypropylene wax, and carnauba wax. Specific examples of the fatty acid soap include sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, sodium stearate, and potassium stearate. Specific examples of the fatty acid metal soap include calcium stearate, zinc stearate, barium stearate, magnesium stearate, and lithium stearate. The fatty acid amide is an amide compound having 2 fatty acids, and specific examples thereof include ethylene dilauramide and ethyleneBisstearamide, ethylenebisbehenamide, N '-distearyladipamide, ethylenebisoleamide, ethylenebiserucamide, hexamethylenebisoleamide, N' -dioleyladipamide. The layered amino acid compound is an amino acid having a hydrocarbon group with 11 or more carbon atoms in its molecular structure or a derivative thereof. Specific examples thereof include N-lauroyl-L-lysine [ C ]₁₁H₂₃CONH(CH₂)₄CH(NH₂)COOH]. Examples of the layered clay mineral include natural or synthetic products of smectite group, vermiculite group, mica group, brittle mica group, pyrophyllite group, and kaolin group. Specific examples of the smectite group include montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stevensite; the vermiculite group includes dioctahedral vermiculite and trioctahedral vermiculite; examples of the mica group include muscovite, paragonite, illite, phlogopite, biotite, lepidolite and lepidolite; examples of the group of the brittle mica include pearl mica and green brittle mica; examples of the pyrophyllite family include pyrophyllite and talc; examples of the kaolin family include kaolin, dickite, nacrite, halloysite, chrysotile, and antigorite. In addition, these layered clay minerals are organically treated, whereby an organic modifier can be introduced between the layers. The organic treatment is carried out by introducing an organic modifier in a state where the layered clay mineral is swollen with water to enlarge the interlayer distance. The organic modifier is an alkylamine or an alkyl quaternary ammonium salt which is adsorbed between layers to form a firm bond, and specific examples thereof include stearyl dimethylamine, distearyl amine, distearyl dimethylamine, stearyl trimethyl ammonium chloride, and distearyl dimethyl ammonium chloride.

The blending ratio of the lubricant (D) in the aqueous lubricating coating agent of the present invention will be described below. When the lubricant (D) is blended, the solid content mass ratio (D)/{ (A) + (B) } of the silicate (A) and the inorganic salt (B) to the lubricant (D) is preferably in the range of 0.01 to 6, and more preferably in the range of 0.1 to 2. Here, if (D)/{ (a) + (B) } is less than 0.01, the friction reducing action expected for the lubricant (D) cannot be sufficiently exhibited, and if (D)/{ (a) + (B) } exceeds 6, the amounts of the silicate (a) and the inorganic salt (B) are relatively small, and high corrosion resistance and high workability may not be sufficiently exhibited.

In the aqueous lubricating coating treatment agent of the present invention, a viscosity modifier may be blended in addition to the silicate (a), the inorganic salt (B), the resin component (C), and the lubricant (D) in order to ensure a uniform coating state and impart leveling property and thixotropy to the lubricant when applied to a substrate. The amount of these components to be blended is preferably 0.1 to 50% by mass based on the mass of the entire solid content. Specific examples of such viscosity modifiers include: smectite clay minerals such as montmorillonite, sauconite, beidellite, hectorite, nontronite, saponite and stevensite; inorganic tackifiers such as fine powder silica, bentonite, and kaolin.

The aqueous lubricating coating agent of the present invention can impart high corrosion resistance before and after processing, but other water-soluble rust inhibitors and inhibitors may be blended for the purpose of further improving corrosion resistance. As a specific example, the following known examples can be used: various organic acids such as oleic acid, dimer acid, tartaric acid, citric acid, and the like; various chelating agents such as EDTA, NTA, HEDTA, DTPA and the like; mixed components of alkanols such as triethanolamine, amine salts of p-tert-butylbenzoic acid, and the like; and combinations of amine carboxylates, amine dibasic acids, alkenyl succinic acids and water-soluble salts thereof, and aminotetrazole and water-soluble salts thereof. These may be used alone or in combination of two or more. The amount of these compounds to be blended is preferably 0.1 to 30% by mass based on the total mass of the solid components.

The liquid medium (solvent, dispersion medium) in the aqueous lubricating coating treatment agent of the present invention is water. In order to shorten the drying time of the lubricant in the drying step, an alcohol having a lower boiling point than water may be blended.

The aqueous lubricating coating agent of the present invention may contain a water-soluble strong alkali component in order to improve the stability of the liquid. Specific examples thereof include lithium hydroxide, sodium hydroxide and potassium hydroxide. These may be used alone or in combination of two or more. The amount of these compounds to be blended is preferably 0.01 to 10% by mass based on the mass of the entire solid content.

In order to disperse the water-insoluble substance, it is also permissible to use a surfactant. However, the amount of addition of the components other than (a), (B), (C) and (D) is preferably not more than 50% by mass of the solid content of the aqueous lubricating coating agent within a range not to lower the required performance. In other words, the total amount of the additives (a), (B), (C) and (D) is preferably 50 mass% or more, more preferably 70 mass% or more, and still more preferably 85 mass% or more based on the solid content of the aqueous lubricating coating agent.

Method for producing aqueous lubricating coating treatment agent

The aqueous lubricating coating agent of the present invention is produced by, for example, adding and mixing a silicate (a), an inorganic salt (B), a resin component (C), a lubricant (D), and the like to water as a liquid medium. The mixing is carried out by a usual method such as propeller stirring and a homogenizer.

Use of aqueous lubricating coating treating agent

The aqueous lubricating coating agent of the present invention is suitably used for plastic working in the cold working field such as forging, wire drawing, tube drawing, roll forming, and pressing.

Metallic material to be used

The aqueous lubricating coating agent of the present invention is applied to metal materials such as iron, steel, stainless steel, copper alloy, aluminum alloy, titanium alloy, and the like. The shape of the metal material is not particularly limited, and not only a raw material such as a bar material or a block material but also a shape after forging (a gear, a shaft, or the like) may be used.

Use as a base coating

The aqueous lubricating coating agent of the present invention can also be used as an undercoat coating agent for other wet lubricants or dry lubricants. By using this as an undercoat film, the workability and corrosion resistance of other wet lubricants and dry lubricants can be improved. The type of lubricant to be combined is not particularly limited, and for example, as a wet lubricant, a usual water-based lubricant coating agent, lime soap, or forging oil as represented by the above patent documents 1 to 4 can be used. As the dry lubricant, for example, a normal lubricating powder or drawing powder containing a higher fatty acid soap, borax, lime, molybdenum disulfide, or the like as a main component can be used.

Method of Using Water-based lubricating coating treating agent

Next, a method of using the aqueous lubricating coating agent of the present invention will be described. The use method comprises a step of cleaning the metal material, a step of applying the aqueous lubricating coating treatment agent, and a drying step. The metal material and the respective steps to be used will be described below.

Purification step (pretreatment step)

Preferably, at least 1 kind of cleaning treatment selected from shot blasting, sand blasting, wet blasting, peeling, alkali degreasing, and acid cleaning is performed before the aqueous lubricating film is formed on the metal material. The cleaning herein refers to a treatment for removing an oxide film grown by annealing or the like and various contaminants (oil or the like).

Application procedure

The step of applying the aqueous lubricating film of the present invention to a metal material is not particularly limited, and a dipping method, a flow coating method, a spray coating method, or the like can be used. The coating time is not particularly limited as long as the metal surface is sufficiently covered with the aqueous lubricating coating treatment agent of the present invention. In order to improve the drying property, the metal material may be heated to 60 to 80 ℃ and then contacted with the aqueous lubricating coating treatment agent for plastic working of the metal material, or the metal material may be contacted with the aqueous lubricating coating treatment agent for plastic working of the metal material heated to 40 to 70 ℃. This can greatly improve the drying property, and can also dry at room temperature and reduce the loss of heat energy in some cases.

The amount of the water-based lubricating coating formed on the metal surface is appropriately controlled by the degree of subsequent processing, and is preferably 0.5 to 40g/m²More preferably 2 to 20g/m²The range of (1). The amount of the adhesive is less than 0.5g/m²In the case of (2), the lubricity becomes insufficient. In addition, if the amount of adhesion exceeds 40g/m²However, the lubricating property is not problematic, but clogging of the mold with dross or the like occurs, which is not preferable. The adhesion amount can be calculated from the mass difference and the surface area of the metal material before and after the treatment. The mass (concentration) of the solid content of the aqueous lubricating coating treatment agent is appropriately adjusted to control the amount of the deposit. A high-concentration aqueous lubricating coating agent was prepared and diluted with water to obtain a target deposition amount. The water for dilution is not particularly limited, and deionized water and distilled water are preferred.

Drying step

The drying step is not particularly limited, and is preferably performed at 60 to 150 ℃ for about 1 to 30 minutes.

Optional step 1 (base coating step)

The aqueous lubricating coating agent of the present invention can prevent seizure between a die and a workpiece during processing, can impart high corrosion resistance before and after processing, and can be subjected to an undercoat coating treatment for further improving the processability and corrosion resistance. The base coating treatment may be a reactive coating or a non-reactive coating. Specific examples of the reactive coating include phosphates, iron oxide, zirconium hydroxide, molybdates, oxalates, tannic acid, and the like. Specific examples of the non-reactive film include silicates, borates, zirconium compounds, vanadium compounds, colloidal silica, resin coatings, and the like.

Optional step 2 (stripping step)

The lubricating coating formed by the aqueous lubricating coating treatment agent of the present invention can be removed by immersion in an aqueous alkaline cleaning agent or by spray cleaning. The alkaline cleaning agent is a solution in which a usual alkaline component such as sodium hydroxide or potassium hydroxide is dissolved in water, and when an aqueous lubricating film is brought into contact with the solution, the aqueous lubricating film is dissolved in the cleaning liquid, and therefore, the film can be easily removed. Therefore, contamination in the subsequent step due to the film removal failure by alkali cleaning is eliminated, and the plating failure and the peeling failure of the oxide film can be prevented from occurring.

Examples

The effects of the present invention will be specifically described by way of examples of the present invention and comparative examples. It is to be noted that the present invention is not limited to these examples.

EXAMPLE A

(1-1) production of aqueous lubricating coating agent

The water-based lubricating coating treatment agents of examples 1 to 16 and comparative examples 1 to 8 were prepared by using the following components in the combination and ratio shown in tables 1 to 2. Comparative example 9 was a phosphate/soap treatment.

< silicate >

(A-1) sodium silicate (Na)₂O·nSiO₂n＝3)

(A-2) lithium silicate (Li)₂O·nSiO₂n＝3.5)

(A-3) Potassium silicate (K)₂O·nSiO₂n＝2.3)

< inorganic salt >

(B-1) sodium tungstate

(B-2) sodium tripolyphosphate

(B-3) Potassium metaborate

< resin component >

(C-1) sodium-neutralizing salt of isobutylene-maleic anhydride copolymer (molecular weight about 165,000)

< lubricating composition >

(D-1) anionic polyethylene wax (average particle diameter 5 μm)

(D-2) nonswelling synthetic mica (average particle diameter 5.0 μm)

(1-2) method of Using Water-based lubricating coating treatment agent

< Standard procedure >

(a) Degreasing: a commercially available degreasing agent (FINE CLEANER E6400, manufactured by JAPONICA Rice-flour-noodles, Japan) was immersed at 60 ℃ for 10 minutes at a concentration of 20g/L

(b) Washing with water: running water, normal temperature, dipping for 20 seconds

(c) Acid washing: 17.5% hydrochloric acid, normal temperature, 20 minutes of immersion

(d) Washing with water: running water, normal temperature, dipping for 20 seconds

(e1) [ e3 ] lubrication treatment: each of the examples and comparative examples is described in detail

(f) And (3) drying: 100 ℃ for 10 minutes

< lubricating treatment in examples 1 to 15 and comparative examples 1 to 8 >

(e1) And (3) lubricating film treatment: (1-1) the aqueous lubricating coating agent prepared in (1-1) was immersed at 60 ℃ for 1 minute

< pretreatment and film treatment in example 16 >

(e1) Substrate treatment: a commercially available zirconium chemical conversion treatment agent (Pellucide 1500, manufactured by Karma Rice-flour-Ling) was immersed at 45 ℃ and pH4.0 for 2 minutes at a concentration of 50g/L

(e2) Washing with water: running water, normal temperature, dipping for 20 seconds

(e3) And (3) lubricating film treatment: (1-1) the aqueous lubricating coating agent prepared in (1-1) was immersed at 60 ℃ for 1 minute

< pretreatment and film treatment of comparative example 9 (phosphate/soap treatment) >

(e1) Formation treatment: a commercially available zinc phosphating agent (Palbond 181X, manufactured by JAPONICA Rice-flour-like Rice-flour noodles) was immersed at 80 ℃ for 7 minutes at a concentration of 75g/L

(e2) Washing with water: running water, normal temperature, dipping for 30 seconds

(e3) Soap treatment: a commercially available reaction soap lubricant (Palube 235, manufactured by Karma Kogyo Co., Ltd.) was immersed at 85 ℃ for 3 minutes at a concentration of 70g/L

The amount of dry skin film is as follows: 10g/m²

(1-3) evaluation test

(1-3-1) spur (spike) test

The workability was evaluated by the piercing test in examples 1 to 16 and comparative examples 1 to 9. The pricking test is carried out according to the method described in Japanese patent application laid-open No. 5-7969. The lubricity was evaluated by the height of the bur and the forming load after the test. The higher the height of the bur and the lower the forming load, the more excellent the lubricity. In this publication, the area magnification in the pricking test is about 10 times. The lubricity of the film was evaluated by measuring the load and the height of the bur during the processing.

Test piece for evaluation: S45C spheroidized annealed material 25mm phi x 30mm

Evaluation criteria:

piercing performance (piercing height (mm)/processing load (kNf) × 100)

The larger the value, the better the lubricity

◎ is 0.96 or more

○, more than 0.94 and less than 0.96

△, more than 0.92 and less than 0.94

▲, more than 0.90 and less than 0.92

X: less than 0.90

(1-3-2) upsetting-ball reducing test (evaluation of burning resistance)

Workability was evaluated by an upset ball reducing test for examples 1 to 16 and comparative examples 1 to 9. The upset-ball diameter reduction test was carried out according to the method described in Japanese patent application laid-open No. 2013-215773. The area magnification in the upset-ball reducing test is 150 times or more at most, and the area magnification is very large compared with the above-mentioned piercing test, and the test is a test that reproduces the strong processing. The amount of burn into the reduced surface was evaluated, and the burn resistance of the film was evaluated by the amount of time required for the burn.

Test piece for evaluation: S10C spheroidized annealed material 14mm phi x 32mm

Bearing ball: 10mm phi SUJ2

Evaluation criteria:

the burning area was evaluated with respect to the entire area of the reduced diameter surface. The evaluation criteria are shown in FIG. 1.

◎ very superior compared to phosphate/soap film

○ superior to phosphate/soap film

△ equal to phosphate/soap skin film

▲, worse than phosphate/soap film

X: very poor compared to phosphate/soap skin films

(1-3-3) Defilmability test

Examples 1 to 16 and comparative examples 1 to 8 were subjected to a mold release property test. Since comparative example 9 is different from the usual method of releasing the film, it was excluded from the test level. In the release test, a cylindrical test piece was upset at a 50% compression ratio using a die having both flat upper and lower surfaces, and then immersed in an alkaline cleaner to peel off the film. After washing with water in the step (d) of (1-2), drying and cooling were performed in the step (f), and the mass of the test piece was measured. After the lubricating treatment (e), the test piece was dried and cooled (f), and the mass of the test piece was measured. The quality of the membrane is converted by the mass difference between the front and the back. After the alkali washing, the specimen was dried and cooled in (f), and the mass of the specimen was measured. The mass of the skin after the degreasing treatment was calculated from the mass after the alkali cleaning and the mass after the acid cleaning.

Test piece for evaluation: S45C spheroidized annealed material 25mm phi x 30mm

Alkali cleaning agent: 2% NaOH in water

Demoulding conditions are as follows: the liquid temperature is 60 ℃, and the dipping time is 2 minutes

Coating residual rate (%) (coating mass after release treatment/coating mass before release treatment) × 100

Evaluation criteria:

the lower the residual rate of the coating film, the better the releasability

◎ the residual rate of the coating is 0%

○ the residual rate of the coating is more than 0 and less than 8%

△, the residual rate of the coating is more than 8% and less than 16%

▲, the residual rate of the coating is more than 16% and less than 25%

X: the residual rate of the coating is more than 25%

(1-3-4) Corrosion resistance test

Examples 1 to 16 and comparative examples 1 to 9 were subjected to a corrosion resistance test. The 5 test pieces were subjected to a lubricating treatment simultaneously using a roller, and the test pieces were exposed indoors for 3 months in an open atmosphere in summer, and the occurrence of rust was observed. The larger the rust area, the worse the corrosion resistance. All of the 5 test pieces were evaluated.

Test piece for evaluation: S45C spheroidized annealed material 25mm phi x 30mm

Evaluation criteria:

◎ rust area is less than 3% (superior to phosphate/soap film)

○ wherein the rust area is more than 3% and not more than 10% (more excellent than phosphate/soap coating)

△ the rust area is more than 10% and less than 20% (same as phosphate/soap skin film)

▲ the rust area is more than 20% and less than 30% (worse than phosphate/soap coating)

X: rust area over 30% (very poor compared to phosphate/soap skin film)

(1-3-5) composite score

The evaluation results of the above 4 tests were scored according to the criteria shown in Table 3, and the total score was summarized.

The test results are shown in tables 4 and 5. Table 5 shows details of the corrosion resistance test. As can be seen from the table: the examples were excellent in workability (a piercing test and a ball reducing test), releasability and corrosion resistance (indoor exposure). Further, with respect to corrosion resistance, the level of sodium tungstate blended tends to be good, and variation in performance is small. The ratio of the silicate (a) to the inorganic salt (B) in comparative examples 1 to 8 is beyond the range of the present embodiment, and the results of the ball diameter reduction test and the corrosion resistance test tend to be inferior. The phosphate film of comparative example 9 was treated with the reactive soap, and showed excellent performance, but was inferior to that of examples.

Hereinafter, the case where the present invention is used as a base film of a dry lubricant and a wet lubricant will be described more specifically together with the effects of the present invention by referring to examples and comparative examples of the present invention. It is to be noted that the present invention is not limited to these examples.

EXAMPLE B

(2-1) production of aqueous lubricating coating agent

The water-based lubricating coating treatment agents of examples 17 to 42 and comparative examples 11 to 18, 20 to 27 were prepared by using the following components in the combinations and ratios shown in tables 6 and 7. Comparative example 10 used only the drawing powder and did not use the lubricating coating of the present invention. Comparative example 19 uses lime soap without using the lubricating film of the present invention. Comparative example 28 is a phosphate/soap treatment. In examples 30 to 42 and comparative examples 19 to 28, the drawing powder was not used.

(2-2) lubrication treatment

< lubricating treatments in examples 17 to 28 and comparative examples 11 to 18 >

The treatment was carried out by the standard procedures described in (1-2).

(e) And (3) lubricating film treatment: (2-1) the aqueous lubricating coating agent prepared in (2-1) was immersed at 60 ℃ for 1 minute

< pretreatment and coating treatment in examples 30 to 41 and comparative examples 20 to 27 >

The treatment was carried out by the standard procedures described in (1-2).

(e1) And (3) lubricating film treatment: (2-1) the aqueous lubricating coating agent prepared in (2-1) was immersed at 60 ℃ for 1 minute

Thereafter, as an upper coating film, a commercially available lime soap (LUB-CAO 2, manufactured by JAPONICA Rice-Scale) (250 g/L) was immersed at 60 ℃ for 1 minute, and dried in the same manner as in (f) to obtain a lime soap coating film amount of 5g/m²。

< pretreatment and film treatment in example 29 >

(e3) And (3) lubricating film treatment: (2-1) the aqueous lubricating coating agent prepared in (2-1) was immersed at 60 ℃ for 1 minute

< pretreatment and film treatment in example 42 >

< pretreatment and film treatment of comparative example 10 >

(e) Pure water washing: deionized water, normal temperature, dipping at 30 DEG C

< pretreatment and film treatment of comparative example 19 >

(e) Lubrication: commercially available lime soap (LUB-CAO 2, manufactured by JAPONICA Rice-flour-noodles) was immersed at 60 ℃ at a temperature of 250g/L for 1 minute

(f) And (3) drying: 100 ℃ for 10 minutes

The amount of the corresponding lime soap leather film is 5g/m²

< pretreatment and coating treatment of comparative example 28 (phosphate/soap treatment) >

(e1) Formation treatment: a commercially available zinc phosphating agent (Palbond 421WD, manufactured by Nippon Karma Rice-flour-paste Co., Ltd.) was immersed at 80 ℃ for 10 minutes at a concentration of 75g/L

The amount of dry skin film is as follows: 10g/m²

(2-3) evaluation test

(2-3-1) wire drawing test (evaluation of lubricity)

Workability was evaluated by a wire drawing test in examples 17 to 42 and comparative examples 10 to 28. A steel wire having a diameter of 3.2mm was drawn through a die having a diameter of 2.76 mm, thereby carrying out wire drawing. In examples 17 to 29 and comparative examples 10 to 18, Missile C40 of Sonpu industries was used as a dry lubricant. The dry lubricant is added to the die box just before drawing the material, causing it to naturally adhere to the material. The residual amounts of the burned and lubricating films of the test materials after drawing were evaluated. The coating was peeled off using the following coating peeling agent, and the coating amount after wire drawing was determined from the mass difference before and after peeling.

Test piece for evaluation: SWCH45K material phi 3.2mm x 20m

Diameter of the die: phi 2.76

Film-peeling agent: commercially available alkaline Release agent (FC-E6463, manufactured by JAPONICA Rice-Linnaeus, Ltd.) at 20g/L

Evaluation criteria:

coating residual rate (%) (coating amount before processing/coating amount after processing) × 100

The film amount before processing does not contain lubricating powder. The amount of the coating after processing contains a lubricant powder.

◎, the residual rate of the coating is more than 85%

○, the residual rate of the coating is more than 75% and less than 85%

△, the residual rate of the coating is more than 65% and less than 75%

▲, the residual rate of the coating is more than 50% and less than 65%

X: the residual rate of the coating is less than 50% or burning occurs

(2-3-2) Corrosion resistance test

Examples 17 to 42 and comparative examples 10 to 28 were evaluated for corrosion resistance. The wire rod subjected to the wire drawing test was exposed indoors for 3 months in an open atmosphere in summer, and the occurrence of rusting was observed. The larger the rust area, the worse the corrosion resistance.

Evaluation criteria:

◎ very superior to phosphate/soap film (rust area 3% or less)

○ is more excellent than phosphate/soap film (rust area is 3% or more but less than 10%)

△ equal to phosphate/soap skin film (rust area more than 10% and less than 20%)

▲ worse than phosphate/soap film (rust area more than 20% and less than 30%)

X: very poor compared to phosphate/soap skin film (rust area over 30%)

The test results are shown in Table 8. In all of the examples, a large amount of coating was left, and the results were found to be good in workability and corrosion resistance. Since the corrosion resistance after drawing is also high, it is understood that a large amount of the lubricating film of the present invention remains even after processing. Comparative examples 10 and 19 were at a level at which the lubricant of the present invention was not used, and were very poor in drawability and corrosion resistance. In comparative examples 11 to 18 and 20 to 27, the ratio of the silicate (a) to the inorganic salt (B) was not properly set, and the residual amount of the coating after drawing and the corrosion resistance were poor. The phosphate film of comparative example 28, which was treated with the reactive soap, exhibited excellent performance, but required wastewater treatment and liquid management, and could not be used in a simple treatment process or apparatus, and generated waste associated with the reaction, which resulted in a large environmental load.

From the above description, it can be seen that: the aqueous lubricant of the present invention can achieve both high workability and high corrosion resistance. Further, the lubricating coating after processing with the cleaning agent also had good releasability. Therefore, the industrial utility value is extremely high.

[ TABLE 1 ]

[ TABLE 2 ]

[ TABLE 3 ]

	Pricking pin	Thinning of ball	Detachability of film	Corrosion resistance
					◎	5	10	5	10
○	4	8	4	8
					△	3	6	3	6
▲	2	4	2	4
					×	1	2	1	2

[ TABLE 4 ]

	Pricking pin	Thinning of ball	Detachability of film	Corrosion resistance	Composite score
						Example 1	◎	◎	◎	◎	30
Example 2	◎	◎	◎	◎	30
						Example 3	◎	◎	◎	◎	30
Example 4	◎	○	○	◎	27
						Example 5	◎	◎	◎	○	28
Example 6	◎	○	○	○	25
						Example 7	○	○	◎	○	25
Example 8	◎	◎	◎	◎	30
						Example 9	◎	◎	◎	◎	30
Example 10	◎	◎	◎	○	28
						Example 11	◎	◎	◎	○	28
Example 12	◎	◎	◎	◎	30
						Example 13	◎	◎	◎	◎	30
Example 14	◎	◎	◎	◎	30
						Example 15	◎	◎	◎	◎	30
Example 16	◎	◎	◎	◎	30
						Comparative example 1	○	▲	×	▲	13
Comparative example 2	○	▲	◎	▲	17
						Comparative example 3	○	△	▲	▲	19
Comparative example 4	○	▲	◎	▲	17
						Comparative example 5	○	▲	▲	▲	14
Comparative example 6	○	▲	◎	×	15
						Comparative example 7	○	▲	◎	▲	17
Comparative example 8	○	▲	◎	×	15
						Comparative example 9	△	△	※	△	20

Comparative example 9 was not evaluated because the mold release method was different.

The overall score for comparative example 9 was calculated as detachability ◎.

[ TABLE 5 ]

N＝1

N＝2

N＝3

N＝4

N＝5

Comprehensive evaluation

Example 1

◎

Example 2

◎

Example 3

◎

Example 4

◎

○

◎

Example 5

◎

○

Example 6

◎

○

Example 7

○

Example 8

◎

Example 9

◎

○

◎

Example 10

◎

○

△

○

Example 11

◎

○

△

○

Example 12

◎

Example 13

◎

Example 14

◎

○

◎

Example 15

◎

Example 16

◎

Comparative example 1

△

▲

×

▲

Comparative example 2

▲

×

▲

Comparative example 3

△

▲

Comparative example 4

▲

Comparative example 5

▲

×

▲

Comparative example 6

▲

×

Comparative example 7

▲

×

▲

Comparative example 8

▲

×

Comparative example 9

△

[ TABLE 6 ]

[ TABLE 7 ]

[ TABLE 8 ].

	Drawability	Corrosion resistance
			Example 17	◎	◎
Example 18	◎	◎
			Example 19	◎	◎
Example 20	◎	◎
			Example 21	○	◎
Example 22	◎	○
			Example 23	○	○
Example 24	○	○
			Example 25	◎	◎
Example 26	◎	◎
			Example 27	◎	○
Example 28	◎	○
			Example 29	◎	◎
Example 30	◎	◎
			Example 31	◎	◎
Example 32	◎	◎
			Example 33	◎	◎
Example 34	○	◎
			Example 35	◎	○
Example 36	○	○
			Example 37	○	○
Example 38	◎	◎
			Example 39	◎	◎
Example 40	◎	○
			EXAMPLE 41	◎	○
Example 42	◎	◎
			Comparative example 10	×	×
Comparative example 11	▲	▲
			Comparative example 12	▲	×
Comparative example 13	△	▲
			Comparative example 14	▲	▲
Comparative example 15	▲	×
			Comparative example 16	▲	×
Comparative example 17	▲	×
			Comparative example 18	▲	×
Comparative example 19	▲	×
			Comparative example 20	△	▲
Comparative example 21	▲	×
			Comparative example 22	△	△
Comparative example 23	△	▲
			Comparative example 24	△	×
Comparative example 25	△	×
			Comparative example 26	△	×
Comparative example 27	△	×
			Comparative example 28	○	△

Claims

1. An aqueous lubricating coating agent characterized by being prepared by mixing a water-soluble silicate (A) and a tungstate (B) so that the solid mass ratio (B)/(A) is in the range of 0.7 to 25,

the aqueous lubricating coating treatment agent contains a lubricant (D) having a solid content mass ratio (D)/{ (A) + (B) } of 0.01 to 6.

2. The aqueous lubricating film-treating agent according to claim 1, which comprises a resin component (C) having a solid content mass ratio (C)/{ (A) + (B) } of 0.01 to 3.

3. The water-based lubricating film-treating agent according to claim 2, wherein the resin component (C) is at least 1 selected from the group consisting of vinyl resins, acrylic resins, epoxy resins, urethane resins, phenolic resins, cellulose derivatives, polymaleic acids, polyolefins and polyesters.

4. The water-based lubricating coating treatment agent according to any one of claims 1 to 3, wherein the lubricant (D) is at least 1 selected from the group consisting of waxes, polytetrafluoroethylene, fatty acid metal soaps, fatty acid amides, molybdenum disulfide, tungsten disulfide, graphite, melamine cyanurate, amino acid compounds having a layered structure, and layered clay minerals.

5. A metal material having an adhesion amount of 0.5g/m formed on a surface thereof²～40g/m²The lubricating coating film of (1) which is formed by applying the aqueous lubricating coating treatment agent according to any one of claims 1 to 4 and drying the coating.