ES2928160T3 - Aqueous lubricating coating agent having excellent corrosion resistance and workability, and metallic material - Google Patents

Abstract

A water-based lubricating coating agent is provided from which a lubricating coating film is obtained which is excellent in corrosion resistance, workability and film removability in practical use. A water-based lubricating coating agent characterized in that a water-soluble silicate (A) and at least one water-soluble inorganic salt (B) selected from the group consisting of a tungstate, a phosphate and a borate are mixed so that the solid content mass ratio (B)/(A) falls within the range of 0.7 to 25. (Automatic translation with Google Translate, no legal value)

Description

DESCRIPTION

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

technical field

The present invention relates to a water-based lubricating coating agent that is applied when performing plastic work to various types of metal materials, and to a metal material with a coating film formed by applying the agent on the material surface. metal and drying agent.

Background art

As plastic working lubricants, so-called chemical conversion coating films, which are composite coating films using phosphate coating films and soaps, are common. However, chemical conversion coating films have problems such as by-products associated with reactions with metallic materials, water effluent treatments such as water rinses, and large spaces for treatments, and in recent years, chemical conversion coating films have been developed. Environmentally friendly water-based dry-in-place type single-component lubricants.

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

Patent Document 2 discloses a water-based lubricating coating agent for plastic working of metal materials, containing an alkali metal borate (A), characterized in that the alkali metal borate (A) includes a lithium borate, the molar ratio of lithium to all alkali metals is 0.1 to 1.0 in the alkali metal borate (A) and the molar ratio (B/M) between a boric acid B and an alkali metal M is from 1.5 to 4.0 in the alkali metal borate (A), and a method of forming a coating film therefrom. This technique is supposed to suppress the crystallization of the coating film, which is caused by moisture absorption of the coating film, thereby enabling the formation of coating films with not only workability but also high corrosion resistance.

Patent document 3 discloses an aqueous lubricant without phosphorus for plastic work, which contains a component A: solid inorganic lubricant, a component B: wax and a component C: inorganic metal salt soluble in water, characterized in that the mass ratio of content of solids (component A / component B) is 0.1 to 5 between component A and component B, and the mass ratio of solids content (component C / (component A component B component C)) of component C it is from 1 to 30% with respect to the total amount of component A, component B and component C. This technique refers to a lubricant that does not contain phosphorus, and is supposed to be capable of achieving a corrosion resistance comparable to that of of coating films by chemical conversion.

Patent Document 4 discloses a water-based lubricating coating agent including a water-soluble inorganic salt (A), a lubricant (B) selected from molybdenum disulfide and graphite, and a wax (C) dissolved or dispersed in water, wherein the ratio (B)/(A) is 1.0 to 5.0 in terms of solid content weight ratio and the ratio (C)/(A) is 0.1 to 1 0.0 by weight ratio of solid content, and a method of forming a coating film therefrom. This technique is supposed to achieve the same level of high workability as chemical conversion coating films by mixing a conventional water-based lubricating coating agent with molybdenum disulfide or graphite.

Patent document 5 discloses a film-forming agent that contains a silicate (A), a polycarboxylate (B), a hydrophilic polymer and/or a hydrophilic organic lamellar structure (C) and a molybdate and/or tungstate (D) , in which the mass ratios between the respective components are: B/A = from 0.02 to 0.6, C/A = from 0.05 to 0.6 and D/A= from 0.05 to 0 ,6.

Patent Document 6 discloses a lubricant composition comprising alkali metal borates and alkali metal sulfates as essential components and further comprising alkali metal salts of fatty acids, alkaline earth metal salts of fatty acids, a solid lubricant, a resin water soluble thermoplastic and optionally sodium silicate.

Patent document 7 discloses a metallic material for plastic work, through which its surface is provided with a lubricating film containing sodium metaborate (A1) and sodium metasilicate (A2), zinc stearate (B), hydroxide calcium (C) and a 1-dodecene/maleic acid anhydride copolymer (D).

Prior art documents

patent bibliography

Patent Document 1: WO 02/012420 A

Patent Document 2: JP 2011-246684 A

Patent Document 3: JP 2013-209625 A

Patent Document 4: WO 02/012419 A

Patent Document 5: JP 2002-363593 A

Patent Document 6: JP H10-36876 A

Patent Document 7: JP 2009-185311 A

Summary of the invention

technical problem

However, even the use of the water-based lubricating coating agents according to patent documents 1 to 7 have the problem of being unable to form a coating film having a combination of high corrosion resistance (in particular, long-term rust prevention property) and heavy-duty workability while comparable to that of chemical conversion coating films in actual environments. In addition, when a water-based lubricating coating agent containing a silicate is used, faulty film removal may occur, thereby causing faulty plating or faulty detachment of oxidized scale.

Solution to the problem

The inventors have found, as a result of earnestly studying in order to solve the above-mentioned problems, that formation of a coating film by combining a water-soluble silicate and a specific water-soluble inorganic salt at a specific ratio provides a high corrosion resistance (particularly a long-term rust-preventing property), workability and adequate film removability which could not be achieved in any way by the individual components, thereby achieving the present invention .

The present invention (1) is a water-based lubricating coating agent characterized in that a water-soluble silicate (A) having a solubility of at least 1 g in 100 g of water at 25°C and an inorganic salt are mixed. soluble in water (B) having a solubility of at least 1 g in 100 g of water at 25°C, which is a tungstate, such that the mass ratio of solids content (B)/(A) is is within the range of 0.7 to 25, wherein the agent includes a resin component (C) which is at least one selected from the group consisting of a vinyl resin, an acrylic resin, an epoxy resin, a resin of urethane, a phenolic resin, a cellulose derivative, a poly(maleic acid), a polyolefin and a polyester, and the mass ratio of solid content (C)/{(A)(B)} is 0, 01 to 3, and in which

The agent includes a lubricant (D) that is at least one selected from the group consisting of a wax, polytetrafluoroethylene, a fatty acid soap, a fatty acid metal soap, a fatty acid amide, molybdenum disulfide, tungsten disulfide , graphite, melamine cyanurate, a layered structure amino acid compound and a layered clay mineral, and the mass ratio of solid content (D)/{(A)(B)} is 0.01 to 6.

The present invention (2) is a metallic material with a lubricating coating film of 0.5 to 40 g/m2 as a coating weight, which is formed on a metallic material surface by applying and drying the lubricating coating agent. water-based plastic working agent according to the invention (1), which is excellent in plastic workability.

Advantageous effects of the invention

The use of the water-based lubricating coating agent according to the present invention provides a lubricating coating film which is excellent in corrosion resistance, workability and film removability in practical use. In addition, the agent is significantly superior compared to conventional water-based lubricating film coatings because all of these characteristics are comparable or superior to those of chemical conversion coating films. materials can be obtained metals in which the coating film with the aforementioned excellent characteristics is formed on the metal material surfaces by applying and drying the water-based lubricating coating agent according to the present invention.

Brief description of the drawings

Figure 1 are indications of the evaluation in a test of the tribological type of ironing with a ball for upsetting (evaluation of the resistance to seizure).

Description of embodiments

Hereinafter, the present invention will be described in detail in the following order.

■ Water-based lubricating coating agent (components or raw materials, compositions, etc.)

■ Method for manufacturing the water-based lubricating coating agent

■ Application of water-based lubricating coating agent

■ Method of using the water-based lubricating coating agent

«Water-based lubricating coating agent>>

A water-based lubricating coating agent according to the present invention is obtained by mixing a water-soluble silicate (A) (hereinafter referred to as silicate (A)) and a water-soluble inorganic salt (B) (hereinafter referred to as inorganic salt (B)), which is a tungstate, such that the mass ratio of solids content (B)/(A) is within the range of 0.7 to 25 Mixing in the range can form a coating film with high corrosion resistance and workability and adequate film removal ability that could not be achieved by the silicate (A) or inorganic salt (B) by themselves. It should be noted that the term "water soluble" in the claims and specification means that the solubility in water at room temperature (25°C) {the mass (g) of a solute dissolved in 100 g of water} is at least less than 1 g, and preferably 10 g or more.

When the silicate (A) and inorganic salt (B) are combined to provide a coating film, the inorganic salt (B) will be finely and homogeneously incorporated into a lattice structure formed by the silicate (A). As a result, the brittle coating film of the silicate (A) becomes flexible to improve workability. In addition, the incorporation of the inorganic salt (B) into the lattice structure of the silicate (A) makes the coating film denser, thereby increasing the barrier performance and therefore improving the corrosion resistance ( in particular, the long-term rust prevention property). Furthermore, the lattice structure of the silicate (A) is appropriately blocked by the inorganic salt (B), thereby improving the film removability.

The ratio between the silicate (A) and the inorganic salt (B) is important to provide the characteristics mentioned above. Characteristics are supplied at a solids (B)/(A) content mass ratio within the range of 0.7 to 25, but preferably in the range of 0.9 to 10.0, and more preferably 1, 1 to 3.0. A (B)/(A) ratio less than 0.7 results in insufficient corrosion resistance and workability being achieved, and also provides a coating film which is inferior in film removability. This is due to the rigid lattice structure formed by the relatively increased amount of the silicate. A (B)/(A) ratio greater than 25 results in insufficient corrosion resistance being achieved, and also results in a coating film that is inferior in adhesion and uniformity. This is due to the fact that the excessively small relative amount of the silicate results in a proper lattice structure not being formed, thereby degrading the barrier performance and degrading the adhesion and uniformity of the coating film.

Furthermore, in particular, when the silicate is combined with a tungstate, the corrosion resistance is significantly improved by the formation of a passivation film that has a self-healing function unique to tungsten. In addition, since it has the function of self-healing, stable corrosion resistance can be achieved even when the coating film becomes defective, for example, due to steels in contact with each other. For this reason, stable corrosion resistance is likely to occur even in the case of processing large amounts of materials simultaneously, such as mass processing and coil processing of wire rods with the use of barrel-shaped cylinders for use. in lubricating agents for cold forging.

Examples of the silicate (A) for use in the coating agent according to the present invention include, for example, lithium silicates, sodium silicates and potassium silicates. These can be used singly, or two or more of them can be combined. In particular, it is preferable to use lithium silicates and/or sodium silicates.

Kinds of the inorganic salt (B) which is a tungstate for use in the coating agent according to the present invention will be specifically provided. Tungstates include, for example, lithium tungstates, sodium tungstates, potassium tungstates, and ammonium tungstates. These can be used singly, or two or more of them can be combined.

Next, the resin component (C) will be described. The resin component (C) is mixed in order to provide a binding action, improve the adhesion between the base material and the coating film, provide leveling property by thickening action, stabilize the dispersant component and improve the spreading property. barrier. The resin component (C) having such functions and properties is at least one selected from the group consisting of vinyl resins, acrylic resins, epoxy resins, urethane resins, phenolic resins, cellulose derivatives, poly(maleic acid), polyolefin and polyester. The resin component (C) used herein has a film-forming property and is usually supplied in a water-soluble or water-dispersible state. These can be used singly, or two or more of them can be combined.

In the water-based lubricating coating agent, the mass ratio of solid content (C)/{(A) (B)} of the resin component (C) with respect to the silicate (A) and inorganic salt ( B) is from 0.01 to 3, and preferably from 0.1 to 1.5. Ratio less than 0.01 may not provide binding action, improve adhesion between base material and coating film, provide leveling property by thickening action, stabilize dispersant component, improve barrier property, or similar, as expected for the resin component (C), while in the case of a ratio greater than 3, the amount of the silicate and the inorganic salt can be relatively reduced, thereby making it possible to exhibit sufficiently high resistance to wear. corrosion and workability.

Next, the lubricant (D) will be described. The lubricant (D) itself has lubricity and produces slip, and has a function of reducing the frictional force between a die for processing and a material to be processed. In general, an increased frictional force during plastic working increases working energy, generates heat, causes seizure, or the like, but when the water-based lubricating coating agent according to the present invention includes the lubricant (D), it is will suppress the increase in friction force. The lubricant (D) having such functions and properties is at least one selected from the group consisting of waxes, polytetrafluoroethylene, fatty acid soaps, fatty acid metal soaps, fatty acid amides, molybdenum disulfide, tungsten disulfide, graphite , melamine cyanurate, layered structure amino acid compounds and layered clay minerals. Among these lubricants, waxes, polytetrafluoroethylene, fatty acid soaps, fatty acid metal soaps, fatty acid amides, melamine cyanurate, layered amino acid compounds and layered clay minerals are preferably mixed. from the perspective of corrosion resistance and stability against liquids. These can be used singly, or two or more of them can be combined. In this regard, specific examples of the waxes include a polyethylene wax, a paraffin wax, a microcrystalline wax, a polypropylene wax and a carnauba wax. Furthermore, specific examples of the fatty acid soaps include sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, sodium stearate and potassium stearate. Furthermore, specific examples of the fatty acid metal soaps include calcium stearate, zinc stearate, barium stearate, magnesium stearate and lithium stearate. Furthermore, fatty acid amides refer to an amide compound having two fatty acids, and specific examples thereof include ethylenebislauric acid amide, ethylenebisstearic acid amide, ethylenebisbehenic acid amide, N-N' acid amide. -distearyladipic, ethylenebisoleic acid amide, ethylenebiserucic acid amide, hexamethylenebisoleic acid amide and N,N'-dioleyladipic acid amide. Furthermore, amino acid compounds of layered structure refer to amino acids that include a hydrocarbon group having 11 or more carbon atoms in the molecular structure, or derivatives thereof. Specific examples thereof include N-lauroyl-L-lysine [CnH ²³ CONH(CH ² ) ⁴ CH(NH ² )COOH]. Layered clay minerals include natural products or synthetic products of a smectite group, a vermiculite group, a mica group, a brittle mica group, a pyrophyllite group, and a kaolinite group. More specific examples thereof include montmorillonite, beidellite, nontronite, saponite, ferric saponite, hectorite, sauconite and stevensite as a smectite group, divemiculite and trivermiculite as a vermiculite group, muscovite, palagonite, illite, phlogopite, biotite and lepidolite as a group. of mica, daisy and clintonite as brittle mica group, pyrophyllite and talc as pyrophyllite group, and kaolinite, dickite, nacrite, halloysite, chrysotile, lizardite and antigorite as kaolinite group. Furthermore, these layered clay minerals can be subjected to organic treatment, thereby introducing an organic denaturant between the layers. The organic treatment is carried out according to a method for introducing the organic denaturant with increased interlayer distance by causing the layered clay minerals to swell with water. The organic denaturant is an alkylamine or alkyl quaternary ammonium salt which adsorbs between the layers to form a strong bond, and specific examples thereof include stearyldimethylamine, distearylamine, distearyldimethylamine, stearyltrimethylammonium chloride and distearyldimethylammonium chloride.

The mixing ratio of the lubricant (D) will be described for the water-based lubricating coating agent according to the present invention. The mass ratio of solids content (D)/{(A)(B)} of lubricant (D) to silicate (A) and inorganic salt (B) is within the range of 0.01 to 6 , and preferably within the range of 0.1 to 2. In this regard, a ratio (D)/{(A)(B)} less than 0.01 results in no exercise of the expected friction-reducing effect of the lubricant (D) sufficiently, while in the case where the ratio is greater than 6, the relatively decreased amount of the silicate (A) and inorganic salt (B) may make it impossible for them to occur. sufficiently high corrosion resistance and workability.

For the water-based lubricating coating agent according to the present invention, in addition to the silicate (A), the inorganic salt (B), the resin component (C) and the lubricant (D), a viscosity modifier can be mixed with in order to provide a leveling property and thixotropy to ensure a uniformly applied state when the lubricant is applied to the base material. It should be noted that the amount of mixing is preferably 0.1 to 50% by mass based on the total mass of solids content. Specific examples of such a viscosity modifier include smectite clay minerals such as montmorillonite, sauconite, beidellite, hectorite, nontronite, saponite, ferric saponite, and stevensite, and inorganic thickeners such as finely divided silica, bentonite, and kaolin.

The water-based lubricating coating agent according to the present invention can provide high corrosion resistance before and after processing, and in order to further improve the corrosion resistance, other inhibitors and water-soluble rust inhibitors can be mixed. Water. As a specific example, known inhibitors can be used, such as various types of organic acids, for example, oleic acid, dimer acid, tartaric acid, citric acid, various types of chelating agents, for example, eDtA, NTA, HEDTA, DTPA. , mixed components of alkanolamines such as triethanolamine, amine salts and the like of p-t-butylbenzoic acid, amine salts of carboxylic acids, diacid amine bases, and combined uses of alkenylsuccinic acid and water-soluble salts thereof with aminotetrazole and salts soluble in water thereof. Furthermore, these can be used singly, or two or more of them can be combined. The amount of mixing is preferably 0.1 to 30% by mass based on the total mass of solids content.

The liquid medium (solvent, dispersion medium) in the water-based lubricating coating agent according to the present invention is water. In addition, an alcohol having a boiling point lower than that of water can be mixed to reduce the drying time period of the lubricant in one drying step.

The water-based lubricating coating agent according to the present invention may contain a strongly alkaline water-soluble component to increase the stability against liquids. Specific examples include lithium hydroxide, sodium hydroxide, and potassium hydroxide. These can be used singly, or two or more of them can be combined. The amount of mixing is preferably 0.01 to 10% by mass based on the total mass of solids content.

To disperse substances insoluble in water, the use of a surfactant is also allowed. However, the additive amounts of components other than components (A), (B), (C) and (D) preferably do not exceed 50% by mass of the solids content in the water-based lubricating coating agent, as long as the required performance is not degraded. On the contrary, the total of the additive amounts of the components (A), (B), (C) and (D) is preferably 50% by mass or more, more preferably 70% by mass or more, and of further preferably 85% by mass or more based on the solids content of the water-based lubricating coating agent.

«Method for manufacturing the water-based lubricating coating agent>>

The water-based lubricating coating agent according to the present invention is made, for example, by adding and mixing the silicate (A) and the inorganic salt (B), in addition to the resin component (C) and the lubricant ( D), etc., to and with water as the liquid medium. Mixing is carried out by a general method such as propeller stirring or a homogenizer.

«Application of Water Based Lubricant Coating Agent>>

The water-based lubricating coating agent according to the present invention is preferably intended for plastic working in a variety of cold working, such as forging, wire drawing, tube drawing, stamped profile forming and pressing.

• Metallic material to be used

The water-based lubricating coating agent according to the present invention is applied to metallic materials such as iron or steel, stainless steel, copper or a copper alloy, aluminum or an aluminum alloy, and titanium or a titanium alloy. The shape of the metal material is not particularly limited, but the agent is applied not only to materials such as rod materials and block materials, but also to forging products (for example, gears and shafts).

• Use as a base coat film

The water-based lubricating coating agent according to the present invention can also be used as an agent basecoat for other wet lubricants or dry lubricants. Using it as a basecoat film can increase the level of workability and corrosion resistance of other wet lubricants and dry lubricants. The kinds of combined lubricants are not particularly limited, but, for example, as wet lubricants, usual water-based lubricating coating agents such as those typified by the above-mentioned patent documents 1 to 4, lime soaps and forging oils can be used. Further, for example, as dry lubricants, such lubricating powders and typical wire drawing powders containing, as their main constituents, a higher fatty acid soap, borax, lime, molybdenum disulfide, or the like can be used.

«Method for using the water-based lubricating coating agent>>

Next, a method for using the water-based lubricating coating agent according to the present invention will be described. The present method for use includes a step of cleaning a metal material, a step of applying a lubricating water-based coating agent, and a step of drying. Next, the metallic material to be used and the respective steps will be described.

• Cleaning stage (pre-treatment stage)

Preferably at least one cleaning treatment selected from the group consisting of shot blasting, sandblasting, wet blasting, stripping, alkali degreasing and acid cleaning is carried out before forming a water-based lubricating coating film in a metallic material. Cleaning herein is intended to remove oxidized scale generated by annealing or the like and various kinds of contamination (such as oils).

• Application stage

The step of applying the water-based lubricating coating agent according to the present invention to a metallic material is not to be considered as particularly limited, but a dipping method, a flow coating method, a spraying method, and the like may be used. The period of time for the application is not particularly limited as long as the metal surface is sufficiently covered with the water-based lubricating coating agent according to the present invention by application. In order to increase the drying performance, the metal material can be heated up to 60 to 80°C and contacted with the water-based lubricating coating agent for plastic working of metal materials, or it can be contacted with The water-based lubricating coating agent for plastic processing of metal materials, which heats up to 40 to 70°C. Therefore, the drying performance can be significantly improved to enable drying at a usual temperature, and the loss of heat energy can also be reduced.

The coating weight of the water-based lubricant coating film formed on the metal surface is appropriately controlled depending on the degree of processing to be performed later, but the coating weight is preferably within the range of 0. 5 to 40 g/m2, more preferably 2 to 20 g/m2. When the coating weight is less than 0.5 g/m2, the lubricity is insufficient. In addition, it is not preferred that the coating weight is more than 40 g/m 2 because clogging of the mold with debris or the like occurs, although there is no problem with lubricity. The coating weight can be calculated from the difference in the mass of the metallic material between before and after processing and the surface area. In order to control the coating weight, the mass (concentration) of solids content of the water-based lubricating coating agent is appropriately adjusted. The desired coating weight is obtained by creating a high concentration of water-based lubricating coating agent and diluting the agent with water. The water for the dilution adjustment is not particularly limited, but is preferably deionized water or distilled water.

• Drying stage

The step is not to be considered particularly limited, but is preferably carried out for about 1 to 30 minutes at 60 to 150°C.

• Optional stage 1 (base coat stage)

The water-based lubricating coating agent according to the present invention can prevent seizure between a mold and a material to be processed in the case of processing, and provide high corrosion resistance before and after processing, and can be carried out A base coat treatment is carried out for the purpose of further improving workability and corrosion resistance. The base coat treatment may be for a reactive type coating film or a non-reactive type coating film. Specific examples of the reactive type coating film include phosphates, iron oxide, zirconium oxide, zirconium hydroxide, molybdates, oxalates, and tannic acid. Specific examples of the non-reactive type coating film include silicates, borates, zirconium compounds, vanadium compounds, colloidal silica, and resin coating films.

• Optional stage 2 (film removal stage)

The lubricating coating film formed from the water-based lubricating coating agent according to the present invention can be removed by immersing the film in a water-based alkaline cleaning agent or by spray cleaning. The alkaline cleaning agent is a liquid of a typical alkaline component such as sodium hydroxide or potassium hydroxide dissolved in water, and when the water-based lubricating coating film is contacted with the cleaning agent, the cleaning agent film Water-based lubricating coating dissolves in the cleaning agent, thereby making it possible to remove the coating film easily. Therefore, defective plating and defective detachment of oxidized scale can be prevented without contamination in later stages due to removal of defective film in alkali cleaning.

examples

Advantageous effects of the present invention will be specifically described with reference to Examples of the present invention together with Reference Examples and Comparative Examples. It should be noted that the present invention should not be construed as limited by these examples.

«Example A>>

(1-1) Manufacture of water-based lubricating coating agent

The water-based lubricating coating agents according to Examples 1 to 9 and 12 to 16, Reference Examples 10 and 11 and Comparative Examples 1 to 8 were prepared by adopting the respective components listed below in the combinations and proportions shown below. shown in Tables 1 to 2. It should be noted that Comparative Example 9 corresponds to a phosphate/soap treatment.

<Silicate>

(A-1) Sodium silicate (Na ² OnSiO ² , n = 3)

(A-2) Lithium silicate (Li ² OnSiO ² , n = 3.5)

(A-3) Potassium silicate (K ² OnSiO ² , n = 2.3)

<Inorganic salt>

(B-1) Sodium tungstate

(B-2) Sodium tripolyphosphate (used in the reference examples)

(B-3) Potassium metaborate (used in the reference examples)

<Resin component>

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

<Lubricant component>

(D-1) Anionic polyethylene wax (average particle size: 5 |im)

(D-2) Non-swelling synthetic mica (average particle size: 5.0 |im)

(1-2) Method of using the water-based lubricating coating agent

<Conventional stages>

(a) Degreasing: commercial degreasing agent (FINECLEANER E6400 from Nihon Parkerizing Co., Ltd.) concentration: 20 g/l, temperature: 60°C, immersion: 10 min

(b) Water rinse: tap water, usual temperature, immersion: 20 s

(c) Acid cleaning: 17.5% hydrochloric acid, usual temperature, immersion: 20 min

(d) Water rinse: tap water, usual temperature, immersion: 20 s

(e l) to (e3) Lubrication treatment: described for each of the examples and comparative examples

(f) Drying: 100°C, 10 min.

<Lubrication treatment in Examples 1 to 9 and 12 to 15, Reference Examples 10 and 11 and Comparative Examples 1 to 8>

(e1) Lubrication coating treatment: water-based lubricant coating agent made in section (1-1), temperature: 60°C, immersion: 1 min

<Pretreatment and coating treatment in Example 16>

(e1) Base treatment: commercially available zirconium chemical conversion agent (PALLUCID 1500 from Nihon Parkerizing Co., Ltd.) concentration: 50 g/l, temperature: 45°C, pH 4.0, immersion: 2 min

(e2) Rinse with water: tap water, usual temperature, immersion: 20 s

(e3) Lubrication coating treatment: water-based lubricant coating agent made in section (1-1), temperature: 60°C, immersion: 1 min

<Pretreatment and coating treatment in comparative example 9 (phosphate/soap treatment)> (e1) Chemical conversion treatment: commercially available zinc phosphate chemical conversion agent (PALBOND 181X from Nihon Parkerizing Co., Ltd.) concentration: 75 g/l, temperature: 80°C, immersion: 7 min (e2) Water rinse: tap water, usual temperature, immersion: 30 s

(e3) Soap treatment: commercially available reactive type soap lubricant (PALUBE 235 from Nihon Parkerizing Co., Ltd.) concentration: 70 g/l, temperature: 85°C, immersion: 3 min

*Dry coating weight: 10 g/m2

(1-3) Assessment test

(1-3-1) Peak test

Examples 1 to 9 and 12 to 16, Reference Examples 10 and 11, and Comparative Examples 1 to 9 were evaluated for workability by a peak test. The peak test was carried out according to the method described in JP H5-7969 A. The lubricity was evaluated with the height of the peak after the test and the formation load. Lubricity is better the higher the peak height and the lower the formation load. Also, according to the publication, the area increase ratio in the spike test is assumed to be about 10 times. The lubricity of the coating film was evaluated by measuring the workload and the peak height.

Test sample for evaluation: 25mm^ x 30mm S45C spheroidizing annealed material

Evaluation criteria:

Peak performance = peak height (mm)/work load (kNf) x 100

The lubricity is more favorable the higher the value.

©: 0.96 or more

OR : 0.94 or more and less than 0.96

△ : 0.92 or more and less than 0.94

▲: 0.90 or more and less than 0.92

X: less than 0.90

(1-3-2) Tribological test of ironing with ball for upsetting (evaluation of resistance to seizure)

Examples 1 to 9 and 12 to 16, Reference Examples 10 and 11 and Comparative Examples 1 to 9 were evaluated for workability by a ball ironing tribological type test for upsetting. The upsetting ball ironing tribological type test was carried out according to the method described in JP 2013-215773 A. The area increase ratio in the upsetting ball ironing tribological type test is assumed to be of 150 times or more at most, and the test has a higher area magnification ratio and reproduces stronger work compared to the spike test mentioned above. The seizure resistance of the cover film in heavy duty was evaluated by evaluating the amount of seizure generated on the ironing surface.

Test sample for evaluation: 14mm^ x 32mm S10C spheroidizing annealed material

Bearing Ball: 10mm SUJ2^

Evaluation criteria:

The entire area of the ironing surface was evaluated to determine how much area had seized. Figure 1 shows the indications for the evaluation.

◎ : Significantly superior to phosphate/soap coating film

O : superior to phosphate/soap coating film

△ : comparable to phosphate/soap coating film

▲: less than phosphate/soap coating film

X: Significantly less than phosphate/soap coating film

(1-3-3) Film removal ability test

Examples 1 to 9 and 12 to 16, Reference Examples 10 and 11 and Comparative Examples 1 to 8 were subjected to a film removability test. It should be noted that Comparative Example 9 was excluded from the test standard due to the difference in the typical film removal method. In the film removability test, a columnar test specimen was upset at 50% compressibility using both upper and lower flat molds, and then dipped into an alkaline cleaning agent to remove the covering film. After (d) rinsing with water in step (1-2), drying (f) was carried out, and the mass of the test sample after cooling was measured. Thereafter, after (e) lubricating treatment, (f) drying was carried out, and the mass of the test sample after cooling was measured. The mass of a coating film was obtained by converting from the difference in mass between before and after the test. After cleaning with alkali, drying (f) was carried out, and the mass of the test sample after cooling was measured. The mass of coating film after the scouring treatment was obtained by converting from the mass after alkali cleaning and the mass after acid cleaning.

Test sample for evaluation: 25mm^ x 30mm S45C spheroidizing annealed material

Alkaline cleaning agent: 2% NaOH aqueous solution

Film removal condition: liquid temperature 60°C, immersion time 2 min

Film residual ratio (%) = (mass of a coating film after film removal treatment/mass of a coating film before film removal treatment) x 100

Evaluation criteria:

Film removal is more preferable the smaller the residual film ratio is.

©: residual film ratio of 0%

O : film residual ratio greater than 0% and less than 8%

△ : film residual ratio of 8% or more and less than 16%

▲: residual film ratio of 16% or more and less than 25%

X: residual film ratio of 25% or more

(1-3-4) Corrosion resistance test

Examples 1 to 9 and 12 to 16, Reference Examples 10 and 11 and Comparative Examples 1 to 9 were subjected to a corrosion resistance test. Five test samples were simultaneously subjected to a lubrication treatment with the use of a barrel-shaped cylinder, and the test samples were exposed indoors for 3 months in an open atmosphere in summer, thereby observing the degree of oxidation . It has been determined that the corrosion resistance is lower the larger the oxidized area is. All five test samples were evaluated.

Test sample for evaluation: 25mm^ x 30mm S45C spheroidizing annealed material

Evaluation criteria:

◎ : oxidized area representing 3% or less (significantly higher than phosphate/soap coating film)

O : Oxidized area which is more than 3% and 10% or less (greater than phosphate/soap coating film)

△ : oxidized area representing more than 10% and 20% or less (comparable to phosphate/soap coating film)

▲: oxidized area which is more than 20% and 30% or less (less than phosphate/soap coating film)

X: oxidized area representing more than 30% (significantly less than phosphate/soap coating film)

(1-3-5) Evaluation of the total score

The four evaluation results were scored based on what is shown in Table 3, and the total scores were listed.

The test results are shown in tables 4 and 5. It should be noted that table 5 shows details of the corrosion resistance test. As is clear from the tables, the examples and reference examples have achieved favorable workability (pecking test, ball ironing test), film removal and corrosion resistance (indoor exposure). In addition, with respect to corrosion resistance, the mixture with sodium tungstate leads to a favorable level, and it also varies less in performance. Comparative Examples 1 to 8, where the ratios of the silicate (A) and inorganic salt (B) are outside the scope of the claims, tend to create inferior results in the iron-on ball test and the resistance test. to corrosion. The phosphate coating film according to Comparative Example 9, subjected to the reactive soap treatment, shows relatively excellent performance, but inferior performance as compared with the examples.

Hereinafter, the present invention will be further and specifically described together with advantageous effects thereof by providing examples of the present invention together with reference examples and comparative examples, for the case of using the present invention as basecoat films for dry lubricants. and wet lubricants. It should be noted that the present invention should not be construed as limited by these examples.

«Example B>>

(2-1) Manufacture of water-based lubricating coating agent

Water-based lubricating coating agents were prepared according to Examples 17 to 26, 29 to 39 and 42, Reference Examples 27, 28, 40 and 41 and Comparative Examples 11 to 18 and 20 to 27 by adopting the respective components. mentioned above in the combinations and proportions shown in Tables 6 and 7. For Comparative Example 10, only wire drawing powder was used without any lubricating coating film according to the present invention. For Comparative Example 19, a lime soap without any lubricating coating film according to the present invention was used. Comparative Example 28 corresponds to a phosphate/soap treatment. It should be noted that no wire drawing powder is used for Examples 30 to 39 and 42, Reference Examples 40 and 41 and Comparative Examples 19 to 28.

(2-2) Lubrication treatment

<Lubrication treatment in Examples 17 to 26, Reference Examples 27 and 28, and Comparative Examples 11 to 18>

Treatment was carried out according to the conventional steps listed in section (1-2).

(e) Lubrication coating treatment: water-based lubricant coating agent made in section (2-1), temperature: 60°C, immersion: 1 min

<Pretreatment and coating treatment in Examples 30 to 39, Reference Examples 40 and 41, and Comparative Examples 20 to 27>

Treatment was carried out according to the conventional steps listed in section (1-2).

(e1) Lubrication coating treatment: water-based lubricant coating agent made in section (2-1), temperature: 60°C, immersion: 1 min

Thereafter, as a top coat coating film, dipping treatment was carried out for 1 min at 60°C with 250 g/L of a commercially available lime soap (LUB-CAO2 from Nihon Parkerizing Co., Ltd. .), and the same drying as (f) drying was carried out to obtain a lime soap coating amount of 5 g/m 2 .

<Pretreatment and coating treatment in Example 29>

(e1) Base treatment: commercially available zirconium chemical conversion agent (PALLUCID 1500 from Nihon Parkerizing Co., Ltd.) concentration: 50 g/l, temperature: 45°C, pH 4.0, immersion: 2 min

(e2) Rinse with water: tap water, usual temperature, immersion: 20 s

(e3) Lubrication coating treatment: water-based lubricant coating agent made in section (2-1), temperature: 60°C, immersion: 1 min

<Pretreatment and coating treatment in Example 42>

(e1) Base treatment: commercially available zirconium chemical conversion agent (PALLUCID 1500 from Nihon Parkerizing Co., Ltd.) concentration: 50 g/l, temperature: 45°C, pH 4.0, immersion: 2 min

(e2) Rinse with water: tap water, usual temperature, immersion: 20 s

(e3) Lubrication coating treatment: water-based lubricant coating agent made in section (2-1), temperature: 60°C, immersion: 1 min

Thereafter, as a top coat coating film, dipping treatment was carried out for 1 min at 60°C with 250 g/L of a commercially available lime soap (LUB-CAO2 from Nihon Parkerizing Co., Ltd. .), and the same drying as (f) drying was carried out to obtain a lime soap coating amount of 5 g/m 2 .

<Pretreatment and coating treatment in Comparative Example 10>

(e) Pure water rinse: deionized water, usual temperature, immersion: 30°C

<Pretreatment and coating treatment in Comparative Example 19>

(e) Lubrication: commercially available lime soap (LUB-CAO2 from Nihon Parkerizing Co., Ltd.) 250 g/l, temperature 60°C, immersion 1 min

(f) Drying: 100°C, 10 min.

*Lime soap coating weight: 5 g/m2

<Pre-treatment and coating treatment in Comparative Example 28 (phosphate/soap treatment)> (e1) Chemical conversion treatment: commercially available zinc phosphate chemical conversion agent (PALBOND 421 WD from Nihon Parkerizing Co., Ltd.) concentration: 75 g/l, temperature: 80°C, immersion: 10 min (e2) Water rinse: tap water, usual temperature, immersion: 30 s

(e3) Soap treatment: commercially available reactive soap lubricant (PALUBE 235 from Nihon Parkerizing Co., Ltd.) concentration: 70 g/l, temperature: 85°C, immersion: 3 min

*Dry coating weight: 10 g/m2

(2-3) Assessment test

(2-3-1) Wire drawing test (lubricity evaluation)

Examples 17 to 26, 29 to 39 and 42, Reference Examples 27, 28, 40 and 41 and Comparative Examples 10 to 28 were evaluated for workability by a wire drawing test. Wire drawing was carried out by drawing ^3.2mm steel wire through a ^2.76 die. In Examples 17 to 26 and 29, Reference Examples 27 and 28 and Comparative Examples 10 to 18, Missile C40 from Matsuura Industry Co., Ltd. was used as a dry lubricant. The dry lubricant was placed in a die box immediately prior to stretching the material to naturally adhere to the material. The evaluation was made from the seizing of the test material and the residual amount of the lubricating film after wire drawing. It should be noted that the amount of coating after wire drawing was obtained from the mass difference between before and after removal by removing the coating film with the use of the following film-removing agent.

Test sample for evaluation: SWCH45K material, ^3.2 mm x 20 m

Die diameter: ^2.76

Film release agent: commercially available alkaline release agent (FC-E6463 from Nihon Parkerizing Co., Ltd.), 20 g/l

Film removal condition: liquid temperature 60°C, immersion time 2 min

Evaluation criteria:

Residual film ratio (%) = (amount of coating before work/amount of coating after work) x 100

*The amount of coating before work does not include any lubricating powder. The amount of coating after work includes the lubricating powder.

◎ : residual film ratio of 85% or more

O : film residual ratio of 75% or more and less than 85%

△ : film residual ratio of 65% or more and less than 75%

▲ : film residual ratio of 50% or more and less than 65%

X: residual film ratio less than 50%, or seizure generated

(2-3-2) Corrosion resistance test

Examples 17 to 26, 29 to 39 and 42, Reference Examples 27, 28, 40 and 41 and Comparative Examples 10 to 28 were evaluated for corrosion resistance. The wire rod subjected to the above-mentioned wire drawing test was exposed indoors for 3 months in an open atmosphere in summer, thereby observing the degree of oxidation. It has been determined that the corrosion resistance is lower the larger the oxidized area is.

Evaluation criteria:

©: Significantly superior to phosphate/soap coating film (oxidized area representing 3% or less)

O : superior to phosphate/soap coating film (oxidized area accounting for 3% or more and less than 10%)

△ : comparable to phosphate/soap coating film (oxidized area accounting for 10% or more and less than 20%)

▲ : less than phosphate/soap coating film (oxidized area accounting for 20% or more and less than 30%)

X: Significantly less than phosphate/soap coating film (oxidized area accounting for 30% or more)

The test results are shown in Table 8. All examples where the coating films practically remained resulted in favorable workability and corrosion resistance. Furthermore, from the high corrosion resistance after wire drawing, it is determined that the lubricating coating film according to the invention practically remains after working. Comparative Examples 10 and 19, having the pattern without the use of the lubricant according to the present invention, are significantly inferior in wire drawability and corrosion resistance. Comparative Examples 11 to 18 and 20 to 27 with inappropriately adjusted ratios of silicate (A) and inorganic salt (B) are inferior in residual amount of coating and corrosion resistance after wire drawing. The phosphate coating film subjected to the reactive soap treatment according to Comparative Example 28 demonstrates excellent performance, but requires wastewater treatment or liquid management, so it cannot be used in simple processing steps or systems, and produces residues with the reaction, thereby resulting in an increased environmental burden.

As is evident from the above description, the use of the water-based lubricant according to the present invention can achieve a balance between high workability and corrosion resistance. In addition, the lubricating coating film after processing with the cleaning agent is also favorably removed. Therefore, the present invention has great potential in the industry.

[Table 1]

[Table 2]

[Table 31

[Table 4]

example d

^{example d}

* Comparative Example 9 was not evaluated due to the different film removal method.

The total score of Comparative Example 9 calculated as film removal ability is ® [Table 5]

Table 6

Table 7

[Table 8]

example d

example d

^{example d}

^{example d}

Claims (2)

Yo. Water-based lubricating coating agent in which a water-soluble silicate (A) having a solubility of at least 1 g in 100 g of water at 25°C and a water-soluble inorganic salt (B) having a solubility of at least 1 g in 100 g of water at 25°C are mixed has a solubility of at least 1 g in 100 g of water at 25°C, which is a tungstate, such that the mass ratio of solids content (B)/(A) is within the range of 0, 7 to 25, wherein the agent comprises a resin component (C), and the mass ratio of solid content (C)/{(A)(B)} is 0.01 to 3, wherein the resin component (C) is at least one selected from the group consisting of a vinyl resin, an acrylic resin, an epoxy resin, a urethane resin, a phenolic resin, a cellulose derivative, a poly( maleic acid), a polyolefin and a polyester, and wherein the agent comprises a lubricant (D), and the mass ratio of solids content (D)/{(A)(B)} is from 0.01 to 6, wherein the lubricant (D) is at least one selected from the group consisting of a wax, polytetrafluoroethylene, a fatty acid soap, a fatty acid metal soap, a fatty acid amide, molybdenum disulfide, tungsten disulfide, graphite, melamine cyanurate, a layered structure amino acid compound and a layered clay mineral. 2. Metal material with a lubricating coating film of 0.5 to 40 g/m2 as coating weight, formed on a metal material surface by applying and drying the water-based lubricating coating agent according to claim 1 .