WO2015146818A1

WO2015146818A1 - Aqueous lubricating coating agent having excellent corrosion resistance and workability, and metal material

Info

Publication number: WO2015146818A1
Application number: PCT/JP2015/058425
Authority: WO
Inventors: 豪畠山; 小見山　忍
Original assignee: 日本パーカライジング株式会社
Priority date: 2014-03-28
Filing date: 2015-03-20
Publication date: 2015-10-01
Also published as: EP3124582A1; MX2016012566A; EP3124582A4; US20170137741A1; JPWO2015146818A1; CN105899650B; CN105899650A; EP3124582B1; JP6243515B2; ES2928160T3

Abstract

[Problem] To provide an aqueous lubricating coating agent which is capable of providing a lubricating coating film that exhibits excellent corrosion resistance, workability and removability in actual use. [Solution] An aqueous lubricating coating agent which is characterized by being obtained by blending (A) a water-soluble silicate salt and (B) at least one water-soluble inorganic salt selected from the group consisting of tungstate salts, phosphate salts and borate salts such that the solid content mass ratio (B)/(A) is within the range of 0.7-25.

Description

Water-based lubricating film treatment agent and metal material with excellent corrosion resistance and workability

The present invention relates to a water-based lubricating film treatment agent applied when plastic processing is performed on various metal materials, and a metal material in which the treatment agent is applied on a metal material surface and dried to form a film.

As a plastic working lubricant, a so-called chemical conversion coating that is a composite coating using a phosphate coating and soap is generally used. However, chemical conversion coatings have problems such as by-products associated with reaction with metal materials, waste water treatment such as washing water, and a long treatment space. In recent years, water-based coating type one-component lubricants that are environmentally friendly. Has been developed.

Patent Document 1 discloses a composition in which (A) a water-soluble inorganic salt and (B) wax are dissolved or dispersed in water, and the solid content mass ratio (B) / (A) is 0.3 to 1.5. An aqueous lubricating film treating agent for plastic working of metal materials and a method for forming the film are disclosed, which are within the range.

Patent Document 2 discloses a water-based lubricating film treating agent containing an alkali metal borate (A), wherein the alkali metal borate (A) contains lithium borate, and the total alkali in the alkali metal borate (A). The molar ratio of lithium to metal is 0.1 to 1.0, and the molar ratio (B / M) of boric acid B and alkali metal M of alkali metal borate (A) is 1.5 to A water-based lubricating film treating agent for plastic working of metal materials and a method for forming the film characterized by 4.0. This technique is said to be able to form a film having not only workability but also high corrosion resistance by suppressing the crystallization of the film that occurs when the film absorbs moisture.

Patent Document 3 contains an A component: an inorganic solid lubricant, a B component: a wax, and a C component: a water-soluble inorganic metal salt, and a solid content mass ratio between the A component and the B component (A component / B Component) is 0.1 to 5, and the solid content mass ratio of the C component to the total amount of the A component, the B component, and the C component (C component / (A component + B component + C component)) is 1 to 30%. There is disclosed a water-soluble lubricant for non-phosphorous plastic working, which is characterized in that. This technique is a lubricant that does not contain phosphorus, and is said to be able to realize corrosion resistance equivalent to that of a chemical conversion coating.

Patent Document 4 contains a water-soluble inorganic salt (A), a lubricant (B) selected from molybdenum disulfide and graphite, and a wax (C), and these are dissolved or dispersed in water. (B) / (A) is a solid content weight ratio of 1.0 to 5.0, and (C) / (A) is a solid content weight ratio of 0.1 to 1.0. A method for forming the film is disclosed. This technology is said to be able to realize high workability equivalent to that of a chemical conversion treatment film by blending molybdenum disulfide or graphite with a conventional water-based lubricating film treatment agent.

Patent Document 5 discloses silicate (A), polycarboxylate (B), water-compatible polymer and / or water-compatible organic lamellar structure (C), molybdate and / or tungstate. (D) and the mass ratio of each component is B / A = 0.02 to 0.6, C / A = 0.05 to 0.6, D / A = 0.05 to 0.6 A film-forming agent is described.

International Publication WO02 / 012420 JP2011-246684A JP2013-209625A International Publication WO02 / 012419 JP 2002-363593 A

However, even when the water-based lubricant coating agent according to Patent Documents 1 to 5 described above is used, high corrosion resistance (particularly long-term rust prevention) comparable to that of a chemical conversion coating in a practical environment and workability during strong processing are simultaneously obtained. There is a problem that a combined film cannot be formed. In addition, when a water-based lubricating film treating agent containing silicate is used, film removal failure occurs, which may cause plating failure or oxide scale peeling failure.

As a result of intensive studies in order to solve the above problems, the present inventors have formed a film in which a water-soluble silicate and a specific water-soluble inorganic salt are combined at a specific ratio, thereby forming these components. The present inventors have found that high corrosion resistance (particularly long-term rust prevention), workability and sufficient film-removability, which could never be achieved by a simple substance, can be obtained.

The present invention (1) comprises a water-soluble silicate (A) and at least one water-soluble inorganic salt (B) selected from the group consisting of tungstate, phosphate and borate, A water-based lubricating film treating agent, wherein the mass ratio (B) / (A) is blended in a range of 0.7 to 25.

The present invention (2) includes the resin component (C), and the solid content mass ratio thereof is (C) / {(A) + (B)} being 0.01 to 3, 1) A water-based lubricating film treating agent.

In the present invention (3), the resin component (C) is at least one selected from the group consisting of vinyl resins, acrylic resins, epoxy resins, urethane resins, phenol resins, cellulose derivatives, polymaleic acid, polyolefins and polyesters. The water-based lubricating film treating agent of the invention (2) characterized by the above.

The present invention (4) includes the lubricant (D), and the solid content mass ratio thereof is (D) / {(A) + (B)} of 0.01 to 6 (1). ) To (3) water-based lubricating film treating agent.

In the present invention (5), the lubricant (D) is a wax, polytetrafluoroethylene, fatty acid soap, fatty acid metal soap, fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, melamine cyanurate, layered structure amino acid compound and layered The water-based lubricating film treating agent of the invention (4), characterized in that it is at least one selected from the group consisting of clay minerals.

In the present invention (6), the water-based lubricating film treating agent for plastic working of the inventions (1) to (5) is applied and dried on the surface of the metal material so that the adhesion amount is 0.5 to 40 g / m ² . It is a metal material that has a lubricating film and is excellent in plastic workability.

If the water-based lubricating film treating agent of the present invention is used, a lubricating film excellent in practical corrosion resistance, workability, and film removal property can be obtained. In addition, their performance is comparable to or better than that of the chemical conversion coating, which is a great advantage over conventional water-based lubricating coatings. By applying the water-based lubricating film treating agent of the present invention and drying, a metal material in which the film having the above-described excellent characteristics is formed on the surface of the metal material can be obtained.

FIG. 1 is a standard for evaluation in the upsetting-ball ironing test (evaluation of seizure resistance).

Hereinafter, the present invention will be described in detail in the following order.
・ Aqueous lubricant film treatment agent (component or raw material, composition, etc.)
・ Manufacturing method of water-based lubricant coating agent ・ Use of water-based lubricant coating agent ・ Method of using water-based lubricant coating agent

≪Water-based lubricant film treatment agent≫
The aqueous lubricant film treating agent of the present invention is selected from the group consisting of water-soluble silicate (A) (hereinafter referred to as silicate (A)), tungstate, phosphate and borate. At least one water-soluble inorganic salt (B) (hereinafter referred to as inorganic salt (B)) is blended so that the solid content mass ratio (B) / (A) is in the range of 0.7 to 25. Do it. By mix | blending in this range, the film | membrane which has high corrosion resistance, workability, and sufficient film-removing property which could not be achieved by silicate (A) or inorganic salt (B) alone can be formed. The term “water-soluble” as used in the claims and the present specification means that the solubility in water at room temperature (25 ° C.) {the mass (g) of solute dissolved in 100 g of water) is at least 1 g, preferably Means 10 g or more.

When the silicate (A) and the inorganic salt (B) are combined to form a film, the inorganic salt (B) is finely and uniformly incorporated into the network structure formed by the silicate (A). Become. As a result, a brittle film of silicate (A) becomes soft and processability is improved. Further, the inorganic salt (B) is incorporated into the network structure of the silicate (A), whereby the film becomes denser, the barrier property is improved, and the corrosion resistance (particularly, long-term rust prevention) is improved. Further, the film removal property is improved by moderately inhibiting the network structure of the silicate (A) by the inorganic salt (B).

The ratio of silicate (A) and inorganic salt (B) is important for the above performance. This performance is exhibited when the solid content mass ratio (B) / (A) is in the range of 0.7 to 25, preferably in the range of 0.9 to 10.0, and 1.1 to 3.0. If it is the range, it is more preferable. When (B) / (A) is less than 0.7, sufficient corrosion resistance and workability cannot be obtained, and a film having poor film removal properties is obtained. This is due to the fact that a relatively large amount of silicate forms a strong network structure. When (B) / (A) exceeds 25, sufficient corrosion resistance cannot be obtained, and the film has poor film adhesion and uniformity. This is because the amount of silicate is relatively small, so that a sufficient network structure cannot be constructed, the barrier property is lowered, and the adhesion and uniformity of the film are lowered.

In particular, when silicate and tungstate are combined, corrosion resistance is remarkably improved by forming a passive film having a self-healing function peculiar to tungsten. Moreover, since it has a self-repairing function, stable corrosion resistance can be obtained even when a film is defective due to contact between steel materials. For this reason, it is easy to exhibit stable corrosion resistance even when a large amount of material is processed at the same time, such as mass processing using a barrel used in a lubricant for cold forging or coil processing of a wire.

Examples of the silicate (A) used in the film treatment agent according to the present invention include lithium silicate, sodium silicate, and potassium silicate. These may be used alone or in combination of two or more. In particular, the use of lithium silicate and / or sodium silicate is preferred.

Specific examples of the inorganic salt (B) used in the film treatment agent according to the present invention will be given 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 includes salts of condensed phosphoric acid such as tripolyphosphoric acid, metaphosphoric acid, and pyrophosphoric acid. Examples of the borate include sodium borate (such as sodium tetraborate), potassium borate (such as potassium tetraborate), and ammonium borate (such as ammonium tetraborate). These may be used alone or in combination of two or more.

Next, the resin component (C) will be described. The resin component (C) is blended for the purpose of binder action, improvement in adhesion between the substrate and the film, imparting leveling property by thickening action, stabilizing the dispersion component, and improving barrier properties. Examples of the resin component (C) having such functions and properties include vinyl resin, acrylic resin, epoxy resin, urethane resin, phenol resin, cellulose derivative, polymaleic acid, polyolefin, and polyester. The resin component (C) used here is not particularly limited as long as it has film-forming properties, and is generally supplied in a water-soluble or water-dispersed state. These may be used alone or in combination of two or more.

The aqueous lubricant film treating agent has a solid content mass ratio of silicate (A), inorganic salt (B) and resin component (C) of 0.01 to 3 (C) / {(A) + (B)}. It is preferable that (C) / {(A) + (B)} is more preferably 0.1 to 1.5. When it is less than 0.01, the binder action expected for the resin component (C), the adhesion between the base material and the film, the leveling property by the thickening action, the stabilization of the dispersion component, the improvement of the barrier property, etc. are sufficiently exhibited. In some cases, when the number exceeds 3, the amount of silicate or inorganic salt becomes relatively small, and high corrosion resistance and workability may not be sufficiently exhibited.

Next, the lubricant (D) will be described. The lubricant (D) itself has lubricity and slipperiness, and has a function of reducing the frictional force between the die during processing and the workpiece. In general, when the frictional force increases during plastic processing, processing energy increases, heat generation, seizure, etc. occur. However, when the lubricant (D) is included in the aqueous lubricant coating agent of the present invention, the increase in frictional force is suppressed. It will be. 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, layered structure Examples include amino acid compounds and layered clay minerals. Among these, from the viewpoints of corrosion resistance and liquid stability, a blend of wax, polytetrafluoroethylene, fatty acid soap, fatty acid metal soap, fatty acid amide, melamine cyanurate, layered structure amino acid compound and layered clay mineral is more preferable. These may be used alone or in combination of two or more. Here, specific examples of the wax include polyethylene wax, paraffin wax, microcrystalline wax, polypropylene wax, and carnauba wax. Specific examples of fatty acid soaps include sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, sodium stearate, and potassium stearate. Specific examples of fatty acid metal soaps include calcium stearate, zinc stearate, barium stearate, magnesium stearate, and lithium stearate. Fatty acid amide is an amide compound having two fatty acids. Specific examples include ethylene bislauric acid amide, ethylene bis stearic acid amide, ethylene bisbehenic acid amide, N-N'-distearyl adipic acid amide, ethylene bis Examples include oleic acid amide, ethylene biserucic acid amide, hexamethylene bis oleic acid amide, and N—N′-dioleyl adipic acid amide. The layered structure amino acid compound is an amino acid having a hydrocarbon group having 11 or more carbon atoms in the molecular structure or a derivative thereof. A specific example is N-lauroyl-L-lysine [C ₁₁ H ₂₃ CONH (CH ₂ ) ₄ CH (NH ₂ ) COOH]. Examples of the layered clay mineral include natural products or synthetic products of the smectite group, vermiculite group, mica group, brittle mica group, pyrophyllite group, and kaolinite group. More specifically, in the smectite group, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite, stevensite, and vermiculite group are di. Vermiculite, tri. Vermiculite, muscovite, paragonite, illite, phlogopite, biotite, red mica, lepidrite, brittle mica group, margarite, clintnite, pyrophyllite group, pyrophyllite, talc, kaolinite, kaolinite, Dickite, nacrite, halloysite, chrysotile, lizardite, antigolite. Further, these layered clay minerals may be subjected to organic treatment to introduce an organic modifier between the layers. The organic treatment is carried out by introducing an organic modifier in a state where the lamellar clay mineral is swollen with water to increase the interlayer distance. The organic modifier is an alkylamine or alkyl quaternary ammonium salt that adsorbs between layers to form a strong bond. Specific examples include stearyl dimethylamine, distearylamine, distearyldimethylamine, stearyltrimethylammonium chloride, distearyldimethyl. Ammonium chloride is mentioned.

The blending ratio of the lubricant (D) of the water-based lubricating film treating agent according to the present invention will be described. When the lubricant (D) is blended, the solid content mass ratio of the silicate (A), the inorganic salt (B), and the lubricant (D) is 0.01 to (D) / {(A) + (B)}. A range of 6 is preferable, and a range of 0.1 to 2 is more preferable. Here, when (D) / {(A) + (B)} is less than 0.01, the friction reducing action expected for the lubricant (D) is not sufficiently exhibited, and when it exceeds 6, the silicate (A) And the amount of the inorganic salt (B) may be relatively reduced, and high corrosion resistance and workability may not be sufficiently exhibited.

In addition to the silicate (A), the inorganic salt (B), the resin component (C), and the lubricant (D), the aqueous lubricant film treatment agent of the present invention is uniformly applied when a lubricant is applied to the substrate. In order to ensure the state, a viscosity modifier can be blended for the purpose of imparting leveling properties and thixotropy. The blending amount of these is preferably 0.1 to 50% by mass relative to the total solid mass. Examples of such viscosity modifiers include, as a specific example, smectite clay minerals such as montmorillonite, soconite, beidellite, hectorite, nontronite, saponite, iron saponite, and stevensite, and inorganic inorganic materials such as finely divided silica, bentonite, and kaolin. A thickener is mentioned.

The water-based lubricating film treatment agent of the present invention can impart high corrosion resistance before and after processing, but may further contain other water-soluble rust preventives and inhibitors for the purpose of further improving the corrosion resistance. Specific examples include various organic acids such as oleic acid, dimer acid, tartaric acid and citric acid, various chelating agents such as EDTA, NTA, HEDTA and DTPA, mixed components of alkanolamines such as triethanolamine, and pt-butylbenzoic acid. Known amines such as amine salts of acids, carboxylic acid amine salts, dibasic amine bases, alkenyl succinic acid and water-soluble salts thereof, and aminotetrazole and water-soluble salts thereof can be used. These may be used alone or in combination of two or more. The blending amount of these is preferably 0.1 to 30% by mass relative to the total solid mass.

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

The aqueous lubricant film treatment agent of the present invention may contain a water-soluble strong alkali component in order to enhance the stability of the liquid. Specific examples include lithium hydroxide, sodium hydroxide, and potassium hydroxide. These may be used alone or in combination of two or more. The blending amount of these is preferably 0.01 to 10% by mass relative to the total solid mass.

It is also acceptable to use a surfactant to disperse the water-insoluble substance. However, it is preferable that the addition amount other than (A), (B), (C), and (D) does not exceed 50% by mass of the solid content of the water-based lubricating coating agent as long as the required performance is not lowered. Conversely, the total amount of addition of (A), (B), (C), and (D) is preferably 50% by mass or more, and 70% by mass or more, based on the solid content of the aqueous lubricant film. It is more preferable that it is 85 mass% or more.

≪Method for producing aqueous lubricant film treatment agent≫
The water-based lubricating film treating agent according to the present invention is mixed, for example, by adding a silicate (A) and an inorganic salt (B), further a resin component (C), a lubricant (D), etc. to water which is a liquid medium. It is manufactured by doing. Mixing is performed by a general method such as propeller stirring or a homogenizer.

≪Use of water-based lubricant coating agent≫
The water-based lubricating film treating agent of the present invention is preferably for plastic working in the cold region such as forging, wire drawing, tube drawing, roll forming, pressing, and the like.

-Metal material to be used The water-based lubricating film treating agent of the present invention is applied to metal materials such as iron or steel, stainless steel, copper or copper alloy, aluminum or aluminum alloy, titanium or titanium alloy. The shape of the metal material is not particularly limited, and is applicable not only to raw materials such as rods and block materials but also to forged shapes (such as gears and shafts).

-Use as a base film The water-based lubricating film treating agent of the present invention can be used as a base film treating agent for other wet lubricants or dry lubricants. By using it as an undercoat, the workability and corrosion resistance of other wet lubricants and dry lubricants can be raised. The type of lubricant to be combined is not particularly limited. For example, a general water-based lubricating film treatment agent represented by Patent Documents 1 to 4, lime soap, and forging oil can be used as a wet lubricant. Further, as the dry lubricant, for example, general lubricating powder or wire drawing powder mainly composed of higher fatty acid soap, borax, lime, molybdenum disulfide or the like can be used.

≪How to use water-based lubricant film treatment agent≫
Next, a method for using the water-based lubricating film treating agent of the present invention will be described. This method of use includes a metal material cleaning step, a water-based lubricating film treating agent application step, and a drying step. Hereinafter, the metal material and each process which are objects of use will be described.

・ Cleaning process (pretreatment process)
Before forming the water-based lubricating film on the metal material, it is preferable to perform at least one cleaning treatment selected from the group consisting of shot blasting, sand blasting, wet blasting, peeling, alkali degreasing, and acid cleaning. The purpose of cleaning here is to remove oxide scales and various types of dirt (oil, etc.) grown by annealing or the like.

-Application process The process of applying the water-based lubricating film of the present invention to a metal material is not particularly limited, but an immersion method, a flow coating method, a spray method, or the like can be used. Application is not limited as long as the metal surface is sufficiently covered with the water-based lubricating film treating agent of the present invention. In order to increase the drying property, the metal material may be heated to 60 to 80 ° C. and brought into contact with the metal-based plastic working water-based lubricant coating agent, or the metal material plastic working water system heated to 40 to 70 ° C. A lubricant film treatment agent may be contacted. By these, drying property improves significantly and drying may be attained at normal temperature, and the loss of heat energy can also be reduced.

The adhesion amount of the water-based lubricating film formed on the metal surface is appropriately controlled depending on the degree of subsequent processing, but the adhesion amount is preferably in the range of 0.5 to 40 g / m ² , more preferably 2 It is in the range of ˜20 g / m ² . When the adhesion amount is less than 0.5 g / m ² , the lubricity is insufficient. On the other hand, if the adhesion amount exceeds 40 g / m ² , there is no problem in lubricity, but clogging of the mold and the like are not preferable. The amount of adhesion can be calculated from the mass difference and surface area of the metal material before and after the treatment. In order to control the amount of adhesion, the solid content mass (concentration) of the water-based lubricating film treating agent is appropriately adjusted. A high concentration aqueous lubricant film is prepared and diluted with water to obtain the desired amount of adhesion. The water to be diluted is not particularly limited, but deionized water and distilled water are preferable.

-Drying step Although not particularly limited , the drying step is preferably carried out at 60 to 150 ° C for about 1 to 30 minutes.

-Optional process 1 (undercoat process)
The water-based lubricating film treating agent of the present invention prevents seizure between the mold and the workpiece during processing and can impart high corrosion resistance before and after processing, but for the purpose of further improving workability and corrosion resistance. An undercoat treatment may be performed. The base film treatment may be a reactive film or a non-reactive film. Specific examples of the reactive coating include phosphate, iron oxide, zirconium oxide, zirconium hydroxide, molybdate, oxalate, and tannic acid. Specific examples of the non-reactive film include silicate, borate, zirconium compound, vanadium compound, colloidal silica, and resin coating film.

-Optional process 2 (film removal process)
The lubricating film formed by the water-based lubricating film treating agent of the present invention can be removed by immersing in a water-based alkaline cleaning agent or by spray cleaning. An alkaline cleaner is a solution in which common alkaline components such as sodium hydroxide and potassium hydroxide are dissolved in water. When an aqueous lubricant film is brought into contact with this, the aqueous lubricant film dissolves in the cleaning solution, so that The film can be removed. Therefore, there is no contamination in the subsequent process due to defective film removal by alkali cleaning, and plating defects and oxide scale peeling defects can be prevented in advance.

The effects of the present invention will be specifically described by giving examples of the present invention together with comparative examples. In addition, this invention is not restrict | limited by these Examples.
Example A

(1-1) Production of Water-Based Lubricant Coating Agents Water-based lubricant coating agents of Examples 1 to 16 and Comparative Examples 1 to 8 were prepared in the combinations and proportions shown in Tables 1 and 2 shown below. Comparative example 9 is a phosphate / soap treatment.

<Silicate>
(A-1) Sodium silicate (Na ₂ O · nSiO ₂ n = 3)
(A-2) Lithium silicate (Li ₂ O.nSiO ₂ n = 3.5)
(A-3) Potassium silicate (K ₂ O.nSiO ₂ n = 2.3)
<Inorganic salt>
(B-1) Sodium tungstate (B-2) Sodium tripolyphosphate (B-3) Potassium metaborate <Resin component>
(C-1) Sodium neutralized salt of isobutylene / maleic anhydride copolymer (molecular weight about 165,000)
<Lubricating component>
(D-1) Anionic polyethylene wax (average particle size 5 μm)
(D-2) Non-swelling synthetic mica (average particle size 5.0 μm)

(1-2) Method of using water-based lubricant coating agent
<Standard process>
(A) Degreasing: Commercially available degreasing agent (Fine Cleaner E6400, manufactured by Nihon Parkerizing Co., Ltd.) concentration 20 g / L, temperature 60 ° C., immersion 10 minutes (b) water washing: tap water, room temperature, immersion 20 seconds (c) acid Washing: 17.5% hydrochloric acid, room temperature, immersion for 20 minutes (d) Water washing: tap water, room temperature, immersion for 20 seconds (e1) to (e3) Lubrication treatment: Described in each example and comparative example (f) Drying : 100 ° C., 10 minutes <Lubrication treatment of Examples 1 to 15 and Comparative Examples 1 to 8>
(E1) Lubricating film treatment: Water-based lubricating film treating agent produced in (1-1) Temperature 60 ° C., immersion 1 minute <Pretreatment and film treatment of Example 16>
(E1) Substrate treatment: Commercial zirconium chemical conversion treatment agent (Pulseed 1500, manufactured by Nihon Parkerizing Co., Ltd.) Concentration 50 g / L, temperature 45 ° C., pH 4.0 immersion 2 minutes (e2) Water washing: tap water, room temperature, immersion 20 Second (e3) Lubricant film treatment: Water-based lubricant film treatment agent produced in (1-1) Temperature 60 ° C., immersion 1 minute <Pretreatment and film treatment of Comparative Example 9 (phosphate / soap treatment)>
(E1) Chemical conversion treatment: Commercially available zinc phosphate chemical conversion treatment agent (Palbond 181X, manufactured by Nihon Parkerizing Co., Ltd.) concentration 75 g / L, temperature 80 ° C., immersion 7 minutes (e2) water washing: tap water, normal temperature, immersion 30 seconds (E3) Soap treatment: Commercially available reactive soap lubricant (Palube 235, manufactured by Nihon Parkerizing Co., Ltd.), concentration 70 g / L, temperature 85 ° C., immersion 3 minutes * Dry film amount: 10 g / m ²

(1-3) Evaluation Test (1-3-1) Spike Test For Examples 1 to 16 and Comparative Examples 1 to 9, workability was evaluated by a spike test. The spike test was conducted according to the method described in Japanese Patent Application Laid-Open No. 5-7969. Lubricity was evaluated by spike height and molding load after the test. The higher the spike height and the lower the molding load, the better the lubricity. According to the publication, the area expansion rate in the spike test is about 10 times. The lubricity of the film was evaluated by measuring the load and spike height during processing.
Test piece for evaluation: S45C spheroidized annealing material 25 mmφ × 30 mm
Evaluation criteria:
Spike performance = spike height (mm) / processing load (kNf) x 100
The greater the value, the better the lubricity ◎: 0.96 or more ○: 0.94 or more and less than 0.96 △: 0.92 or more and less than 0.94 ▲: 0.90 or more but less than 0.92 ×: Less than 0.90 (1-3-2) Upsetting-Ball ironing test Evaluation)
Examples 1 to 16 and Comparative Examples 1 to 9 were evaluated for workability by an upsetting-ball ironing test. The upsetting-ball ironing test was performed according to the method described in JP2013-215773A. In the upsetting-ball ironing test, the area expansion rate is 150 times or more at maximum, and the area expansion rate is very large compared to the spike test described above, and this is a test that reproduces strong machining. By evaluating the amount of seizure entering the ironing surface, the anti-seizure performance of the film during strong processing was evaluated.
Test piece for evaluation: S10C spheroidized annealing material 14 mmφ × 32 mm
Bearing ball: 10mmφ SUJ2
Evaluation criteria:
It was evaluated how much area burned with respect to the entire area of the ironing surface. The standard of evaluation is shown in FIG.
◎: Remarkably superior to phosphate / soap coating ○: Superior to phosphate / soap coating △: Equivalent to phosphate / soap coating ▲: Inferior to phosphate / soap coating ×: From phosphate / soap coating Remarkably inferiority (1-3-3) Film removal test A film removal test was performed on Examples 1 to 16 and Comparative Examples 1 to 8. Comparative Example 9 was excluded from the test level because the general film removal method was different. In the film removal test, a cylindrical test piece was mounted using a flat mold on both the upper and lower sides, and the film was peeled off by being immersed in an alkaline detergent after being placed at a compression rate of 50%. In (1-2) step (d), after washing with water, (f) was dried, and after cooling, the mass of the test piece was measured. Thereafter, (e) after the lubrication treatment, (f) was dried and the mass of the test piece was measured after cooling. The film mass was converted by the mass difference before and after that. After washing with alkali (f), drying was performed, and the mass of the test piece was measured after cooling. The film mass after degreasing treatment was converted from the mass after alkali washing and the mass after pickling.
Test piece for evaluation: S45C spheroidized annealing material 25 mmφ × 30 mm
Alkaline detergent: 2% NaOH aqueous solution film removal condition: liquid temperature 60 ° C., immersion time 2 minutes Film remaining rate (%) = (film weight after film removal / film weight before film removal) × 100
Evaluation criteria:
The lower the film remaining rate, the better the film removal performance ◎: The film remaining rate is 0%
○: Film remaining ratio is over 0 and less than 8% Δ: Film remaining ratio is 8% or more and less than 16% ▲: Film remaining ratio is 16% or more and less than 25% ×: Film remaining ratio is 25% or more (1- 3-4) Corrosion Resistance Test Corrosion resistance tests were conducted on Examples 1 to 16 and Comparative Examples 1 to 9. Using a barrel, five test pieces were lubricated at the same time, and the test pieces were exposed indoors in an open atmosphere in summer for 3 months to observe the occurrence of rust. It was judged that the larger the rusting area, the lower the corrosion resistance. Evaluation was carried out on all five test pieces.
Test piece for evaluation: S45C spheroidized annealing material 25 mmφ × 30 mm
Evaluation criteria:
A: Rust area 3% or less (remarkably superior to phosphate / soap film)
○: Rust area over 3%, 10% or less (better than phosphate / soap film)
Δ: Rust area over 10%, 20% or less (equivalent to phosphate / soap film)
▲: Rust area over 20%, 30% or less (inferior to phosphate / soap film)
×: Rust area more than 30% (remarkably inferior to phosphate / soap film)
(1-3-5) Overall score evaluation The above four evaluation results 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 the details of the corrosion resistance test. As is apparent from the table, the examples had good workability (spike test, ball ironing test), film removal property, and corrosion resistance (indoor exposure). Moreover, regarding the corrosion resistance, the level of blending sodium tungstate tended to be good, and the performance variation was small. In Comparative Examples 1 to 8, the ratio of the silicate (A) to the inorganic salt (B) was outside the scope of the present invention, but the results of the ball ironing test and the corrosion resistance test tended to be inferior. What performed the reaction soap process to the phosphate membrane | film | coat of the comparative example 9 was inferior compared with an Example, although the comparatively outstanding performance was shown.

Hereinafter, the case where the present invention is used as an undercoat of a dry lubricant and a wet lubricant will be described more specifically together with the effects of the present invention by giving examples of the present invention together with comparative examples. In addition, this invention is not restrict | limited by these Examples.
Example B

(2-1) Manufacture of water-based lubricating film treating agent Water-based lubricating film treating agents of Examples 17 to 42 and Comparative Examples 11 to 18, and 20 to 27 in the combinations and proportions shown in Tables 6 and 7 above. Was prepared. Comparative Example 10 used only the wire drawing powder without the lubricating film of the present invention. In Comparative Example 19, lime soap was used without 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, no wire drawing powder was used.

(2-2) Lubrication treatment <Lubrication treatment of Examples 17 to 28 and Comparative Examples 11 to 18>
Processed by standard steps as described in (1-2).
(E) Lubricant film treatment: Water-based lubricant film treatment agent produced in (2-1) Temperature 60 ° C., immersion 1 minute <Pretreatment and film treatment of Examples 30 to 41 and Comparative Examples 20 to 27>
Processed by standard steps as described in (1-2).
(E1) Lubricating film treatment: Water-based lubricating film treating agent produced in (2-1) Temperature 60 ° C., immersion 1 minute, and then 250 g of commercially available lime soap (LUB-CAO2, Nippon Parkerizing Co., Ltd.) as the upper layer film / L Temperature 60 ° C., immersion 1 minute treatment, drying similar to (f) was performed to obtain 5 g / m ² of lime soap film.
<Pretreatment and film treatment of Example 29>
(E1) Substrate treatment: Commercial zirconium chemical conversion treatment agent (Pulseed 1500, manufactured by Nihon Parkerizing Co., Ltd.) Concentration 50 g / L, temperature 45 ° C., pH 4.0 immersion 2 minutes (e2) Water washing: tap water, room temperature, immersion 20 Second (e3) Lubricant film treatment: Water-based lubricant film treatment agent produced in (2-1) Temperature 60 ° C., immersion 1 minute <Pretreatment and film treatment of Example 42>
(E1) Substrate treatment: Commercial zirconium chemical conversion treatment agent (Pulseed 1500, manufactured by Nihon Parkerizing Co., Ltd.) Concentration 50 g / L, temperature 45 ° C., pH 4.0 immersion 2 minutes (e2) Water washing: tap water, room temperature, immersion 20 Second (e3) Lubricating film treatment: Water-based lubricating film treating agent produced in (2-1) Temperature 60 ° C., immersion 1 minute, and then, as an upper layer film, commercially available lime soap (LUB-CAO2, manufactured by Nihon Parkerizing Co., Ltd.) 250 g / L Temperature 60 ° C., immersion 1 minute treatment was performed, and the same drying as (f) was performed to obtain a lime soap film amount of 5 g / m ² .
<Pretreatment and film treatment of Comparative Example 10>
(E) Pure water washing: deionized water, room temperature, immersion 30 ° C.
<Pretreatment and Film Treatment of Comparative Example 19>
(E) Lubrication: Commercially available lime soap (LUB-CAO2, manufactured by Nihon Parkerizing Co., Ltd.) 250 g / L Temperature 60 ° C., immersion 1 minute (f) Drying: 100 ° C., 10 minutes * Lime soap film amount 5 g / m ²
<Pretreatment and film treatment of Comparative Example 28 (phosphate / soap treatment)>
(E1) Chemical conversion treatment: commercially available zinc phosphate chemical conversion treatment agent (Palbond 421WD, manufactured by Nihon Parkerizing Co., Ltd.) concentration 75 g / L, temperature 80 ° C., immersion 10 minutes (e2) water washing: tap water, normal temperature, immersion 30 seconds (E3) Soap treatment: Commercially available reactive soap lubricant (Palube 235, manufactured by Nihon Parkerizing Co., Ltd.), concentration 70 g / L, temperature 85 ° C., immersion 3 minutes * Dry film amount: 10 g / m ²

(2-3) Evaluation test (2-3-1) Wire drawing test (Evaluation of lubricity)
For Examples 17 to 42 and Comparative Examples 10 to 28, workability was evaluated by a wire drawing test. Drawing was performed by drawing a steel wire having a diameter of 3.2 mm through a die having a diameter of 2.76. In Examples 17 to 29 and Comparative Examples 10 to 18, a missile C40 manufactured by Matsuura Kogyo Co., Ltd. was used as a dry lubricant. A dry lubricant was placed in the die box just before the material was pulled out so that it naturally adhered to the material. Evaluation was performed from seizure of the test material after wire drawing and the remaining amount of the lubricating film. The amount of the film after wire drawing was determined from the difference in mass before and after the film was peeled off using the following film peeling agent.
Test piece for evaluation: SWCH45K material φ3.2 mm × 20 m
Die diameter: φ2.76
Film stripper: Commercially available alkaline stripper (FC-E6463, manufactured by Nihon Parkerizing Co., Ltd.), 20 g / L
Film removal conditions: liquid temperature 60 ° C., immersion time 2 minutes Evaluation criteria:
Film residual ratio (%) = (film amount before processing / film amount after processing) × 100
* The amount of coating before processing does not include lubricating powder. The coating amount after processing includes lubricating powder.
◎: Film remaining ratio 85% or more ○: Film remaining ratio 75% or more, less than 85% △: Film remaining ratio 65% or more, less than 75% ▲: Film remaining ratio 50% or more, less than 65% ×: Film remaining ratio 50 %, Or seizure occurred (2-3-2) Corrosion resistance test Examples 17 to 42 and Comparative Examples 10 to 28 were evaluated for corrosion resistance. The wire subjected to the above wire drawing test was exposed indoors for 3 months in an open atmosphere in the summer, and observed for the occurrence of rust. It was judged that the larger the rusting area, the lower the corrosion resistance.
Evaluation criteria:
A: Remarkably superior to phosphate / soap film (rust area 3% or less)
○: Superior to phosphate / soap film (rust area 3% or more, less than 10%)
Δ: Same as phosphate / soap film (rust area 10% or more, less than 20%)
▲: Inferior to phosphate / soap film (rust area 20% or more, less than 30%)
X: Remarkably inferior to phosphate / soap film (rust area 30% or more)

Table 8 shows the test results. In all of the examples, a lot of film remained, and the workability and corrosion resistance were good. From the fact that the corrosion resistance after wire drawing is also high, it can be seen that a large amount of the lubricating film of the present invention remains after processing. Comparative Examples 10 and 19 were at a level where the lubricant of the present invention was not used, but the wire drawability and corrosion resistance were greatly inferior. In Comparative Examples 11 to 18 and 20 to 27, the ratio of the silicate (A) to the inorganic salt (B) was set inappropriately, but the film remaining amount after wire drawing and the corrosion resistance were inferior. The sample obtained by subjecting the phosphate film of Comparative Example 28 to reactive soap treatment has excellent performance, but wastewater treatment and liquid management are required, and it cannot be used in simple treatment processes or equipment. This creates a large environmental impact.

As is clear from the above explanation, when the aqueous lubricant of the present invention is used, both high workability and corrosion resistance can be achieved. Furthermore, the film removal property of the lubricating film after processing with a cleaning agent is also good. Therefore, the industrial utility value is extremely large.

Claims

A water-soluble silicate (A) and at least one water-soluble inorganic salt (B) selected from the group consisting of tungstates, phosphates and borates are obtained by solid content mass ratio (B) / ( A water-based lubricating film treating agent comprising A) in a range of 0.7 to 25.
The water-based lubricating film treatment according to claim 1, comprising a resin component (C) and having a solid content mass ratio of (C) / {(A) + (B)} of 0.01 to 3. Agent.
3. The resin component (C) is at least one selected from the group consisting of vinyl resins, acrylic resins, epoxy resins, urethane resins, phenol resins, cellulose derivatives, polymaleic acid, polyolefins and polyesters. The water-based lubricating film treating agent as described in 1.
The lubricant (D) is included, and the solid content mass ratio thereof is (D) / {(A) + (B)} being 0.01 to 6, according to any one of claims 1 to 3. The water-based lubricating film treating agent as described.
The lubricant (D) is 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, layered structure amino acid compound and layered clay mineral. The aqueous lubricant film treatment agent according to claim 4, wherein the treatment agent is an aqueous lubricant film treatment agent according to claim 4.
A lubricating film having an adhesion amount of 0.5 to 40 g / m 2 is formed on the surface of the metal material by applying and drying the water-based lubricating film treatment agent for plastic working according to any one of claims 1 to 5. Metal material.