CN102011110A - Iron group metal material after black surface treatment and manufacturing method thereof - Google Patents

Abstract

The present invention provides a black surface-treated iron-based metal material formed with a black thin film excellent in corrosion resistance and sliding performance and free of chromium. Provided on the surface of the iron-based metal material are: a ferric oxide layer formed by chemical conversion treatment; a chemical conversion treatment layer formed on the ferric oxide layer containing at least One, the substance is: phosphate containing at least one element selected from zinc, tin, iron, manganese and calcium; containing titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, oxides of at least one element selected from molybdenum and tungsten; and fluorides containing at least one element selected from titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum, and tungsten; and A solid lubricating layer formed on said chemical conversion treatment layer.

Description

Iron-based metal material with black surface treatment and manufacturing method thereof

technical field

The present invention relates to an iron-based metal material with a black surface treatment and a manufacturing method thereof. Chromium-containing black film (film).

Background technique

In optical mechanical parts, measuring equipment parts, firearms, telecommunications equipment parts, motorcycle mechanical parts, automotive mechanical parts, decorations, etc., as well as mechanical devices represented by semiconductor manufacturing equipment and food manufacturing equipment For direct linkages and the like, iron-based metal materials are used. For the purpose of improving corrosion resistance and sliding performance, various surface treatments are performed on these iron-based metal materials. For applications that also require reduction of light reflectance and design performance, it is necessary to make the surface of the iron-based metal material black .

As a technique for making the surface of such an iron-based metal material black, the following proposals are proposed: for example, use of chromium plating containing chromic anhydride in a specific ratio; sodium hydroxide; fluorosilicic acid or fluorosilicide; and nitric acid or nitrate liquid, utilize electrolysis to carry out the method of black chrome plating (for example, refer to patent document 1); use contains chromium chloride; Sodium sulfite and/or potassium sulfite; ); after zinc-nickel plating, use anodic electrolysis, cathodic treatment, alternate electrolysis or anodic oxidation to make it black, and then apply a water-dispersible organic resin to obtain a black steel sheet (for example, refer to Patent Document 3); and After the phosphate chemical conversion treatment film is formed on the surface of the metal material, the phosphate chemical conversion treatment film is subjected to anodic electrolysis in a solution containing at least one of thiomolybdate ions and thiotungstate ions at pH 5 to 14 treatment, a method of forming a black precipitate thin film (for example, refer to Patent Document 4), and the like. In addition, there is also known a low-temperature electrolytic chromium plating treatment method called RAYDENT (registered trademark) treatment.

Patent Document 1: Japanese Patent Laid-Open Publication No. Sho 58-11792

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-119826

Patent Document 3: Japanese Patent Laid-Open Publication No. 2002-127302

Patent Document 4: Japanese Patent Laid-Open Publication No. Hei 11-256357

However, the method of Patent Document 1 uses hexavalent chromium, which causes inflammation of digestive organs, lungs, etc., and has carcinogenicity, teratogenicity, toxicity, etc., and has problems in terms of work safety and the environment. In addition, the chrome-plated product obtained by the method of Patent Document 1 cannot be said to have satisfactory performance in terms of sliding performance.

Although the method of Patent Document 2 does not use hexavalent chromium, since trivalent chromium is contained in the formed thin film, it cannot be said to be completely chromium-free, and there are still problems in terms of work safety and the environment. In addition, the chrome-plated product obtained by the method of Patent Document 2 cannot be said to have satisfactory performance in terms of sliding performance.

The method of Patent Document 3 requires a large-scale facility for performing electrolysis after zinc-nickel plating, and thus poses an economical problem due to its high cost.

The method of Patent Document 4, like Patent Document 3, requires large-scale equipment for electrolysis, and the obtained product cannot be said to have sufficient performance in terms of corrosion resistance.

In addition, the レイデント (registered trademark) treatment cannot be said to be completely chromium-free because chromium is contained in the formed thin film, and there are still problems in terms of work safety and the environment. In addition, since the Reident (registered trademark) treatment generally performs electrolysis at an extremely low temperature of 10° C. or lower, there are also economical problems due to power costs, waste liquid treatment costs, and the like.

Contents of the invention

Therefore, in view of the above problems, it is an object of the present invention to provide a black surface-treated iron-based metal material formed with a black film excellent in corrosion resistance and sliding properties and free of chromium. Furthermore, an object of the present invention is to provide a method for producing a black-surface-treated iron-based metal material, which can produce the black-surface-treated iron-based metal material with a relatively simple process and at low cost, without using a power supply device for electrolysis, etc. Processed ferrous metal materials.

The inventors of the present invention have carried out intensive research in order to solve the above-mentioned problems, and as a result found that: on the surface of the iron-based metal material, a layer of iron tetraoxide (Magnetite) layer, a chemical conversion treatment layer (chemical conversion treatment) ) and the order of the solid lubricating layer to set the above three layers is effective, the ferriferric oxide layer is formed by chemical conversion treatment, the chemical conversion treatment layer is composed of zinc phosphate, etc., and the solid lubricating layer is made of fluororesin etc., the present invention has been completed so far.

That is, the black surface-treated iron-based metal material of the present invention is characterized in that, on the surface of the iron-based metal material, there are: a layer of ferric oxide formed by chemical conversion treatment; a chemical conversion treatment layer formed on the surface of the iron-based metal material Formed on the ferric oxide layer, containing at least one selected from phosphate, oxide and fluoride, the phosphate contains at least one element selected from zinc, tin, iron, manganese and calcium, The oxide contains at least one element selected from titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, and the fluoride contains at least one element selected from titanium, zirconium, hafnium, indium, tin At least one element selected from , bismuth, vanadium, nickel, cerium, molybdenum and tungsten; and a solid lubricating layer formed on the chemical conversion treatment layer.

Preferably, the ferric oxide layer also contains lithium-containing iron oxide.

Preferably, the chemical conversion treatment layer contains at least one crystalline phosphate selected from zinc phosphate, zinc iron phosphate, manganese phosphate, manganese iron phosphate and zinc calcium phosphate. Furthermore, it is preferable that the chemical conversion treatment layer contains at least one amorphous compound selected from zirconium oxide, titanium oxide, zirconium fluoride, titanium fluoride, and iron phosphate. Preferably, the thickness of the ferric oxide layer is 0.1 μm˜5 μm.

Preferably, the crystal size of the crystalline phosphate contained in the chemical conversion treatment layer is 5 μm or less. Furthermore, it is preferable that the thickness of the chemical conversion treatment layer containing the amorphous compound is 0.01 μm to 3 μm.

In addition, the method for producing the black surface-treated iron-based metal material of the present invention is characterized in that it includes the step of: making the surface of the iron-based metal material with at least one selected from sodium hydroxide and potassium hydroxide. A process of contacting with an aqueous solution of an oxidizing agent to form a ferric oxide layer on the surface of the iron-based metal material; making the ferric oxide layer of the iron-based metal material contact with the iron-based metal material containing zinc, iron, manganese , calcium, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten in contact with a chemical conversion treatment liquid to form a chemical conversion on the ferroferric oxide layer a process of treating the layer; and a process of coating a solid lubricant on the chemical conversion treatment layer of the iron-based metal material to form a solid lubricant layer.

In the method for producing the black surface-treated iron-based metal material of the present invention, preferably, the aqueous solution for forming the ferric oxide layer further contains lithium hydroxide.

According to the present invention, it is possible to provide: a black surface-treated iron-based metal material formed with a black film that is excellent in corrosion resistance and sliding performance and does not contain chromium; process and a low-cost method for manufacturing the black surface-treated iron-based metal material.

Detailed ways

Hereinafter, the black surface-treated iron-based metal material and its manufacturing method of the present invention will be described in detail.

In the iron-based metal material with black surface treatment of the present invention, the surface of the iron-based metal material is provided with: a layer of ferric oxide formed by chemical conversion treatment; a layer of chemical conversion treatment formed on the layer of ferric oxide Formed, containing at least one selected from phosphate, oxide and fluoride, the phosphate contains at least one element selected from zinc, tin, iron, manganese and calcium, the oxide contains titanium, At least one element selected from zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, the fluoride containing , at least one element selected from molybdenum and tungsten; and a solid lubricating layer formed on the chemical conversion treatment layer.

The black surface-treated iron-based metal material of the present invention adopts such a layer structure, which can show a good black appearance without hindering the black color of ferric oxide. The rear skid mark part also maintains a good black appearance.

In the present invention, the iron-based metal material to be formed into a black thin film is not particularly limited, and examples include: steel materials such as cold-rolled steel sheets and hot-rolled steel sheets; Special steel such as bearing steel. Before the black surface treatment, these ferrous metal materials can be degreased according to need to make their surfaces clean. The degreasing treatment is not particularly limited, and known methods such as using a solvent degreasing agent, an aqueous degreasing agent, and an emulsion degreasing agent can be employed. In addition, the iron-based metal material after the degreasing treatment may be subjected to known pickling treatment as necessary.

Tetroxide as the first layer can be formed by a method called blackening treatment using an aqueous solution (hereinafter sometimes referred to as a blackening agent) mainly composed of at least one of sodium hydroxide and potassium hydroxide and an oxidizing agent. Specifically, the triiron (Fe ₃ O ₄ ) layer only needs to bring the surface of the iron-based metal material into contact with the blackening agent. As such a blackening agent, commercially available products can be used as they are, and examples of commercially available products include "Palbratsuku A", "Palbratsuku 3901", "Palbratsuku 3903" and "Palbratsu CA";"Stenbratsu919-gt" manufactured by Aisolite Research Institute, "Ebonoluss-52" manufactured by Meltec Co., Ltd., etc.

The method of making the surface of the iron-based metal material contact with the blackening agent is not particularly limited, and can be exemplified: spraying the blackening agent onto the surface of the iron-based metal material; immersing the iron-based metal material in the blackening agent Impregnation treatment; steam treatment using steam; and pouring treatment of pouring blackening agent on the surface of iron-based metal materials, etc.

The formation temperature of the ferric oxide layer is preferably 70°C to 170°C, more preferably 80°C to 160°C, and most preferably 90°C to 150°C. If the forming _temperature is lower than 70°C, a layer of triiron tetroxide (Fe ₃ O ₄ ) having a uniform composition, black appearance, and thickness may not be obtained. O ₄ ) may turn into ferric oxide (Hematite) (Fe ₂ O ₃ ), and a black thin film may not be obtained.

The thickness of the ferric oxide layer is preferably 0.1 μm to 5 μm, more preferably 0.2 μm to 3 μm, most preferably 0.3 μm to 2 μm. If the thickness of the triiron tetroxide layer is less than 0.1 μm, a uniform black appearance may not be obtained. On the other hand, if it is more than 5 μm, the effect is saturated, which may be economically disadvantageous.

In addition, it is also possible to introduce lithium as a cation by adding lithium hydroxide or lithium carbonate to the blackening agent. If a blackening agent that introduces lithium as a cation is used, not only ferric oxide (Fe ₃ O ₄ ), but also lithium-containing iron oxides (Li ₅ Fe ₅ O ₈ , Li ₂ Fe ₃ O ₄ , Li ₂ Fe ₃ O ₅ , LiFe ₅ O ₈ , LiFeO ₂ ). The corrosion resistance can be further improved by including the lithium-containing iron oxide in the ferric iron tetroxide layer.

The concentration of lithium in the blackening agent is, for example, 0.01% by mass to 1% by mass, preferably 0.05% by mass to 0.7% by mass, more preferably 0.1% by mass to 0.4% by mass as lithium content. If the concentration of lithium is less than 0.01% by mass, the effect of improving the corrosion resistance due to the addition of lithium may not be exhibited in some cases. On the other hand, if it exceeds 1% by mass, the effect will be saturated, which may be economically disadvantageous. In addition, sometimes It also prevents the film from turning black.

In this way, by contacting the surface of the iron-based metal material with the blackening agent, the iron in the iron-based metal material is oxidized, and a layer composed of triiron tetroxide or a layer composed of triiron tetroxide can be formed on the surface of the iron-based metal material. and lithium-containing iron oxide layer. The layer composed of the ferric iron tetroxide or the layer composed of ferric ferric oxide and lithium-containing iron oxide is black, has excellent adhesion to iron-based metal materials, and not only has the effect of improving corrosion resistance, but also has the effect of improving corrosion resistance. It plays a role in controlling the chemical reactivity when forming the chemical conversion treatment layer as the second layer described later. In addition, the triiron tetroxide layer in the present invention is formed by chemical conversion treatment, and is a layer having a uniform composition, black appearance, and thickness, which is different from an oxide film called black scale that is formed when manufacturing steel.

By making a chemical conversion treatment solution containing at least one element selected from zinc, iron, manganese, calcium, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, and as the first The chemical conversion treatment layer as the second layer can be formed by chemical reaction to precipitate the compound containing the element. The form of the thin film constituting the chemical conversion treatment layer may be crystalline or amorphous (amorphous). Usually, relying only on the ferric oxide film formed by blackening treatment, the corrosion resistance of iron-based metal materials is poor, so in the past, it was necessary to coat anti-rust oil on the iron-based metal materials after blackening treatment. However, in the present invention, since the chemical conversion treatment film is formed on the ferric oxide layer, a temporary anti-rust effect can be obtained, so it is not necessary to apply anti-rust oil.

As a specific method for forming a crystalline thin film as a chemical conversion treatment layer, phosphating treatment using an acidic aqueous solution containing phosphate ions as anions and zinc, calcium, and manganese as cations may be mentioned. Choose at least one. For the purpose of increasing the reaction rate, it is preferable to further add transition metal ions such as nickel and cobalt; oxidizing agents such as nitric acid and nitrous acid; and etching components such as fluorine ions and complex fluorine ions to the acidic aqueous solution. As the acidic aqueous solution for phosphate treatment in which the types and contents of the above-mentioned anions and cations are appropriately combined, commercially available products can be used as they are, and examples of commercially available products include: manufactured by Nippon Parker Seisei Co., Ltd. "Palbond 860", "Palbond L3020", "Palfoos M1A", "Palfoos M5", "Palbondo 880", "Palbondo SX35", "Palbondo L47" and "Fericoat 7".

Usually, at least one of the following compounds is contained in the crystalline thin film thus formed.

・Zinc phosphate (Phophait: Zn ₃ (PO ₄ ) ₂ 4H ₂ O)

Zinc iron phosphate (phosphophyllite: Zn ₂ Fe(PO ₄ ) ₂ 4H ₂ O)

・Manganese Phosphate (Permanite: Mn ₅ (PO ₃ (OH)) ₂ (PO ₄ ) ₂ 4H ₂ O)

Ferromanganese phosphate ((Mn _1-x Fe _x ) ₅ H ₂ (PO ₄ ) ₄ 4H ₂ O, in the formula, x indicates that the iron-based metal material is etched during the chemical conversion treatment, so that the iron component is contained in the film In. 0<x<1)

・Calcium zinc phosphate (CaZn ₂ (PO ₄ ) ₂ 2H ₂ O)

Among them, a crystalline thin film containing ferromanganese phosphate is preferable from the viewpoint of having a property of improving slidability.

The method of making phosphate treatment acidic aqueous solution contact with the ferric oxide layer as the first layer is not particularly limited, and can be exemplified: the phosphate treatment is sprayed on the surface of the ferric oxide layer with an acidic aqueous solution; Immersion treatment of immersing an iron-based metal material having a ferric oxide layer formed therein in an acidic aqueous solution for phosphate treatment; steam treatment using steam; and pouring an acidic aqueous solution for phosphate treatment on the surface of the ferric oxide layer watering treatment, etc.

The formation temperature of the crystalline thin film as the chemical conversion treatment layer is preferably 30°C to 120°C, more preferably 35°C to 110°C, and most preferably 40°C to 100°C. If the formation temperature is less than 30°C, the formation of the thin film may not be sufficient. On the other hand, if the formation temperature exceeds 120°C, the effect is saturated, which is often economically disadvantageous. In addition, it may cause etching during the chemical conversion reaction. Too much, and the adhesion tends to deteriorate.

Since the crystalline thin film as a chemical conversion treatment layer has unevenness due to crystallization, it is inappropriate to discuss the thickness, and it is important to focus on the crystallite size. The crystal size of the crystalline phosphate is preferably 5 μm or less, more preferably 4 μm or less, most preferably 3 μm or less. If the crystal size is larger than 5 μm, good corrosion resistance and sliding properties tend not to be obtained.

In this way, the acidic aqueous solution contains phosphate ions as anions and at least one selected from zinc, calcium and manganese as cations. If a chemical conversion treatment layer is formed on the ferroferric oxide layer, the crystal size of the crystalline phosphate can be made small, and the corrosion resistance and sliding performance can be greatly improved. The chemical conversion treatment layer contains zinc phosphate, zinc iron phosphate , manganese phosphate, manganese ferrophosphate and zinc calcium phosphate at least one crystalline phosphate. In addition, it was also confirmed that in the present invention, significantly less sludge was generated during the phosphate treatment. This is believed to be due to the chemical reactivity of the resulting film being controlled by the ferric oxide layer. Therefore, the present invention has the advantages of being able to reduce the number of troublesome sludge removal operations and reduce the amount of sludge discharged as industrial waste.

As a specific method for forming an amorphous thin film as a chemical conversion treatment layer, phosphate treatment using an acidic aqueous solution containing phosphate ions as anions and containing iron, tin, zirconium, titanium and At least one selected from hafnium is used as a cation. For the purpose of increasing the reaction rate, it is preferable to further add transition metal ions such as nickel and cobalt; oxidizing agents such as nitric acid and nitrous acid; and etching components such as fluorine ions and complex fluorine ions to the acidic aqueous solution. As the acidic aqueous solution for phosphate treatment which appropriately combines the types and contents of the above-mentioned anions and cations, commercially available products can be used as they are. Manufactured "Palfoos 1077", "Palfoos 525T" and "Palfoos K5100", etc.

Usually, at least one of the following compounds is contained in the amorphous thin film thus formed.

·Iron phosphate

·Tin phosphate

·Zirconium phosphate

·Titanium phosphate

·Hafnium Phosphate

In addition, as another method of forming an amorphous thin film as a chemical conversion treatment layer, a method using an acidic aqueous solution containing nitrate ions, sulfate ions, fluorine ions, complex fluorine ions, and At least one selected from carbonate ions is used as an anion, and at least one selected from iron, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum, and tungsten is contained as a cation. The acidic aqueous solution can be prepared by appropriately combining the types and contents of the compounds corresponding to the anions and cations, and commercially available products can also be used as they are.

The compounds contained in the thus formed amorphous thin film are oxides, sulfides and/or fluorides, representative substances of which are described below.

·Titanium oxide

·Zirconium oxide

·Hafnium Oxide

·Indium oxide

·Tin oxide

· Bismuth oxide

·Vanadium oxide

·Nickel oxide

·Ceria

·Molybdenum oxide

·Tungsten oxide

·Iron sulfide

· Zirconium fluoride

·Titanium fluoride

·Hafnium fluoride

·Indium fluoride

Among the above-mentioned compounds, it is preferable to contain any one of zirconium hydroxide, titanium hydroxide, zirconium fluoride, titanium fluoride, zirconium oxide, and titanium oxide from the viewpoint of having properties capable of improving corrosion resistance. kind of amorphous film. In addition, the amorphous thin film may contain a part containing titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum, and Compounds of at least one element selected from tungsten.

The method for making the described acidic aqueous solution contact with the ferric oxide layer as the first layer is not particularly limited, and can be exemplified: spraying the acidic aqueous solution onto the surface of the ferric oxide layer; Immersion treatment in which the iron-based metal material of the tri-iron layer is immersed in an acidic aqueous solution; steam treatment using steam; and pouring treatment in which an acidic aqueous solution is poured on the surface of the ferric oxide layer.

The formation temperature of the amorphous thin film as the chemical conversion treatment layer is usually 10°C to 100°C, preferably 15°C to 80°C, more preferably 20°C to 60°C. If the formation temperature is less than 10°C, the formation of a thin film may not be sufficient. On the other hand, if it exceeds 100°C, the effect is saturated, which is often disadvantageous in terms of economy. In addition, it may cause excessive etching during the chemical conversion treatment reaction. , and sometimes the adhesion becomes poor.

The thickness of the amorphous thin film as the chemical conversion treatment layer is preferably 0.01 μm to 3 μm, more preferably 0.03 μm to 2 μm, and most preferably 0.05 μm to 1 μm. If the thickness of the amorphous film is less than 0.01 μm, good corrosion resistance and sliding properties may not be obtained. On the other hand, if it is more than 3 μm, the effect is saturated, which is often disadvantageous in terms of economy. In addition, it may impair black color. Exterior.

A chemical conversion treatment layer composed of an amorphous thin film can be formed on the ferric oxide layer by contacting the ferric oxide layer with an acidic aqueous solution containing phosphoric acid ions as anions and containing At least one selected from , calcium and manganese as cations; or the acidic aqueous solution contains at least one selected from nitrate ions, sulfate ions, fluoride ions, complex fluoride ions and carbonate ions as anions, and contains iron, At least one selected from titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum, and tungsten is used as the cation. The chemical conversion treatment layer composed of an amorphous thin film is the same as the chemical conversion treatment layer composed of crystalline phosphate, which can improve corrosion resistance and sliding performance, and can be combined with the ferric oxide layer as the first layer and the iron oxide layer as the first layer. The solid lubricating layer of the third layer was also excellent in adhesion. In addition, since it was found that the chemical conversion treatment layer composed of an amorphous thin film has the effect of improving corrosion resistance and sliding performance even if it is a very thin film, it also has the effect of significantly reducing the dimensional change accompanying the formation of the thin film. Small pluses. In addition, it has been clarified that for the formation of the amorphous thin film, the problem of sludge adhering to the thin film at the time of forming the chemical conversion treatment layer composed of crystalline phosphate can be remarkably alleviated, and due to the accompanying chemical conversion treatment The etching reaction to the material is extremely small, so a thin film with a non-rough surface can be formed.

A solid lubricant layer as a third layer can be formed by applying a known solid lubricant and, if necessary, baking. Generally, a solid lubricant is formed by dispersing a large amount of solid lubricating fine particles in a binder solution which is formed by dissolving a binder resin in a solvent. Examples of solid lubricating fine particles include molybdenum disulfide, tungsten disulfide, silicon carbide, boron nitride, silicon nitride, zinc oxide, lead oxide, tin oxide, graphite fluoride, calcium fluoride, graphite, mica (natural Silicate minerals), fullerene (nano carbon), copper powder, nickel powder, lead powder, tin powder, silver powder, gold powder, zinc powder, indium powder, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluorinated Alkyl vinyl ether copolymer (PFA), melamine cyanuric acid (MCA: roughly 1:1 organic adduct of melamine and isocyanuric acid), polyimide powder, nylon, high-density polyethylene powder, organic molybdenum compound , fats, soaps, waxes (tallow, lithium stearate, beeswax, etc.), fatty acids, and phthalocyanines, etc. Among them, dilute solid lubricating fine particles are preferable from the viewpoint of stably obtaining good sliding performance. Molybdenum sulfide, graphite and PTFE. In addition, examples of the binder resin include polyamide-imide resin, polyimide resin, epoxy resin, furan resin, melamine resin, acrylic resin, urethane resin, and the like. Examples of the solvent include xylene, toluene, butanol, isobutanol, isopropanol, dioxane, methyl ethyl ketone, n-methyl-2-pyrrolidone, and the like. Such a solid lubricant can be directly used on the market, for example, "HMB-2" manufactured by Kawaechi Laboratories Co., Ltd. containing molybdenum disulfide; Manufactured "HMB-18"; "HMB-34" manufactured by Kawaeup Laboratories Co., Ltd., which contains molybdenum disulfide and graphite; "TC-7109BK" manufactured by Daikin Air Conditioning Co., Ltd., which contains PTFE and graphite, etc. .

The coating method of the solid lubricant can adopt a known method, and as a known method, it can be exemplified: spray coating, brush coating, roller coating, and forming a layer of ferric oxide as the first layer and a layer of ferric oxide as the second layer. A method in which the iron-based metal material of the chemical conversion treatment layer is immersed in a solid lubricant, etc. After the solid lubricant is applied, the solid lubricant layer can be formed by baking at an appropriate temperature and time if necessary.

The thickness of the solid lubricating layer is preferably 0.2 μm to 50 μm, more preferably 0.5 μm to 30 μm, most preferably 0.7 μm to 15 μm. If the thickness of the solid lubricating layer is less than 0.2 μm, good sliding properties may not be obtained in some cases. On the other hand, if it is more than 50 μm, the effect is saturated, which is often disadvantageous in terms of economy. In addition, due to the generation of a large amount of wear powder, it may affect the sliding performance. Performance is adversely affected.

Known additives such as dispersants, antifoamers, stabilizers, flame retardants, hardening accelerators, and pigments can be appropriately added to the solid lubricant within the range that does not impair the effects of the present invention. However, since the black surface-treated iron-based metal material of the present invention is characterized by good black color, these additives are limited to those that make the solid lubricant black or colorless and transparent.

A solid lubricant layer can be formed by coating a solid lubricant on the chemical conversion treatment layer and, if necessary, baking. The solid lubricating layer can endow the iron-based metal material with excellent sliding performance.

Between the steps of forming the first to third layers of the present invention, washing with water, drying, antirust oil coating, degreasing, etc. may be performed as necessary. The preferred production process in the present invention is: degreasing of iron-based metal material→water washing→formation of the first layer→water washing→formation of the second layer→water washing→drying→formation of the third layer.

In addition, before forming the first layer and/or the second layer, surface adjustment may be performed for the purpose of promoting thin film formation or the like. Especially in the case of forming a crystalline phosphate as the second layer, before forming the second layer, the effect of promoting the formation of a thin film and making the crystal size finer can be obtained by performing surface adjustment using a generally used surface modifier. As the surface conditioner, "Preparen X", "Preparen 55", "Preparen Z", "Preparen VM", "Preparen XG" and "Preparen 35" manufactured by Nippon Parker Seisei Co., Ltd. may, for example, be mentioned.

In addition, in order to improve corrosion resistance, sliding performance, etc., an intermediate coating layer may be provided between the above-mentioned second layer and third layer. The intermediate coating can be formed by applying the following aqueous solution, dispersion liquid or solvent (hereinafter sometimes referred to as coating type treatment liquid) on the chemical conversion treatment layer as the second layer, and drying it as necessary layer. In addition, the intermediate coating layer may be formed in two or more layers. The aqueous solution, dispersion or solvent contains at least one selected from, for example, metal silicates such as sodium silicate, lithium silicate, potassium silicate, calcium silicate, and aluminum silicate Salt; silicon oxides such as silicon monoxide and silica sol (silicon dioxide); chlorotri-C _1-2 alkoxysilane, glycidyl ether oxyalkyl-tri-C _1-2 alkoxysilane, di (Glycidyl ether oxyalkyl) diC _1-2 base alkoxysilane, 3-aminopropyldiethoxymethylsilane, aminoalkyl-triC _1-2 base alkoxy silane, di( Aminoalkyl) diC _1-2 yl alkoxysilane, ethylene tri-C _1-2 yl alkoxysilane, methyltrimethoxysilane, (meth)acryloyloxyalkyl-tri-C _1-2 Silane coupling agents such as base alkoxysilane, tetraethyl silicate and bis((meth)acryloxyalkyl)-diC _1-2 base alkoxysilane; ethyl polysilicate, Silicone ester compounds such as propyl polysilicate and butyl polysilicate, silicone resins; isopropyl tricapryl titanate, isopropyl tris(dioctyl pyrophosphate acyloxy) titanate, Titanium-isopropoxyoctanediol (チタニウム-i-propokysiokuchilengricollet), isopropyl (N-aminoethylaminoethyl) titanate, tetraoctyl bis(ditridecyl) Phosphoryloxy)titanate, tetrakis(2,2-dialkyloxymethyl-1-butyl)bis(ditridecyl)phosphoryloxytitanate, bis(dioctyl pyro Phosphate acyloxy)oxyacetic acid titanate (Bis (dioctyl pyrophosphoryloxy) ethylene titanate, isopropyl dimethyl Acryloyloxy isostearoyl titanate (Isopropiljimeta Acryl Isosteroid titanate), Isopropyl isostearoyl diacryloxy titanate , isopropyl tris (dioctyl phosphate acyloxy) titanate, isopropyl tris (cumyl phenyl) titanate (ISO PROPILTRIC MIL FENIL CHITANET), tetraisopropyl bis (dioctyl) titanate Phosphoric acid acyloxy) titanate, tetra(monoethylethanolate) titanium, tetra(monobutylethanolate) titanium, tetra(acetylacetonate) titanium, tetra-n-butyl titanate and other titanate coupling agents and organic titanium compounds; organic vanadium compounds such as vanadium acetylacetonate; organic nickel compounds such as nickel acetylacetonate; and organic cerium compounds such as cerium acetylacetonate.

The method of coating the coating-type treatment liquid on the chemical conversion treatment layer is not particularly limited, and examples thereof include rod coating, curtain coating, extrusion coating, roll coating, dip coating, Known methods such as spray coating, spin coating, gravure coating, and die coating (die coating).

The thickness of the intermediate coating layer is preferably 0.05 μm to 10 μm as a dry film, more preferably 0.1 μm to 5 μm, and most preferably 0.3 μm to 3 μm. If the thickness of the intermediate layer is less than 0.05 μm, the effect of improving corrosion resistance and sliding performance may not be sufficiently obtained. On the other hand, if it is more than 10 μm, the effect is saturated, which may be economically disadvantageous.

In addition, acrylic resins, urethane resins, epoxy resins, phenolic resins, polyester resins, polyimide resins, and the like may be added as optional components to the treatment liquid. The ionicity of each resin is not particularly limited, and any of anionic, cationic, and nonionic resins may be used.

In addition, in the case of forming the intermediate coating layer instead of the chemical conversion treatment layer, that is, on the surface of the iron-based metal material, a layer of ferric oxide formed by chemical conversion treatment, an intermediate coating layer, and In the case of a solid lubricating layer, although the corrosion resistance and sliding performance of the black surface-treated iron-based metal material of the present invention cannot be obtained, a good black appearance can be obtained, and the corrosion resistance and sliding performance are also excellent. Iron-based metal material with a black finish that is adequate for practical use.

Since the black surface-treated iron-based metal material of the present invention is formed with a thin film exhibiting a very good black appearance, has excellent corrosion resistance and sliding properties, and does not contain chromium, the present invention is required for composition to reduce reflection to light High efficiency, excellent appearance, improved corrosion resistance, improved sliding performance and improved rotational performance of optical mechanical parts, measuring equipment parts, firearms, telecommunications parts, motorcycle mechanical parts, automotive mechanical parts, decoration It is very useful for components such as direct linkage devices of mechanical devices represented by semiconductor manufacturing equipment and food manufacturing machinery.

In addition, since the present invention can form a black multilayer film having the above-mentioned excellent properties at a relatively simple process and at low cost without using a power supply device for electrolysis, the present invention has wide applications.

Example

The effect of the black surface-treated iron-based metal material of the present invention will be specifically described below by way of examples and comparative examples. In addition, the iron-based metal material, degreasing agent, blackening agent for film formation, chemical conversion treatment liquid and solid lubricating paint used in the examples can be arbitrarily selected from commercially available materials and reagents, and have no impact on the present invention. limited.

Outline of Manufacturing Process

Embodiments 1-10 and 17-20, comparative examples 6-7 are implemented according to the following procedures.

Alkaline degreasing → washing with water → forming the first layer → washing with water → forming the second layer → washing with water → drying → forming the third layer → baking

Embodiments 11-16 are implemented according to the following procedures.

Alkaline degreasing→Washing→Forming the first layer→Washing→Forming the second layer→Washing→Drying→Forming the middle coating layer→Drying, baking→Forming the third layer→Baking

Reference examples 1-4 are implemented according to the following procedures.

Alkaline degreasing→Water washing→Forming the first layer→Washing→Drying→Forming the middle coating layer→Drying, baking→Forming the third layer→Baking

Comparative Examples 1 to 5 were implemented according to the following procedures.

Alkaline degreasing→water washing→film formation→water washing→drying→forming solid lubricating coating film (third layer)→baking

In Comparative Example 8, a solid lubricating coating (third layer) was formed by washing with water and drying after alkali degreasing.

For each of the materials obtained in Examples and Comparative Examples, the blackness of appearance, corrosion resistance and sliding performance were evaluated by the following methods. In addition, regarding the thickness of the layers, after the third layer was formed, the thickness of each layer was measured by observing the cross-section of the film using a metal microscope. In addition, for Examples and Comparative Examples in which the crystalline thin film was formed in the second layer, the crystal size was measured with a scanning electron microscope after the second layer was formed.

Appearance (blackness) evaluation

Iron-based metal materials use cold-rolled steel sheets (abbreviated as SPC: JIS G 3141, 70×150×0.8mm, where 0.8mm is the thickness), and perform alkali degreasing before forming a thin film. Alkaline degreasing is to dilute the Faincleina (registered trademark) 4360 manufactured by Japan Parker Seisei Co., Ltd. to 2% with tap water, heat the diluted aqueous solution to 60°C, and put the cold-rolled steel plate in the heated solution Wash in water after soaking in water for 10 minutes.

In Examples 1 to 23 and Comparative Examples 1 to 7, the appearance (blackness) of the layer formed on each cold-rolled steel sheet was evaluated visually. In addition, in Examples, the first to third layers were evaluated, in Comparative Examples 1 to 5, only the solid lubricating layer was formed, and in Comparative Examples 6 and 7, the first and second layers were evaluated. commented.

The appearance (blackness) was evaluated according to the following criteria.

(evaluation standard)

○: Uniform black

△: Unevenness, pale (スケ) black

×: not black

Corrosion Resistance Evaluation

Iron-based metal materials use cold-rolled steel sheets (abbreviated as SPC: JIS G 3141, 70×150×0.8mm, where 0.8mm is the thickness), and perform alkali degreasing before forming a thin film. Alkaline degreasing is to dilute the Faincleina (registered trademark) 4360 manufactured by Japan Parker Seisei Co., Ltd. to 2% with tap water, heat the diluted aqueous solution to 60°C, and put the cold-rolled steel plate in the heated solution Wash in water after soaking in water for 10 minutes.

The surface of each of the cold-rolled steel sheets obtained in Examples and Comparative Examples was cross-cut with a sharp knife, and then sprayed with 5% by mass brine for 240 hours. After spraying, the cross-cut portion and the general surface without cross-cut were evaluated according to the following criteria.

(evaluation standard)

◎: There is no red rust on the general surface at all, and there is no swelling, peeling, etc. at the cross-cut portion

○: There is no red rust at all on the general surface, and slight swelling, peeling, etc.

△: Point-like red rust occurs on the general surface, swelling, peeling, etc.

×: Red rust is generated on the entire general surface and the entire cross section

Sliding performance evaluation

The iron-based metal material is carbon steel for mechanical structure (abbreviated as S45C: JIS G 4051, φ22×8mm, polished, processed into Ra10nm, Ry50nm), and alkali degreasing is performed before forming a thin film. Alkali degreasing is to dilute Fain Cryone (registered trademark) 4360 manufactured by Japan Parker Seisei Co., Ltd. to 2% with tap water, heat the diluted aqueous solution to 60°C, and heat the carbon steel for mechanical structure. Washed with water after soaking in the solution for 10 minutes.

Sliding properties of the carbon steel materials for machine structures obtained in Examples and Comparative Examples were evaluated using an SRV tester manufactured by Optimol Instruments. For the evaluation, a non-lubricated evaluation using no lubricating oil or the like was employed. The sliding test was carried out under the sliding test conditions shown below, and the coefficient of friction, the performance of abrading the mating material (saihand material aggressiveness), and the appearance of the sliding marks after the sliding test were evaluated.

(Sliding test conditions)

Matching material: SUJ2 steel ball (φ10mm)

Load: 15N (Hertz surface pressure (ヘルツ surface pressure): 116Kg/mm ² )

Stroke: 2mm

Rate: 5Hz

Test time: 15 minutes

Test temperature: room temperature (in the atmosphere)

The friction coefficient is the average value of the calculated and measured friction coefficients (measurement upper limit: 0.64). The property to abrade the mating material is the calculated area of the mating material sliding trace after the sliding test. In addition, the observation of the appearance of the sliding marks after the sliding test was evaluated according to the following criteria.

(evaluation standard)

◎: Uniform heavy black

○: Uniform light black

△: Although black, partly has metallic luster

×: metallic luster (exposed raw materials)

Example 1

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 148°C, and degrease the iron-based metal with alkali The material is immersed for 60 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Use titanium hydrofluoride reagent, nitric acid reagent and hydrofluoric acid reagent to prepare an acidic chemical conversion treatment solution with a titanium concentration of 2000 mg/L, a nitric acid concentration of 10000 mg/L, and a fluorine concentration of 7 mg/L as free fluorine. Then, the chemical conversion treatment liquid is heated to 50° C., and the pH is adjusted to 3.0 with an ammonia water reagent. In the adjusted chemical conversion treatment liquid, the iron-based metal material formed on the first layer is immersed for 300 seconds to form the following: Titanium oxide is the main component of the second layer.

After applying a solid lubricating paint ("HMB-18" manufactured by Kawaechi Laboratories Co., Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Bake at 130° C. for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 2

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 145°C, and degrease the iron-based metal with alkali The material is immersed for 50 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Use zircon hydrofluoric acid (zirconfurt hydrochloric acid) reagent, nitric acid reagent and hydrofluoric acid reagent to prepare an acid chemical with a concentration of zirconium of 300 mg/L, a concentration of nitric acid of 7000 mg/L, and a concentration of fluorine as free fluorine of 10 mg/L. Conversion treatment fluid. Then, the chemical conversion treatment solution is heated to 40° C., and adjusted to pH 4.2 with an ammonia water reagent. In the adjusted chemical conversion treatment solution, the iron-based metal material formed on the first layer is immersed for 180 seconds to form the following: Zirconia-based second layer.

After applying a solid lubricant paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 3

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 150°C, and degrease the iron-based metal with alkali The material is immersed for 60 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Use hafnium oxide reagent, nitric acid reagent and hydrofluoric acid reagent to prepare an acidic chemical conversion treatment solution with a hafnium concentration of 1500 mg/L, a nitric acid concentration of 6000 mg/L, and a fluorine concentration of 15 mg/L as free fluorine. Then, the chemical conversion treatment solution is heated to 45° C., and adjusted to pH 4.5 with an ammonia water reagent. In the adjusted chemical conversion treatment solution, the iron-based metal material formed on the first layer is immersed for 600 seconds to form the following: The second layer is mainly composed of hafnium oxide.

After applying a solid lubricating paint ("HMB-2" manufactured by Kawaechi Laboratories Co., Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Bake at 200°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 4

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 147°C, and degrease the iron-based metal with alkali The material is immersed for 30 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Using indium oxide reagent, nitric acid reagent and hydrofluoric acid, prepare an acidic chemical conversion treatment solution with an indium concentration of 50 mg/L, a nitric acid concentration of 8000 mg/L, and a fluorine concentration of 20 mg/L as free fluorine. Then, the chemical conversion treatment liquid is heated to 45° C., and the pH is adjusted to 3.5 with ammonia water reagent. In the adjusted chemical conversion treatment liquid, the iron-based metal material after forming the first layer is immersed for 300 seconds to form The second layer mainly composed of indium oxide.

After applying a solid lubricating paint ("HMB-18" manufactured by Kawaechi Laboratories Co., Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Bake at 130° C. for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 5

Dilute "Palbratsu A" manufactured by Nippon Parkase Seiki Co., Ltd. with tap water to a degree of 80.5% by mass, use the diluted solution as a blackening agent, heat to 135°C, and degrease the iron-based metal with alkali The material is immersed for 20 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute the calcium phosphate-based chemical conversion treatment solution ("Palbond 860" manufactured by Japan Parker Seisei Co., Ltd.) to a concentration of 6% by mass with tap water, adjust the total acidity to 21 points, and then heat to 70°C. In the final chemical conversion treatment solution, the iron-based metal material formed on the first layer was immersed for 300 seconds to form zinc-calcium phosphate (phosphatite (シヨルツアイト)) and zinc phosphate (phosphatite (ホパイト)) The second layer of principal components.

After applying a solid lubricant paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 6

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 135°C, and degrease the iron-based metal with alkali The material is immersed for 3 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute a surface conditioner for zinc phosphate treatment ("Preparen X" manufactured by Nippon Parker Seisei Co., Ltd.) to a concentration of 0.3% by mass with tap water, and place the iron after forming the first layer in the diluted surface conditioner. Immerse the metal material for 30 seconds. Then, the zinc phosphate chemical conversion treatment solution ("Parbond L3020" manufactured by Nippon Parker Seisei Co., Ltd.) was diluted to a concentration of 4.8% by mass with tap water, and 0.5% by mass of Nippon Parker Seisei Co., Ltd. was added. After additive 4813 and 1.7% by mass of additive 4856 manufactured by Japan Parker Seisei Co., Ltd., the total acidity is adjusted to 23 points, and the free acidity is adjusted to 0.9 points, and then added to the chemical conversion treatment solution heated to 45°C The accelerant 131 that the 0.042 mass % Japan Parker Seto Co., Ltd. manufactures, in the chemical conversion treatment liquid after adding accelerant, the ferrous metal material that has carried out surface adjustment is dipped for 90 seconds, forms with zinc phosphate ( The second layer mainly consists of phosphozincite (hopaito) and zinc iron phosphate (phosphophyllite).

After applying a solid lubricating paint ("HMB-2" manufactured by Kawaechi Laboratories Co., Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Bake at 200°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 7

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 147°C, and degrease the iron-based metal with alkali The material is immersed for 90 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute the ferric phosphate chemical conversion treatment solution ("Paulfos 1077" manufactured by Japan Parker Seiki Co., Ltd.) to a concentration of 5% by mass with tap water, adjust the total acidity to 10 points, adjust the acid consumption point to 0.4 points, Heating to 50° C., and immersing the iron-based metal material formed in the first layer in the heated chemical conversion treatment solution for 90 seconds to form the second layer mainly composed of iron phosphate.

After applying a solid lubricating paint ("HMB-18" manufactured by Kawaechi Laboratories Co., Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Bake at 130° C. for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 8

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 145°C, and degrease the iron-based metal with alkali The material is immersed for 30 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute the surface conditioner for manganese phosphate treatment ("Preparen 55" manufactured by Nippon Parker Seisei Co., Ltd.) with tap water to a concentration of 0.3% by mass, and add the iron after forming the first layer to the diluted surface conditioner. Immerse the metal material for 30 seconds. Then, the manganese phosphate series surface treatment reagent (" パルフェオス M1A " manufactured by Japan Parker Seiki Co., Ltd.) is diluted to a concentration of 14% by mass with tap water, the total acidity is adjusted to 50 points, and the free acidity is adjusted to 8.6 points, Adjust the acid ratio (total acidity/free acidity) to 5.8, adjust the concentration of the iron component to 1.5g/L, and then heat to 97°C. In the heated chemical conversion treatment solution, put the surface-adjusted iron The metallic material was dipped for 900 seconds to form a second layer mainly composed of manganese phosphate (Hiyu-riolite) and ferromanganese phosphate.

After applying a solid lubricant paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 9

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 142°C, and degrease the iron-based metal with alkali The material is immersed for 40 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Use tin chloride reagent and hydrochloric acid reagent to prepare an acidic chemical conversion treatment solution with a tin concentration of 300 mg/L and a chlorine concentration of 1000 mg/L. Then, the chemical conversion treatment solution is heated to 40°C, and the pH is adjusted to 4.2 with an ammonia water reagent. In the adjusted chemical conversion treatment solution, the iron-based metal material formed on the first layer is immersed for 300 seconds to form The second layer mainly composed of tin oxide.

After applying a solid lubricating paint ("HMB-18" manufactured by Kawaechi Laboratories Co., Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Bake at 130° C. for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 10

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 148°C, and degrease the iron-based metal with alkali The material is immersed for 60 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Use bismuth nitrate reagent and nitric acid reagent to prepare an acidic chemical conversion treatment solution with a bismuth concentration of 300 mg/L and a nitric acid concentration of 6000 mg/L. Then, the chemical conversion treatment liquid is heated to 50° C., and the pH is adjusted to 4.8 with an ammonia water reagent. In the adjusted chemical conversion treatment liquid, the iron-based metal material formed on the first layer is immersed for 180 seconds to form the following: Bismuth oxide is the main component of the second layer.

After applying a solid lubricant paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 11

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 132°C, and degrease the iron-based metal with alkali The material is immersed for 30 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Using hydrofluoric zircon reagent, nitric acid reagent and hydrofluoric acid reagent, prepare an acidic chemical conversion treatment solution with a concentration of zirconium of 150 mg/L, a concentration of nitric acid of 9000 mg/L, and a concentration of fluorine as free fluorine of 6 mg/L. Then, the chemical conversion treatment solution is heated to 45° C., and the pH is adjusted to 3.5 with ammonia water reagent. In the adjusted chemical conversion treatment solution, the iron-based metal material formed on the first layer is immersed for 90 seconds to form The second layer mainly consists of zirconia.

Using 3-aminopropyldiethoxymethylsilane (“D1980” manufactured by Tokyo Kasei Kogyo Co., Ltd.), a coating-type treatment solution having a silicon oxide-converted concentration of 2% by mass was prepared. Then, the coating-type treatment liquid was directly coated on the second layer of the iron-based metal material at room temperature, and kept at 150° C. for 30 minutes to form an intermediate coating layer.

After applying a solid lubricating paint ("HMB-2" manufactured by Kawaeup Laboratories Co., Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sunatsuku Co., Ltd.) , baked at 200°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 12

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 145°C, and degrease the iron-based metal with alkali The material is immersed for 75 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute the calcium phosphate-based chemical conversion treatment solution ("Palbond 860" manufactured by Japan Parker Seisei Co., Ltd.) to a concentration of 6% by mass with tap water, adjust the total acidity to 21 points, and then heat to 70°C. In the final chemical conversion treatment solution, the iron-based metal material formed on the first layer was immersed for 300 seconds to form zinc-calcium phosphate (phosphatite (シヨルツアイト)) and zinc phosphate (phosphatite (ホパイト)) The second layer of principal components.

Silica sol (Nissan Chemical Industry Co., Ltd. "Snowtex (registered trademark) N") was diluted to prepare a coating-type treatment solution having a silicon oxide-converted concentration of 5% by mass. Then, the coating-type treatment liquid was directly coated on the second layer of the iron-based metal material at room temperature, and kept at 120° C. for 20 minutes to form an intermediate coating layer.

After applying a solid lubricant coating ("HMB-18" manufactured by Kawaeup Laboratories Co., Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.) , baked at 130°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 13

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 140°C, and degrease the iron-based metal with alkali The material is immersed for 40 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute a surface conditioner for manganese phosphate treatment ("Preparen 55" manufactured by Nippon Parker Seisei Co., Ltd.) with tap water to a concentration of 0.3% by mass, and in the diluted surface conditioner, place the first layer of The ferrous metal material is dipped for 30 seconds. Then, the manganese phosphate system chemical conversion treatment solution ("Paulfos M1A" manufactured by Japan Parker Seisei Co., Ltd.) was diluted to a concentration of 14% by mass with tap water, the total acidity was adjusted to 50 points, and the free acidity was adjusted to 8.6 points , adjust the acid ratio (total acidity/free acidity) to 5.8, adjust the concentration of iron components to 1.5g/L, and then heat to 98°C. In the heated chemical conversion treatment solution, the surface-adjusted iron The metallic material was dipped for 600 seconds to form a second layer mainly composed of manganese phosphate (Hiyu-riolite) and ferromanganese phosphate.

Using ethyl polysilicate, methyltrimethoxysilane, and tetraethylsilicate (“SB-4611” manufactured by Tama Chemical Industry Co., Ltd.), a coating with a concentration of 2% by mass in terms of silicon oxide was prepared. type treatment fluid. Then, the coating-type treatment liquid was directly coated on the second layer of the iron-based metal material at room temperature, and kept at 110° C. for 15 minutes to form an intermediate coating layer.

After applying a solid lubricating paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 14

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 147°C, and degrease the iron-based metal with alkali The material is immersed for 30 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute the ferric phosphate chemical conversion treatment solution ("Paulfos 1077" manufactured by Japan Parker Seiki Co., Ltd.) to a concentration of 5% by mass with tap water, adjust the total acidity to 10 points, adjust the acid consumption point to 0.4 points, After heating to 55°C, the iron-based metal material formed on the first layer was immersed in the heated chemical conversion treatment solution for 75 seconds to form the second layer mainly composed of iron phosphate.

Titanium-isopropoxy octane glycol ("TOG" manufactured by Nippon Soda Co., Ltd.) was used to prepare a coating-type treatment liquid having a concentration of 2% by mass in terms of titanium oxide. Then, the coating-type treatment liquid was directly coated on the second layer of the iron-based metal material at room temperature, and kept at 180° C. for 30 minutes to form an intermediate coating layer.

After applying a solid lubricating paint ("HMB-2" manufactured by Kawaeup Laboratories Co., Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sunatsuku Co., Ltd.) , baked at 200°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 15

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 147°C, and degrease the iron-based metal with alkali The material is immersed for 45 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Using hydrofluoric zircon reagent, nitric acid reagent and hydrofluoric acid reagent, prepare an acidic chemical conversion treatment solution with a concentration of zirconium of 200 mg/L, a concentration of nitric acid of 9000 mg/L, and a concentration of fluorine as free fluorine of 13 mg/L. Then, the chemical conversion treatment liquid is heated to 43° C., and the pH is adjusted to 4.0 with an ammonia water reagent. In the adjusted chemical conversion treatment liquid, the iron-based metal material formed on the first layer is immersed for 120 seconds to form The second layer mainly consists of zirconia.

Using ethyl polysilicate, methyltrimethoxysilane, and tetraethylsilicate ("SB-4611" manufactured by Tama Chemical Industry Co., Ltd.), a coating with a concentration of 3% by mass in terms of silicon oxide was prepared. type treatment fluid. Then, the coating-type treatment liquid was directly coated on the second layer of the iron-based metal material at room temperature, and kept at 130° C. for 30 minutes to form an intermediate coating layer.

After applying a solid lubricating paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 16

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 143°C, and degrease the iron-based metal with alkali The material is immersed for 35 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute a surface conditioner for zinc phosphate treatment ("Preparen Z" manufactured by Nippon Parker Seisei Co., Ltd.) to a concentration of 0.1% by mass with tap water, and in the diluted surface conditioner, the The ferrous metal material is dipped for 30 seconds. Then, the zinc phosphate chemical conversion treatment solution ("Parbond L3020" manufactured by Nippon Parker Seisei Co., Ltd.) was diluted to a concentration of 4.8% by mass with tap water, and 0.5% by mass of Nippon Parker Seisei Co., Ltd. was added. Additive 4813, 1.7% by mass of additive 4856 made by Japan Parker Seisei Co., Ltd., adjust the total acidity to 23 points, adjust the free acidity to 0.9 points, and then heat to 40 ° C. After the heating, the chemical conversion treatment In the solution, add 0.042% by mass of accelerator 131 manufactured by Japan Parker Seisei Co., Ltd., and in the chemical conversion treatment solution after adding the accelerator, immerse the iron-based metal material with the surface adjustment for 120 seconds to form the following: The second layer mainly consists of zinc phosphate (hopaito) and zinc iron phosphate (phosphophyllite).

Silica sol ("Snowtex (registered trademark) N" manufactured by Nissan Chemical Industries, Ltd.) was diluted to prepare a coating-type treatment solution having a SiO ₂ concentration of 3% by mass. Then, the coating-type treatment liquid was directly coated on the second layer of the iron-based metal material at room temperature, and kept at 120° C. for 20 minutes to form a first intermediate coating layer.

Using 3-aminopropyldiethoxymethylsilane (“D1980” manufactured by Tokyo Kasei Kogyo Co., Ltd.), a coating-type treatment solution having a silicon oxide-converted concentration of 1% by mass was prepared. Then, the coating-type treatment liquid was directly coated on the first intermediate coating layer of the iron-based metal material at room temperature, and kept at 150° C. for 30 minutes to form a second intermediate coating layer.

Using a coating gun (low-pressure spray gun "MGB40" manufactured by Asahi Sanatsuku Co., Ltd.), apply a solid lubricant paint ("HMB-2" manufactured by Kawahip Laboratories Co., Ltd.) on the second intermediate coating layer of iron-based metal materials ), bake at 200°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 17

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, add 15 g/L of lithium hydroxide monohydrate to it, and stir well to dissolve the lithium hydroxide monohydrate. Use the diluted solution in which lithium hydroxide monohydrate is dissolved as a blackening agent. After heating the blackening agent to 147°C, immerse the iron-based metal material after alkali degreasing treatment for 60 minutes. On the surface of the iron-based metal material, a first layer mainly composed of ferric iron tetroxide and containing lithium-containing iron oxide is formed.

Using hydrofluoric zircon reagent, nitric acid reagent and hydrofluoric acid reagent, prepare an acidic chemical conversion treatment solution with a concentration of zirconium of 120 mg/L, a concentration of nitric acid of 8000 mg/L, and a concentration of fluorine as free fluorine of 10 mg/L. Then, the chemical conversion treatment solution is heated to 52° C., and the pH is adjusted to 3.9 with an ammonia water reagent. In the adjusted chemical conversion treatment solution, the iron-based metal material formed on the first layer is immersed for 900 seconds to form the following: Zirconia-based second layer.

After applying a solid lubricating paint ("HMB-18" manufactured by Kawaechi Laboratories Co., Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Bake at 130° C. for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 18

Dilute "Palbratsu A" manufactured by Japan Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, add 12 g/L lithium hydroxide monohydrate therein, stir well to dissolve the lithium hydroxide monohydrate, and put The diluted solution in which lithium hydroxide monohydrate is dissolved is used as a blackening agent. After heating the blackening agent to 147°C, the iron-based metal material after the alkali degreasing treatment is immersed for 40 minutes. On the surface of the iron-based metal material is formed a first layer mainly composed of ferric iron tetroxide and containing lithium-containing iron oxide.

Dilute a surface conditioner for manganese phosphate treatment ("Preparen VM" manufactured by Nippon Parker Seisei Co., Ltd.) to a concentration of 0.5% by mass with tap water, and in the diluted surface conditioner, place the first layer of The ferrous metal material is dipped for 45 seconds. Then, the manganese phosphate system chemical conversion treatment solution ("Paulfos M5" manufactured by Japan Parker Seisei Co., Ltd.) was diluted to a concentration of 11% by mass with tap water, the total acidity was adjusted to 8 points, and the free acidity was adjusted to 1.3 points , adjust the acid ratio (total acidity/free acidity) to 6.2, use accelerator 131 manufactured by Japan Parker Seisei Co., Ltd., and adjust the concentration of the accelerator to 2.5 points, then heat to 85 ° C, after heating, the chemical In the conversion treatment solution, the surface-adjusted iron-based metal material was immersed for 600 seconds to form a second layer mainly composed of manganese phosphate (Hiyu-riolite) and ferromanganese phosphate.

After applying a solid lubricant paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 19

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 150°C, and degrease the iron-based metal with alkali The material is immersed for 70 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Use sodium molybdate reagent and sulfuric acid reagent to prepare an acidic chemical conversion treatment solution with a molybdenum concentration of 8000mg/L and a sulfuric acid concentration of 10000mg/L. Then, the chemical conversion treatment liquid is heated to 60° C., and the pH is adjusted to 2.9 with an ammonia water reagent. In the adjusted chemical conversion treatment liquid, the iron-based metal material formed on the first layer is immersed for 180 seconds to form The second layer mainly composed of molybdenum oxide.

After applying a solid lubricating paint ("HMB-18" manufactured by Kawaechi Laboratories Co., Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Bake at 130° C. for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Example 20

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat the blackening agent to 147°C, and then perform alkali degreasing treatment After immersing the iron-based metal material for 30 minutes, a first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Use sodium tungstate reagent, phosphoric acid reagent and sulfuric acid reagent to prepare an acidic chemical conversion treatment solution with a tungsten concentration of 15000mg/L, a phosphoric acid concentration of 10000mg/L and a sulfuric acid concentration of 1000mg/L. Then, the chemical conversion treatment liquid is adjusted to pH 1.0 with sodium hydroxide reagent, and in the adjusted chemical conversion treatment liquid at normal temperature, the iron-based metal material after forming the first layer is immersed for 100 seconds to form a oxidized The second layer is mainly composed of tungsten.

After applying a solid lubricant paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the second layer of the iron-based metal material using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Reference example 1

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 145°C, and degrease the iron-based metal with alkali The material is immersed for 75 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Add 300 parts by mass of deionized water and 2 parts by mass of anionic reactive surfactant in the reactor, stir with a homogenizer (ホモミキサ 1), and simultaneously add 50 parts by mass of deionized water and The mixture of the potassium persulfate of 1 mass part; And the deionized water of 287 mass parts, the reactive emulsifier of 4 mass parts, the methyl methacrylate of 60 mass parts, the styrene of 158 mass parts, the 2 -A mixture of ethylhexyl acrylate, 4.5 parts by mass of methacrylic acid, 4.5 parts by mass of 2-hydroxyethyl methacrylate, and 45 parts by mass of glycidyl methacrylate to obtain a water-dispersible acrylic resin. Using a vanadium acetylacetonate reagent, the concentration of vanadium was 5000 mg/L, and the water-dispersible acrylic resin was 2000 mg/L to prepare a coating type treatment liquid. Then, the coating-type treatment liquid was directly coated on the first layer of the iron-based metal material at room temperature, and then dried at 100° C. for 15 minutes to form an intermediate coating layer.

After applying a solid lubricant coating ("HMB-18" manufactured by Kawaeup Laboratories Co., Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.) , baked at 130°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Reference example 2

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 150°C, and degrease the iron-based metal with alkali The material is immersed for 65 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Add 100 parts by mass of polyester polyol with a number average molecular weight of 5000, 5 parts by mass of 2,2-dimethyl-1,3- Propylene glycol, 20 mass parts of 2,2-dimethylolpropionic acid, 100 mass parts of 4,4-cyclohexylmethane diisocyanate and 100 mass parts of N-methyl-2-pyrrolidone are reacted to obtain A urethane prepolymer having a free isocyanato group (isocyanato group) content of 5% relative to the non-volatile components. Then, add 16 mass parts of 1,4-butanediamine and 10 mass parts of triethylamine into 500 mass parts of deionized water, and stir with a homogenizer while adding the urethane prepolymer Emulsify and disperse, and finally add deionized water to prepare a water-dispersible urethane resin with a non-volatile content of 25% by mass. Using the nickel acetylacetonate reagent, the nickel concentration was 7000 mg/L, and the water-dispersible urethane resin was 3000 mg/L to prepare a coating type treatment liquid. Then, the coating-type treatment liquid was directly coated on the first layer of the iron-based metal material at room temperature, and then dried at 150° C. for 20 minutes to form an intermediate coating layer.

After applying a solid lubricating paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Reference example 3

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 145°C, and degrease the iron-based metal with alkali The material is immersed for 70 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Add 300 mass parts of deionized water and 2 mass parts of anionic reactive surfactants in the reactor, stir with a homogenizer, and add 50 mass parts of deionized water and 1 mass part of The mixture of potassium persulfate; and the deionized water of 287 mass parts, the reactive emulsifier of 4 mass parts, the methyl methacrylate of 60 mass parts, the styrene of 158 mass parts, the 2-ethylhexyl of 18 mass parts A mixture of acrylate, 4.5 parts by mass of methacrylic acid, 4.5 parts by mass of 2-hydroxyethyl methacrylate, and 45 parts by mass of glycidyl methacrylate gave a water-dispersible acrylic resin. Using a cerium acetylacetonate reagent, the concentration of cerium was 8500 mg/L, and the water-dispersible acrylic resin was 3000 mg/L to prepare a coating type treatment liquid. Then, the coating-type treatment liquid was directly coated on the first layer of the iron-based metal material at room temperature, and then dried at 130° C. for 30 minutes to form an intermediate coating layer.

After applying a solid lubricating paint ("HMB-2" manufactured by Kawaeup Laboratories Co., Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sunatsuku Co., Ltd.) , baked at 200°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Reference example 4

Dilute "Palbratsu A" manufactured by Nippon Parker Seisei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 147°C, and degrease the iron-based metal with alkali The material is immersed for 30 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Using ethyl polysilicate, methyltrimethoxysilane, and tetraethylsilicate ("SB-4611" manufactured by Tama Chemical Industry Co., Ltd.), a coating type with a concentration of 4% by mass in terms of silicon oxide was prepared. Treatment solution. Then, the coating type treatment solution was directly coated on the first layer of the iron-based metal material at room temperature, and kept at 110° C. for 15 minutes to form an intermediate coating layer.

After applying a solid lubricant coating ("HMB-18" manufactured by Kawaeup Laboratories Co., Ltd.) on the intermediate coating layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.) , baked at 130°C for 1 hour to form the third layer. The main components and layer thickness of each layer are shown in Table 1, and the evaluation results are shown in Table 3.

Comparative example 1

According to the method of the examples in Patent Document 2 (Japanese Patent Laid-Open Publication No. 2007-119826), a black chrome-plated thin film is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

After applying a solid lubricant coating ("TC-7109BK" manufactured by Daikin Industries, Ltd.) to the black chrome-plated thin film of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form a solid lubricating layer. The main components and layer thickness of each layer are shown in Table 2, and the evaluation results are shown in Table 4.

Comparative example 2

A low-temperature electrolytic chromium plating treatment called Reident (registered trademark) treatment is applied to the iron-based metal material after the alkali degreasing treatment to form a black chromium film on the surface.

After applying a solid lubricant paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) to a black chrome thin film made of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form a solid lubricating layer. The main components and layer thickness of each layer are shown in Table 2, and the evaluation results are shown in Table 4.

Comparative example 3

Dilute "Palbratsu A" manufactured by Nippon Parkase Sei Co., Ltd. with tap water to a concentration of 80.5% by mass, use the diluted solution as a blackening agent, heat to 147°C, and degrease the iron-based metal with alkali The material is immersed for 25 minutes, and the first layer mainly composed of ferric iron tetroxide is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

After applying a solid lubricant paint ("TC-7109BK" manufactured by Daikin Industries, Ltd.) on the first layer of iron-based metal materials using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.), Keep at 100°C for 15 minutes, then bake at 280°C for 1 hour to form a solid lubricating layer. The main components and layer thickness of each layer are shown in Table 2, and the evaluation results are shown in Table 4.

Comparative example 4

Using hydrofluoric zircon reagent, nitric acid reagent and hydrofluoric acid reagent, prepare an acidic chemical conversion treatment solution with a concentration of zirconium of 250 mg/L, a concentration of nitric acid of 5000 mg/L, and a concentration of fluorine as free fluorine of 7 mg/L. Then, heat the chemical conversion treatment solution to 40°C and adjust the pH to 4.3 with ammonia water reagent. In the adjusted chemical conversion treatment solution, immerse the iron-based metal material after the alkali degreasing treatment for 180 seconds to form an oxidized Zirconium-based film.

Using a coating gun (low-pressure spray gun "MGB40" manufactured by Asahi Sanatsuku Co., Ltd.), a solid lubricant coating ("TC-7109BK manufactured by Daikin Industries, Ltd. ”), keep at 100°C for 15 minutes, and then bake at 280°C for 1 hour to form a solid lubricating layer. The main components and layer thickness of each layer are shown in Table 2, and the evaluation results are shown in Table 4.

Comparative Example 5

Dilute a surface conditioner for manganese phosphate treatment ("Preparen VM" manufactured by Nippon Parker Seisei Co., Ltd.) to a concentration of 0.3% by mass with tap water, and add iron after alkali degreasing treatment to the diluted surface conditioner. Immerse the metal material for 30 seconds. Then, the manganese phosphate system chemical conversion treatment solution ("Paulfos M1A" manufactured by Japan Parker Seisei Co., Ltd.) was diluted to a concentration of 14% by mass with tap water, the total acidity was adjusted to 50 points, and the free acidity was adjusted to 8.6 points , adjust the acid ratio (total acidity/free acidity) to 5.8, adjust the concentration of the iron component to 1.5g/L, and then heat to 98°C. In the heated chemical conversion treatment liquid, the surface-adjusted The iron-based metal material was immersed for 900 seconds to form a thin film mainly composed of manganese phosphate (Permanite) and ferromanganese phosphate.

Using a coating gun (low-pressure spray gun "MGB40" manufactured by Asahi Sanatsuku Co., Ltd.), a solid lubricant coating (manufactured by Daikin Industries, Ltd. "TC-7109BK"), keep at 100°C for 15 minutes, and then bake at 280°C for 1 hour to form a solid lubricating layer. The main components and layer thickness of each layer are shown in Table 2, and the evaluation results are shown in Table 4.

Comparative example 6

According to the method of the embodiment of Patent Document 2 (Japanese Patent Laid-Open Publication No. 2007-119826), a black chrome-plated film is formed on the surface of the iron-based metal material after the alkali degreasing treatment.

Dilute a surface conditioner for manganese phosphate treatment ("Preparen 55" manufactured by Nippon Parker Seisei Co., Ltd.) with tap water to a concentration of 0.3% by mass, and in the diluted surface conditioner, the black chrome-plated film was formed The ferrous metal material is dipped for 30 seconds. Then, the manganese phosphate system chemical conversion treatment solution ("Paulfos M1A" manufactured by Japan Parker Seisei Co., Ltd.) was diluted to a concentration of 14% by mass with tap water, the total acidity was adjusted to 50 points, and the free acidity was adjusted to 8.6 points , adjust the acid ratio (total acidity/free acidity) to 5.8, adjust the concentration of the iron component to 1.5g/L, and then heat to 98°C. In the heated chemical conversion treatment liquid, the surface-adjusted The iron-based metal material was immersed for 900 seconds to form a thin film mainly composed of manganese phosphate (Permanite) and ferromanganese phosphate.

Using a coating gun (low-pressure spray gun "MGB40" manufactured by Asahi Sanatsuku Co., Ltd.), a solid lubricant coating (manufactured by Daikin Industries, Ltd. "TC-7109BK"), keep at 100°C for 15 minutes, and then bake at 280°C for 1 hour to form a solid lubricating layer. The main components and layer thickness of each layer are shown in Table 2, and the evaluation results are shown in Table 4.

Comparative Example 7

A low-temperature electrolytic chromium plating treatment called Reident (registered trademark) treatment is applied to the iron-based metal material after the alkali degreasing treatment to form a black chromium film on the surface.

Dilute a surface conditioner for manganese phosphate treatment ("Preparen 55" manufactured by Nippon Parker Seisei Co., Ltd.) with tap water to a concentration of 0.3% by mass, and in the diluted surface conditioner, the black chromium film formed The ferrous metal material is dipped for 30 seconds. Then, the manganese phosphate system chemical conversion treatment solution ("Paulfos M1A" manufactured by Japan Parker Seisei Co., Ltd.) was diluted to a concentration of 14% by mass with tap water, the total acidity was adjusted to 50 points, and the free acidity was adjusted to 8.6 points , adjust the acid ratio (total acidity/free acidity) to 5.8, adjust the concentration of iron components to 1.5g/L, and then heat to 98°C. In the heated chemical conversion treatment solution, the surface-adjusted iron The metallic material was dipped for 900 seconds to form a thin film mainly composed of manganese phosphate (Hiyu-riolite) and ferromanganese phosphate.

Using a coating gun (low-pressure spray gun "MGB40" manufactured by Asahi Sanatsuku Co., Ltd.), a solid lubricant coating (manufactured by Daikin Industries, Ltd. "TC-7109BK"), keep at 100°C for 15 minutes, and then bake at 280°C for 1 hour to form a solid lubricating layer. The main components and layer thickness of each layer are shown in Table 2, and the evaluation results are shown in Table 4.

Comparative example 8

Apply a solid lubricant coating ("TC-7109BK" manufactured by Daikin Industries, Ltd.) to the surface of the ferrous metal material after alkali degreasing treatment using a coating gun ("MGB40" low-pressure spray gun manufactured by Asahi Sanatsuku Co., Ltd.) Finally, keep it at 100°C for 15 minutes, and then bake it at 280°C for 1 hour to form a solid lubricating layer. The main components and layer thickness of each layer are shown in Table 2, and the evaluation results are shown in Table 4.

Table 1

*1: In the case of forming a crystalline thin film on the second layer, the crystal size is indicated.

*2: Crystal size

Table 2

Note) Since it was not clearly confirmed that it is a crystalline thin film, the crystal size cannot be determined.

*1: In the case of forming a crystalline thin film on the second layer, the crystal size is indicated.

*2: Crystal size

table 3

Table 4

From Table 3 and Table 4, it is clear that in the examples, the first layer has a good and uniform black appearance, and the second layer and the third layer also maintain a good and uniform black appearance. On the other hand, Comparative Examples 1 to 3 had a good black film. In Comparative Example 4, Comparative Example 5, and Comparative Example 8, no black thin film was obtained. In Comparative Example 6 and Comparative Example 7, the appearance that the black thin film obtained in the formation of the first layer was partially peeled due to the formation of the second layer to form spots was observed.

It is clear from Table 3 and Table 4 that good corrosion resistance can be obtained in all examples. On the other hand, in Comparative Example 1, good corrosion resistance was obtained, but the other Comparative Examples were significantly inferior in corrosion resistance compared to Examples.

It is clear from Table 3 and Table 4 that in the examples, good results were obtained in all items such as the coefficient of friction, the performance of abrading the mating material, and the observation of the appearance of sliding marks. For the coefficient of friction, the coefficient of friction is stable from the beginning to the end of the test, and there is no fluctuation up and down. With respect to the performance of wearing the mating material, the slip mark area of the mating material is very small, giving good results. Regarding the observation of the appearance of the sliding marks, after the sliding test, the sliding marks had a uniform black color. On the other hand, in the comparative example, it was clearly inferior to the example.

From the above results, it can be clearly seen that compared with the prior art, the black surface-treated iron-based metal material obtained by the present invention can obtain excellent corrosion resistance and sliding performance.

Claims (9)

1. a Ferrious material material of handling through black surface is characterized in that,

The surface of described Ferrious material material is provided with: magnetite layer, handle formation by chemical conversion; Layer is handled in chemical conversion, on described magnetite layer, form, contain from phosphoric acid salt, oxide compound and fluorochemical, select at least a, described phosphoric acid salt contains at least a element of selecting from zinc, tin, iron, manganese and calcium, described oxide compound contains at least a element of selecting from titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, described fluorochemical contains at least a element of selecting from titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten; And solid lubricant layer, handle formation on the layer in described chemical conversion.

2. the Ferrious material material of handling through black surface according to claim 1 is characterized in that described magnetite layer also contains the ferriferous oxide of lithium.

3. the Ferrious material material of handling through black surface according to claim 1 and 2, it is characterized in that described chemical conversion is handled layer and contain at least a crystallinity phosphoric acid salt of selecting from zinc phosphate, zinc iron phosphate, manganous phosphate, iron manganese phosphate and calcium zinc orthophosphate activated by thallium.

4. the Ferrious material material of handling through black surface according to claim 1 and 2 is characterized in that, described chemical conversion is handled layer and contain at least a amorphous compound of selecting from zirconium white, titanium oxide, Zirconium tetrafluoride, titanium fluoride and tertiary iron phosphate.

5. the Ferrious material material of handling through black surface according to claim 1 and 2 is characterized in that the thickness of described magnetite layer is 0.1 μ m～5 μ m.

6. the Ferrious material material of handling through black surface according to claim 3 is characterized in that handling the phosphatic crystal size of described crystallinity that contains in the layer in described chemical conversion is below the 5 μ m.

7. the Ferrious material material of handling through black surface according to claim 4 is characterized in that the thickness that layer is handled in described chemical conversion is 0.01 μ m～3 μ m.

8. the manufacture method of a Ferrious material material of handling through black surface is characterized in that the operation that comprises has:

The surface that makes described Ferrious material material contacts with the aqueous solution that contains at least a and oxygenant of selecting from sodium hydroxide and potassium hydroxide, forms the operation of magnetite layer on the surface of described Ferrious material material;

The described magnetite layer of described Ferrious material material is contacted with the chemical conversion treatment solution that contains at least a element of selecting from zinc, iron, manganese, calcium, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, on described magnetite layer, form the operation that layer is handled in chemical conversion; And

Applying solid lubricant on the layer is handled in described chemical conversion at described Ferrious material material, forms the operation of solid lubricant layer.

9. the manufacture method of the Ferrious material material of handling through black surface according to claim 8 is characterized in that the described aqueous solution that is used to form described magnetite layer also contains lithium hydroxide.