WO2019167816A1

WO2019167816A1 - Metal material for plastic working

Info

Publication number: WO2019167816A1
Application number: PCT/JP2019/006682
Authority: WO
Inventors: 康宏岡田; 睦柳; 充青山
Original assignee: 日本パーカライジング株式会社
Priority date: 2018-02-28
Filing date: 2019-02-22
Publication date: 2019-09-06
Also published as: TW201938842A; JPWO2019167816A1; KR20200106187A; JP7132321B2; KR102513657B1; CN111771014A; CN116200733A

Abstract

The present invention addresses the problem of providing a metal material for plastic working, which has excellent welding resistance. The above-described problem is able to be solved by a metal material for plastic working, which has a first coating film on the surface of the metal material, while having a second coating film in or on the surface of the first coating film, and wherein the second coating film serves as a surface layer and contains a compound that has a benzene ring to which at least one carboxy group is directly bonded, or a salt or peroxide of the compound.

Description

Metal materials for plastic working

The present invention is a plastic working having a coating necessary for performing plastic working such as forging (including cold, warm, hot forging), wire drawing, and pipe drawing on steel materials or other metal materials. It relates to a metal material.

In the plastic processing of metal materials, the mold and the metal material for plastic processing may be seized. The seizure not only does not give the desired molded product, but also changes the dimensions of the mold due to the influence of the seized metal, and the number of times that the mold can be used is shortened. Therefore, the mold must be remanufactured, reducing cost effectiveness. Therefore, a metal material for plastic working which is excellent in seizure resistance is required.

For example, Patent Document 1 discloses a lubricant for warm and hot plastic working containing an alkali metal salt of an aromatic carboxylic acid compound having two or more carboxy groups, several types of water-soluble polymer compounds, and water. Is disclosed.
Patent Document 2 discloses a lubricant for warm and hot forging containing a specific compound in which two aromatic rings having two carboxy groups located at ortho positions are bonded.
Patent Document 3 discloses an aqueous cold plasticity containing an aromatic carboxylate formed of sodium hydroxide or potassium hydroxide and having a melting point of 90 ° C. or more, a water-soluble polymer compound and / or wax, and water. A processing lubricant composition is disclosed.

Japanese Unexamined Patent Publication No. 2015-89938 Japanese Unexamined Patent Publication No. 2015-89939 Japanese Unexamined Patent Publication No. 2015-17171

An object of the present invention is to provide a metal material for plastic working excellent in seizure resistance.

As a result of intensive studies to solve the above problems, the present inventors have a first coating on the surface or surface of the metal material, and a second coating on the surface or surface of the first coating, 2 film is a surface layer, and the second film is a compound having a benzene ring to which at least one carboxy group is directly bonded, a salt thereof, or a metal material for plastic working containing a peroxide thereof, which has excellent seizure resistance. The present inventors have found that this is a metal material for plastic working and has completed the present invention.

The present invention (1)
A first coating on or on the surface of the metal material;
Having a second film on or on the surface of the first film;
The second film is a surface layer,
The second film is a metal material for plastic working including a compound having a benzene ring to which at least one carboxy group is directly bonded, a salt thereof, or a peroxide thereof.

According to the present invention, it is possible to provide a metal material for plastic working which is excellent in an effect (seizure resistance) of preventing seizure due to friction between a mold and a metal material for molding that occurs during plastic working.

It is a figure which shows the seizure resistance evaluation criteria of the test piece which performed the processing performance evaluation test (drawing substitute photograph).

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

<Metal materials for plastic working>
The metal material for plastic working according to one embodiment of the present invention includes a metal material, a first film on the surface or surface of the metal material, and at least one carboxy group directly bonded to the surface or surface of the first film. And a second film containing a compound having a benzene ring or a salt thereof or a peroxide thereof. Moreover, between the 1st membrane | film | coat and the 2nd membrane | film | coat, you may have a membrane | film | coat with which the single layer or the some layer was laminated | stacked, and the 2nd membrane | film | coat should just exist in the surface layer.

The plastic working in the present specification is not particularly limited as long as it is a publicly known plastic working. For example, forging (cold, warm, hot), extrusion, wire drawing, tube drawing, drawing, drawing, etc. Examples include machining, bending, joining, shearing, and sizing. Among these, the metal material for plastic working according to the present invention is suitable for plastic working in which the load applied to the metal material is particularly large, such as forging, wire drawing and pipe drawing.

1. 1. Structure of metal material for plastic working 1-1. Metal Material The metal material is not particularly limited, but is usually a metal material that is subjected to plastic working. Examples thereof include iron, iron alloys (steel, stainless steel, etc.), aluminum, aluminum alloys, magnesium, magnesium alloys, titanium, titanium alloys, copper, copper alloys, tin, tin alloys, zinc, zinc alloys, and the like.

The metal material may be a plating material having a plating film as long as the effects of the present invention are not impaired. The material of the plating film is not particularly limited. For example, a metal such as nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead, zinc, tin, or antimony, or an alloy of a plurality of metals, and inevitable impurities are used. A metal or an alloy of a plurality of metals can be used.

When the plating film is artificially formed, a known method can be used, for example, electroplating (electrolytic plating, electroplating), electroless plating, hot dipping, vapor phase plating, mechanical plating, Thermal spraying etc. are mentioned.

The thickness of the plating film is not particularly limited, and is, for example, 0.1 μm or more and 1000 μm or less.

Further, an oxide film may be formed on the surface of the metal material. The oxide film is not particularly limited, and may be a natural oxide film that naturally occurs in the atmosphere or an artificially formed oxide film.

The method for forming an artificial oxide film is not particularly limited. For example, a method using an anodic oxidation performed by energizing a metal material as an anode in an electrolyte solution, a method immersed in a strongly acidic liquid, a method using electropolishing, plasma Examples include a method using electrolysis. The oxide film may be sealed by a vapor method, a pure water boiling water method, a nickel acetate method, a dichromic acid method, a sodium silicate method, or the like.

The thickness of the oxide film is not particularly limited, and is, for example, 0.001 μm or more and 100 μm or less.

The shape of the metal material is not particularly limited, and may be not only a shape such as a rod or block material but also a shape after processing (gear, shaft, etc.).

1-2. The first coating is not particularly limited, and for example, a chemical conversion coating or a coating film can be used.

1-2-1. Chemical conversion film The film deposition mechanism of chemical conversion treatment is, for example, as follows. When the metal material is brought into contact with the chemical conversion treatment agent, the surface of the metal material is etched (dissolved) by H ⁺ ions which are acid components (etching components) in the chemical conversion treatment agent, thereby increasing the pH in the vicinity of the surface. As the pH in the vicinity of the surface rises, the metal component etched from the metal material existing in the vicinity of the surface and the component contained in the chemical conversion liquid are deposited on the surface of the metal material as insoluble salts. This insoluble salt forms a film.

The chemical conversion film is not particularly limited, and includes, for example, phosphate, oxalate, aluminate, chromate, molybdate, zirconium compound, titanium compound, vanadium compound, and hafnium compound. In addition, these may be comprised with the single salt and may be comprised with the some salt. The chemical conversion film is preferably composed of phosphate, oxalate and aluminate, and more preferably composed of zinc phosphate and iron oxalate.

The phosphate is not particularly limited. For example, zinc phosphate, zinc iron phosphate, nickel phosphate, manganese phosphate, manganese iron phosphate, calcium phosphate, cobalt phosphate, magnesium phosphate, aluminum phosphate, phosphoric acid Sodium, potassium phosphate, ammonium phosphate, etc. are mentioned. The phosphate is preferable when the metal material is steel or stainless steel.

The oxalate is not particularly limited, and examples thereof include sodium oxalate, potassium oxalate, iron oxalate, and ammonium oxalate. The oxalate is preferable when the metal material is stainless steel.

The aluminate is not particularly limited, and examples thereof include lithium aluminate, sodium aluminate, potassium aluminate, magnesium aluminate, and calcium aluminate. The aluminate is preferred when the metal material is aluminum or an aluminum alloy.

Although the adhesion amount of the chemical conversion film is not particularly limited, for example, it is 0.5 g / m ² or more and 20.0 g / m ² or less, preferably 2.0 g / m ² or more and 10.0 g / m ² or less. is there. The amount of adhesion can be adjusted by changing contact conditions such as the composition and concentration of the chemical conversion treatment agent, the contact method, the contact temperature, and the contact time.

1-2-2. Coating film A coating film is a film formed by applying a coating type coating agent on the surface of a metal material.

The material of the coating film is not particularly limited as long as it can be formed on the surface or surface of the metal material according to the present embodiment, and the second film can be formed on the surface or surface. Examples of the coating film formed using the coating-type coating agent include a coating film formed by coating-type chromate treatment with a treatment liquid containing chromic acid, dichromic acid or a salt thereof as a main component; Coating film formed by coating-type non-chromate treatment that does not contain chromic acid or dichromic acid; Coating film by silane coupling agent alone; Coating film such as silica or colloidal silica modified by silane coupling agent; Urethane resin Organic resin film containing epoxy resin, acrylic resin, olefin resin such as polyethylene, polypropylene, ethylene-acrylic acid copolymer, styrene resin such as polystyrene, polyester or copolymer or modified product thereof; Lithium oxide, glass such as sodium silicate, metal oxyacid salt, metal hydroxide compound, metal phosphate , Inorganic coatings containing metal fluoride compounds (excluding plating coatings and oxide coatings); lubricants for solvents such as water and oil, and base polymers such as copolymers containing styrene and maleic acid / maleic anhydride And a coating film in which is dispersed.

The solid lubricant is not particularly limited, and examples thereof include waxes such as polyethylene wax and polypropylene wax; layered clay minerals such as smectite, vermiculite, mica, brittle mica, pyrophyllite, and kaolinite; polytetrafluoroethylene; fatty acid metal Soap, fatty acid amide; molybdenum disulfide; tungsten disulfide; graphite; and melamine cyanurate.

1-3. Second coating 1-3-1. Material The 2nd membrane | film | coat which concerns on this embodiment contains at least 1 or more types of the compound which has a benzene ring which the at least 1 carboxy group directly couple | bonded in the structure, its salt, or its peroxide. In the present specification, a compound having a benzene ring to which at least one carboxy group is directly bonded may be referred to as an aromatic carboxylic acid compound.

Here, the benzene ring in the present invention is not limited to a single benzene ring such as a benzene compound, but a condensed polycyclic aromatic carbonized carbon in which a plurality of benzene rings are directly condensed such as naphthalene or anthracene. Hydrogen is also included.

The aromatic carboxylic acid compound is not particularly limited as long as it does not inhibit the effect of the present invention. Isoduric acid, anisic acid, o-cresotic acid, m-cresotic acid, p-cresotic acid, o-pyrocatechuic acid, β-resorcylic acid, gentisic acid, γ-resorcylic acid, protocatechuic acid, α-resorcylic acid, vanillic acid, Isovanillic acid, veratrmic acid, 2,3-dimethoxybenzoic acid, orthoric acid, m-hemipic acid, gallic acid, syringic acid, asaronic acid, homophthalic acid, homoisophthalic acid, homoterephthalic acid, phthalonic acid, isophthalonic acid, terephthalonic acid , Cumic acid, ubitoic acid, benzoic acid, phthalic acid, salicylic acid, etc.In addition, these may be included independently and multiple may be included.

Among the salts of aromatic carboxylic acid compounds, the ammonium salts, sodium salts, lithium salts, and potassium salts of the aromatic carboxylic acid compounds, which are excellent in the effect of preventing seizure during plastic working (seizure resistance), are more preferable.

In addition, when a plurality of carboxy groups are directly bonded to the benzene ring, at least a part or all of the salt of the aromatic carboxylic acid compound may be a salt. For example, in the case of a sodium salt of phthalic acid having two carboxy groups, sodium phthalate in which one carboxy group forms a salt with sodium, and disodium phthalate in which both carboxy groups form a salt with sodium Can be included.

The peroxide of the aromatic carboxylic acid compound is a compound having a peroxide structure in at least one carboxy group directly bonded to the benzene ring of the aromatic carboxylic acid compound. For example, when the aromatic carboxylic acid compound is benzoic acid, the peroxide is perbenzoic acid.

When a plurality of carboxy groups are directly bonded to the benzene ring, at least a part of the peroxide of the aromatic carboxylic acid compound may have a peroxide structure.

The aromatic carboxylic acid compound or a salt thereof or a peroxide thereof is not necessarily contained in the raw material, and may be contained in the formed second film. For example, a case where a compound having a benzene ring having a carboxy group bonded thereto is produced by reacting with an anhydride of carboxylic acid directly bonded to the benzene ring (for example, phthalic anhydride) with water or alcohol.
The content of the aromatic carboxylic acid compound in the second film is not particularly limited, and compounds other than the aromatic carboxylic acid compound, such as other resins, in the second film are not limited within the range that does not impair the effects of the present invention. You may contain. When the second film contains a compound other than the aromatic carboxylic acid compound, the content of the aromatic carboxylic acid compound in the second film may be 0.5% by weight or more and 10% by weight or more. Is preferred. The second film may be formed only from the aromatic carboxylic acid compound.

1-4. The film contained between the first film and the second film The metal material for plastic working can include a film in which a single layer or a plurality of layers are laminated between the first film and the second film.
The type of coating, material, combination of materials, combination of coating methods, number of layers, thickness of each coating, etc. of the coating contained between the first coating and the second coating inhibit the effect of the present invention. As long as it is not, it is not particularly limited.

The film included between the first film and the second film may include a chemical conversion film, a coating film, a plating film, an oxide film, and the like. For example, after forming a plating film on the first film by vapor phase plating such as vapor deposition, a chemical conversion film can be further formed on the plating film.

2. Manufacturing method of metal material for plastic working The manufacturing method of the metal material for plastic working which is another embodiment of the present invention includes a first film forming step of forming a first film at least on the surface of the metal material or the surface, and And a second film forming step of forming a second film on or on the surface of the first film.

A water washing process may be included before and after each process in the first film forming process, and a drying process may be included after the first film is formed. The same applies to the second film forming step, and a water washing step may be included before and after each step, and a drying step may be included after forming the second film. Furthermore, when forming the surface treatment layer between the first film and the second film, a water washing process may be included between the processes, or a drying process may be included after the film is formed.

If necessary, a step of forming a single layer or a layered layer of a plurality of layers may be included after forming the first coating and before forming the second coating.

Furthermore, a cleaning step may be included before and after each step. Moreover, you may implement a cleaning process in multiple times.

2-1. First Film Forming Process The first film forming process may include at least one of a chemical film forming process and a coating film forming process.

2-1-1. Chemical conversion film formation process The chemical conversion film formation process includes at least a contact process in which a chemical conversion treatment agent is brought into contact with the metal material surface to form a first film as a chemical conversion film. As a contact method, a well-known method can be used and it is not specifically limited. For example, there are an electrolytic treatment method performed by passing an electric current, and a treatment method performed without flowing an electric current, such as an immersion treatment method, a spray treatment method, and a pouring treatment method.

The (contact) temperature of the metal material and the chemical conversion treatment agent is not particularly limited, but is preferably 10 ° C. or higher and 98 ° C. or lower, and more preferably 20 ° C. or higher and 50 ° C. or lower.

The contact time is not particularly limited, but is preferably 30 to 300 seconds, and more preferably 60 to 180 seconds.

2-1-2. Coating Film Forming Process The coating film forming process includes at least a process of forming a first film as a coating film by bringing a treatment agent for forming a film into contact with the metal material surface or surface. As a contact method, a well-known method can be used and it is not specifically limited. For example, a rolling method, a dipping method, a flow coating method, a spray method, a brush coating, a liquid electrostatic coating method, a bar coating, a powder coating and the like can be performed to form a coating film. More specifically, for example, if the metal material is a sheet, it is preferable to perform a roll coating method or a spray coating method. Moreover, if the metal material is a molded article, it is preferable to carry out an immersion method. When the raw material contains a solid, the treatment agent may be prepared after dissolving or dispersing the solid raw material in advance in a solvent such as water or an organic solvent.

The adhesion amount of the coating film is not particularly limited, for example, 0.5 g / ^{m 2} or more 50.0 g / ^{m 2} or less, preferably, 2.0 g / ^{m 2} or more 20.0 g / ^{m 2} or less, More preferably, it is 2.0 g / m ² or more and 10.0 g / m ² or less. The adhesion amount can be adjusted by changing the contact conditions such as the composition and concentration of the treatment agent, the contact method, the contact temperature and the contact time.

The contact condition of the treatment agent is not particularly limited. For example, the temperature of the treatment agent when contacting the treatment agent is 10 ° C. or more and 80 ° C. or less, preferably 25 ° C. or more and 75 ° C. or less, more preferably 25 ° C. or more and 60 ° C. or less. The temperature is not limited. The contact time can be appropriately set, but is usually 2 seconds or more and 180 seconds or less.

The first film forming step can include a drying step, if necessary. The drying method may be a known method and is not particularly limited. For example, natural drying, reduced pressure drying, convection heat drying (for example, natural convection heat drying, forced convection heat drying), radiation drying (for example, near infrared drying, far infrared drying), ultraviolet curing drying, electron beam curing Examples thereof include drying and vapor curing. A plurality of these may be combined.

Also, the drying time can be appropriately selected depending on the composition of the treatment agent. The drying time is preferably in the range of 1 second to 1800 seconds, and more preferably in the range of 10 seconds to 1200 seconds.

The drying temperature may be a normal drying temperature, and the maximum ultimate temperature (PMT) of the metal material is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 80 ° C. or higher and 150 ° C. or lower. When the drying temperature is less than 60 ° C., moisture as a main solvent of the surface treatment agent remains, and the film may not be fixed on the surface of the metal material. In such a case, it is also possible to maintain a temperature of less than 60 ° C. until the water volatilizes. The drying temperature of 60 [deg.] C. or higher is preferred because continuing to dry until moisture evaporates reduces productivity.

2-2. Method for forming a film contained between first film and second film A method for producing a film contained between the first film and the second film comprises a desired single layer on the surface of the first film. Or the film formation process which forms the film | membrane which laminated | stacked the several layer is included. The film forming step is not particularly limited, and a known method corresponding to the film to be formed can be used. For example, a chemical conversion treatment step for forming a chemical conversion film, a contact step and a drying step for a metal material formed with a treatment agent for forming a coating film and a first film, a plating treatment step for forming a plating film, and the like can be mentioned. The processing conditions of each process are not specifically limited, The processing conditions according to each membrane | film | coat and its formation method can be used.

2-3. Second film forming step The second film forming step includes a step of bringing a treatment agent for forming the second film into contact with the surface or the surface of the first film formed on the surface or the surface of the metal material. As a contact method, a well-known method can be used, It does not specifically limit, The method similar to the contact method in the said coating-film formation process can be used. When the raw material contains a solid, the treatment agent may be prepared after dissolving or dispersing the solid raw material in advance in a solvent such as water or an organic solvent.

The formation process of a 2nd membrane | film | coat can include a drying process as needed. The drying method is not limited to the contact method of the coating film, and the same method as the drying method of the coating film can be used.

Further, the drying time can be appropriately selected depending on the composition of the treatment agent, but from the viewpoint of productivity and film formation, preferably within the range of 1 second or more and 1800 seconds or less, 10 seconds or more, More preferably within the range of 1200 seconds or less.

The drying temperature may be a normal drying temperature, and the maximum ultimate temperature (PMT) of the metal material is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 80 ° C. or higher and 150 ° C. or lower. When the drying temperature is 60 ° C. or higher, it is difficult for moisture, which is the main solvent of the surface treatment agent, to remain, and the coating is easily fixed on the surface of the metal material.

The adhesion amount of the second film is not particularly limited, but is, for example, 0.1 g / m ² or more and 20.0 g / m ² or less, preferably 2.0 g / m ² or more and 15.0 g / m ² or less. is there. The adhesion amount can be adjusted by changing the contact conditions such as the composition and concentration of the treatment agent, the contact method, the contact temperature and the contact time.

2-4. Cleaning process The cleaning process includes, for example, washing the surface of each film contained between the metal material, the first film, and the first film and the second film with water (for example, hot water), solvent cleaning, alkali It is a process of cleaning by degreasing and pickling.

The purpose of the cleaning process is to remove oil, dirt, and scale that adheres to the metal material, the first coating, and the surface of each coating contained between the first coating and the second coating or the surface. Will be implemented. Further, the surface of the metal material or the surface thereof may be coated with rust preventive oil for the purpose of rust prevention, and in that case, the purpose of removing the rust preventive oil is also included. By performing the cleaning step, the surface or the surface can be cleaned, and the treatment agent for the film laminated on the surface or the surface can be brought into uniform contact with the surface. In addition, when there is no oil or dirt on the surface or the surface, and the chemical conversion treatment agent and the paint can be uniformly contacted, it is not particularly necessary to perform this cleaning step.

3. Plastic working method The plastic working method according to the present embodiment is not particularly limited. For example, forging, extrusion, wire drawing, tube drawing, drawing, drawing, bending, joining, shearing, and sizing Known methods such as

Hereinafter, the effects of the present invention will be specifically described by giving examples and comparative examples of the present invention. In addition, this invention is not restrict | limited by these Examples.

(1-1) Metal Material The shape of the metal material used in Examples 1 to 19 and Comparative Examples 1 to 4 is shown in Reference Documents (Akinori Takahashi, Hitoshi Hirose, Shinobu Komiyama, Takeshi Wang: Lecture at the 62nd Japan Plastic Working Association A barrel-like shape having an upsetting ratio of 45% used in the ball ironing friction test method disclosed in the collection of papers, (2011), 89/90).
As the metal material, S10C material was used in Examples 1 to 10 and Comparative Examples 1, 3 and 4, and SUS430 material was used in Examples 11 to 19 and Comparative Example 2.

(1-2) Preparation of Various Surface Treatment Agents Surface treatment agents for forming the first film and the second film of Examples 1 to 19 were prepared in combinations shown in Table 1. Hereinafter, the surface treatment agent for forming the first film will be described as surface treatment agent A, and the surface treatment agent for forming the second film will be described as surface treatment agent B.

・ Surface treatment agent A
The surface treating agent A of Examples 1 to 10 was prepared. First, Palbond 181XM (manufactured by Nippon Parkerizing Co., Ltd.) was added to deionized water so that the concentration was 90.0 g / L. Then, the numerical value of the total acidity obtained by the titration method was divided by the numerical value of the free acidity obtained in the same manner, and this was determined to be 6.5 as the acid ratio (total acidity / free acidity).
Next, it adjusted so that the density | concentration (a unit is a point) of the promoter using the accelerator 131 (made by Nippon Parkerizing Co., Ltd.) might be 2.5 points.
The concentration of the accelerator 131 was measured using a glass instrument called a saccharometer (capacity: 50 mL). Concentration measurement was performed by filling a saccharometer with a surface treatment agent added with an accelerator and adding 5 g of a reagent 205 (manufactured by Nihon Parkerizing Co., Ltd.) that reacts with the accelerator contained in the surface treatment agent. At this time, if the surface treatment agent contains an accelerator, gas is generated. The volume of the generated gas indicates the concentration of the accelerator, and when the amount of the generated gas is 1 mL, the concentration of the accelerator contained in the surface treatment agent (in units) is 1 point.

The surface treating agent A of Examples 11 to 19 was prepared. First, using Felbond A1 and Felbond A2 (both manufactured by Nihon Parkerizing Co., Ltd.), the former concentration is 40.0 g / L and the latter concentration is 20.0 g / L. Added to. Next, the concentration of the accelerator using accelerator 16 (manufactured by Nippon Parkerizing Co., Ltd.) was adjusted to 1.0 point.
Concentration of accelerator 16 was obtained by collecting the surface treatment solution in a beaker with a 25 mL hole pipette, adding 50 mL of deionized water, 25.0 mL of reagent 54 (manufactured by Nihon Parkerizing Co., Ltd.) and indicator 10 (manufactured by Nihon Parkerizing Co., Ltd.). In addition, titration was performed with the titrant 53 (manufactured by Nihon Parkerizing Co., Ltd.) until the liquid became dark blue. The dripping amount of the titrant 53 required so far was defined as the accelerator concentration (unit: point).

・ Surface treatment agent B
The surface treating agent B was prepared by adding the aromatic carboxylic acid compound described in Table 1 or a salt thereof or a peroxide thereof to distilled water. The concentration of the aromatic carboxylic acid compound of B or its salt or its peroxide in the surface treatment agent is such that the adhesion amount of the second film formed by the surface treatment agent B is 4.0 g / m ² , 8.0 g / m. ² and 12 g / m ² .

In Comparative Examples 1 to 4, the following were used as surface treatment agents for forming a single film.
Surface treatment agent in Comparative Example 1: Surface treatment agent A in Examples 1 to 10
Surface treatment agent in Comparative Example 2: Surface treatment agent A of Examples 11-19
Surface treatment agent in Comparative Example 3: Mineral oil (paraffinic mineral oil, 8 cst (centistokes) at 40 ° C.)
Surface treatment agent in Comparative Example 4: Surface treatment agent B of Examples 2 and 12

(1-3) Metal Material Cleaning Treatment The surfaces of the metal materials used in the examples and comparative examples were cleaned by the following method.

The concentration of a commercially available degreasing agent (Fine Cleaner E6400, manufactured by Nihon Parkerizing Co., Ltd.) was adjusted to 20 g / L using tap water and heated to a constant temperature of 60 ° C. The metal material was immersed in the degreasing agent for 10 minutes for degreasing. Subsequently, the degreasing agent and dirt remaining after being immersed in tap water at 25 ° C. for 20 seconds were washed with water. Next, the metal material after washing with water was immersed in 17.5% hydrochloric acid at 25 ° C. for 10 minutes to remove stains that could not be removed by washing with water. Furthermore, it was immersed in 25 degreeC tap water for 20 seconds, and the hydrochloric acid adhering to a metal material was washed away.

(1-4) Method for Forming First Film and Second Film in Examples 1 to 19 The first film and the second film were formed on the metal material subjected to the cleaning treatment by the following method.

Examples 1 to 10
The washed metal material was immersed in a surface treatment agent A adjusted to 80 ° C. for 10 minutes to form a first film. Subsequently, the metal material on which the first film was formed was immersed in tap water at 25 ° C. for 30 seconds and washed with water. Table 1 shows the amounts of the first coatings of Examples 1 to 10. The amount of adhesion was calculated by measuring the weight of the metal material before and after forming the first film, dividing the difference as the adhesion weight, and dividing by the surface area of the original metal material.

Further, the metal material on which the first film was formed was immersed in a surface treatment agent B heated to 60 ° C. for 15 seconds, taken out and then naturally dried to form a second film, and the plastic working of Examples 1 to 10 was performed. Metal material for use. The amount of adhesion of the second film is shown in Table 1. The amount of adhesion was calculated by measuring the weight of the metal material before and after the formation of the second film, taking the difference as the adhesion weight, and dividing by the surface area of the original metal material.

Examples 11 to 19
The washed metal material was immersed in a surface treatment agent A adjusted to 90 ° C. for 10 minutes to form a first film. Subsequently, the metal material on which the first film was formed was immersed in tap water at 25 ° C. for 30 seconds and washed with water. Table 1 shows the amounts of the first coatings of Examples 11 to 19. The amount of adhesion was calculated by the same method as in Examples 1-10.

Further, the metal material on which the first film was formed was immersed in a surface treatment agent B heated to 60 ° C. for 15 seconds, taken out, and then naturally dried to form a second film. Metal material for use. The amount of adhesion of the second film in Examples 11 to 19 is shown in Table 1. The amount of adhesion was calculated by the same method as in Examples 1-10.

(1-5) Method for Forming Single Film of Comparative Examples 1-4 In Comparative Example 1, a single film was formed in the same manner as the method for forming the first film of Examples 1-10, The metal material was immersed in tap water at 25 ° C. for 30 seconds and washed with water to obtain the metal material for plastic working of Comparative Example 1.
In Comparative Example 2, a single film was formed by the same method as the first film formation method of Examples 11 to 19, followed by immersing the metal material in tap water at 25 ° C. for 30 seconds and washing with water. The metal material for plastic working of Comparative Example 2 was used.
Comparative Example 3 was taken out after being immersed in mineral oil heated to 40 ° C. for 10 seconds and wiped off excess mineral oil so that the amount of the mineral oil adhered (g / m ² ) was 4.0 g / m ² . The metal material for plastic working of Comparative Example 3 was used.
In Comparative Example 4, a single film was formed in the same manner as the second film forming method of Examples 2 and 12, and then the metal material was immersed in tap water at 25 ° C. for 30 seconds and washed with water. The metal material for plastic working of Example 4 was used.
Table 1 shows the adhesion amounts of the single films of Comparative Examples 1 to 4.

(1-6) Evaluation Test (1-6-1) Ball Ironing Test Evaluation of seizure resistance and lubricity was performed based on the ball ironing friction test method disclosed in the above-mentioned reference.

The evaluation test was performed by ironing (strengthening processing) using three ball-shaped molds (SUJ-2 bearing balls with a diameter of 10 mm) for the protruding side surface portion of the barrel-shaped test piece after film formation. ) In the seizure resistance evaluation of each test piece, the appearance of the latter half of the ironing process in which an increase in surface area was recognized was visually determined according to the evaluation criteria shown in FIG. 1 (A is the best). The lubricity of each test piece was evaluated according to the following evaluation criteria.
In this example, since there is no difference in the corrosion resistance before and after the plastic working (comparison of rusting conditions in the same environment), the second film after the plastic working remains and protects the first film. It was.

<Evaluation criteria for lubricity>
Lubricity was evaluated by comparing the maximum load value obtained during ironing with the range of the maximum load value based on the following evaluation criteria. The smaller the maximum load value, the better the lubricity.
A: The maximum load value is less than 38 kN.
B: The maximum load value is 38 kN or more and less than 40 kN.
C: The maximum load value is 40 kN or more and less than 42 kN.
D: The maximum load value is 42 kN or more.

Although the present invention will be described in detail with reference to specific examples, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. It is.

Claims

A first coating on the surface or surface of the metal material, and a second coating on the surface or surface of the first coating,
The second film is a surface layer,
The metal film for plastic working, wherein the second film contains a compound having a benzene ring to which at least one carboxy group is directly bonded, a salt thereof, or a peroxide thereof.