JP2011058032A - Surface-treated black ferrous metal material and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface-treated black ferrous metal material on which a chromium-free black coating film is formed, wherein that the black coating film is excellent in corrosion resistance and slidability. <P>SOLUTION: The surface-treated black ferrous metal material has, on a surface of a ferrous metal material; a magnetite layer formed by a chemical conversion treatment; a chemical conversion treatment layer formed on the magnetite layer; and a solid lubricating layer formed on the chemical conversion treatment layer, wherein the chemical conversion treatment layer contains at least one chosen from a phosphate containing at least one element chosen from zinc, tin, iron, manganese and calcium, an oxide containing at least one element chosen from titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten and a fluoride containing at least one element chosen from titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a black surface-treated iron-based metal material having a black coating that is excellent in corrosion resistance and slidability and does not contain chromium on the surface of an iron-based metal material, and a method for producing the same.

  Optical machine parts, measuring machine parts, firearms, telecommunications parts, machine parts for motorcycles, machine parts for automobiles, decorations, and linear motion devices for equipment such as semiconductor production equipment and food production equipment For example, ferrous metal materials are used. These iron-based metallic materials have been subjected to various surface treatments for the purpose of improving corrosion resistance and slidability, but the surface is blackened in applications that require low light reflectivity and design. It is necessary to do.

  As a technique for blackening the surface of such an iron-based metal material, for example, a chromium plating solution containing chromic anhydride, sodium hydroxide, silicofluoric acid or silicofluoride, and nitric acid or nitrate in a specific ratio is used. A method of performing black chrome plating by electrolysis (for example, see Patent Document 1), black by electrolysis using a chromium plating solution containing chromium chloride, sodium sulfite and / or potassium sulfite, and potassium iodide. A method of applying chromium plating (for example, see Patent Document 2), after zinc-nickel plating, blackening by anodic electrolysis, cathodic treatment, alternating electrolysis or anodizing, and then applying a water-dispersible organic resin, A method of obtaining (for example, see Patent Document 3), forming a phosphate chemical conversion film on the surface of a metal material, and then thiomolybdate ion A method for forming a black deposit film by subjecting a phosphate chemical film to anodic electrolysis in a solution containing at least one kind of thiotungstate ion and having a pH of 5 to 14 (for example, see Patent Document 4) Has been proposed. Furthermore, a low-temperature electrolytic chrome plating method called Raydent (registered trademark) treatment is also known.

JP 58-11792 A JP 2007-11826 Gazette JP 2002-127302 A JP-A-11-256357

However, the method of Patent Document 1 uses hexavalent chromium that causes inflammation of the digestive organs, lungs, and the like, and has carcinogenicity, teratogenicity, toxicity, etc., and there are concerns about environmental problems in terms of work safety. The Furthermore, it cannot be said that the chrome-plated product obtained by the method of Patent Document 1 has satisfactory performance with respect to slidability.
Although the method of Patent Document 2 does not use hexavalent chromium, it cannot be said that it is completely chromium-free because the film to be formed contains trivalent chromium. Still concerned. Furthermore, it cannot be said that the chrome-plated product obtained by the method of Patent Document 2 has satisfactory performance with respect to slidability.
The method of Patent Document 3 requires a large-scale facility for performing electrolysis after zinc-nickel plating, which causes an economic problem due to high costs.
Similarly to Patent Document 3, the method of Patent Document 4 requires a large facility for performing electrolysis, and the obtained product cannot be said to have sufficient performance with respect to corrosion resistance.
In addition, since the RAYDENT (registered trademark) treatment contains chromium in the formed film, it cannot be said that it is completely chromium-free, and there are still concerns about environmental problems in terms of work safety. In addition, since Raydent (registered trademark) treatment is usually carried out at an extremely low temperature of 10 ° C. or less, there is an economic problem due to power costs, waste liquid treatment costs, and the like.

  Accordingly, the present invention has been made in view of the above-described problems, and an object thereof is to provide a black surface-treated iron-based metal material having a black film that is excellent in corrosion resistance and slidability and does not contain chromium. And Another object of the present invention is to provide a method for producing such a black surface-treated iron-based metal material at a low cost in a relatively simple process without using a power supply facility for electrolysis. To do.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a magnetite layer formed by chemical conversion treatment on the surface of the iron-based metal material, a chemical conversion treatment layer made of zinc phosphate, etc., a fluororesin, etc. It has been found that it is effective to provide a solid lubricating layer composed of the above in this order, and the present invention has been completed.

That is, the black surface-treated iron-based metal material of the present invention is formed on the surface of the iron-based metal material by a chemical conversion treatment, and is formed on the magnetite layer, and is selected from zinc, tin, iron, manganese, and calcium. An oxide containing at least one element selected from the group consisting of phosphate, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, and titanium, zirconium, A chemical conversion treatment layer containing at least one selected from fluorides containing at least one element selected from hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, and formed on the chemical conversion treatment layer Specially provided solid lubrication layer. To.
The magnetite layer preferably further contains a lithium-containing iron oxide.
The chemical conversion treatment layer preferably contains at least one crystalline phosphate selected from zinc phosphate, zinc iron phosphate, manganese phosphate, manganese iron phosphate, and zinc calcium phosphate. The chemical conversion treatment layer preferably contains at least one amorphous compound selected from zirconium oxide, titanium oxide, zirconium fluoride, titanium fluoride, and iron phosphate.
The magnetite layer preferably has a thickness of 0.1 μm to 5 μm.
The crystal size of the crystalline phosphate contained in the chemical conversion treatment layer is preferably 5 μm or less. Moreover, it is preferable that the thickness of the said chemical conversion treatment layer containing an amorphous compound is 0.01 micrometer-3 micrometers.

Further, in the method for producing a black surface-treated iron-based metal material of the present invention, the surface of the iron-based metal material is brought into contact with an aqueous solution containing at least one selected from sodium hydroxide and potassium hydroxide and an oxidizing agent, A step of forming a magnetite layer on the surface of the iron-based metal material; and a magnetite layer of the iron-based metal material, zinc, iron, manganese, calcium, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, Contacting with a chemical conversion treatment solution containing at least one element selected from cerium, molybdenum, and tungsten to form a chemical conversion treatment layer on the magnetite layer; and a solid lubricant on the chemical conversion treatment layer of the iron-based metal material And a step of forming a solid lubricating layer.
In the method for producing a black surface-treated iron-based metal material of the present invention, the aqueous solution used for forming the magnetite layer preferably further contains lithium hydroxide.

  According to the present invention, a black surface-treated iron-based metal material that is excellent in corrosion resistance and slidability and has a black coating containing no chromium, and a power supply facility for electrolysis of the black surface-treated iron-based metal material are used. In addition, it is possible to provide a method of manufacturing at a low cost by a relatively simple process.

Hereinafter, the black surface-treated iron-based metal material of the present invention and the manufacturing method thereof will be described in detail.
The black surface-treated iron-based metal material of the present invention is formed on the surface of the iron-based metal material by a chemical conversion treatment, and is formed on the magnetite layer, and at least selected from zinc, tin, iron, manganese and calcium. Phosphate containing one element, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and oxide containing at least one element selected from titanium and zirconium, hafnium, A conversion treatment layer containing at least one selected from fluorides containing at least one element selected from indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, and formed on the conversion treatment layer And a solid lubricating layer.
By adopting such a layer structure, the black surface-treated iron-based metal material of the present invention exhibits a good black appearance without hindering the black color of magnetite, and also has excellent corrosion resistance and slidability. A good black appearance can be maintained even in the sliding trace portion after the dynamic test.

  In the present invention, the iron-based metallic material that is a target for forming a black film is not particularly limited. For example, steel materials such as cold-rolled steel sheets and hot-rolled steel sheets; steel bars, section steels, steel strips, steel pipes, wires, Special-purpose steels such as cast forgings and bearing steels are listed. Prior to the black surface treatment, these iron-based metal materials may be subjected to a degreasing treatment as necessary to clean the surface. The degreasing treatment is not particularly limited, and a known method using a solvent-based degreasing agent, an aqueous degreasing agent, an emulsion degreasing agent, or the like can be employed. Moreover, you may give a well-known pickling process to the iron-type metal material after a degreasing process as needed.

The magnetite (Fe ₃ O ₄ ) layer as the first layer is a black using an aqueous solution (hereinafter sometimes referred to as a black dyeing agent) mainly composed of at least one of sodium hydroxide and potassium hydroxide and an oxidizing agent. It can be formed by a method called dyeing treatment. Specifically, the surface of the iron-based metal material may be brought into contact with a black dyeing agent. As such a black dyeing agent, commercially available products can be used as they are, for example, “Pal Black A” and “Pal Black 3901”, “Pal Black 3903”, “Pal Black 3903” manufactured by Nippon Parkerizing Co., Ltd. Black CA "," Sten Black 919-gt "manufactured by Isolate Science Laboratory," Ebonol ss-52 "manufactured by Meltech Co., Ltd., and the like.

  The method of bringing the surface of the iron-based metal material into contact with the black dyeing agent is not particularly limited. For example, spraying the black dyeing agent on the surface of the iron-based metal material, dipping the iron-based metal material in the black dyeing agent. Immersion treatment to be performed, steam treatment using steam, and a pouring treatment in which a black dyeing agent is poured onto the surface of the iron-based metal material.

The formation temperature of the magnetite layer is preferably 70 ° C to 170 ° C, more preferably 80 ° C to 160 ° C, and most preferably 90 ° C to 150 ° C. When the formation temperature is less than 70 ° C., there are cases where uniform composition, magnetite (Fe ₃ O ₄₎ having a black appearance and thickness layer is not obtained, while when it exceeds 170 ° C., magnetite (Fe ₃ O ₄ ) may change to hematite (Fe ₂ O ₃ ), and a black film may not be obtained.

  The thickness of the magnetite layer is preferably 0.1 μm to 5 μm, more preferably 0.2 μm to 3 μm, and most preferably 0.3 μm to 2 μm. When the thickness of the magnetite layer is less than 0.1 μm, a uniform black appearance may not be obtained. On the other hand, when the thickness exceeds 5 μm, the effect may be saturated and economically disadvantageous.

Further, lithium may be introduced as a cation by adding lithium hydroxide or lithium carbonate to the black dyeing agent. When a black dye containing lithium as a cation is used, not only magnetite (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 ). By including this lithium-containing iron oxide in the magnetite layer, the corrosion resistance can be further improved.
The lithium concentration in the black dyeing agent is, for example, 0.01% by mass to 1% by mass, preferably 0.05% by mass to 0.7% by mass, and more preferably 0.1% by mass as pure lithium. % To 0.4% by mass. If the lithium concentration is less than 0.01% by mass, the effect of improving corrosion resistance due to the addition of lithium may not appear. On the other hand, if it exceeds 1% by mass, the effect may be saturated and economically disadvantageous. Moreover, the blackening of the film may be inhibited.

  In this way, the iron in the iron-based metal material is oxidized by bringing the surface of the iron-based metal material into contact with the black dyeing agent, and the layer composed of magnetite or the layer composed of magnetite and lithium-containing iron oxide is iron-based. It can be formed on the surface of a metal material. The layer made of magnetite or the layer made of magnetite and lithium-containing iron oxide has a black color, is excellent in adhesion to an iron-based metal material, and has an effect of improving corrosion resistance. It plays the role of controlling the chemical reactivity when forming the chemical conversion treatment layer. The magnetite layer in the present invention is a layer having a uniform composition, black appearance and thickness formed by chemical conversion treatment, and is different from an oxide film called black skin formed at the time of manufacturing a steel material.

  The chemical conversion treatment layer as the second layer is a chemical conversion containing at least one element selected from zinc, iron, manganese, calcium, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten. It can be formed by a method in which a treatment liquid is brought into contact with a magnetite layer as a first layer and a compound containing the above-described element is precipitated by a chemical reaction. The form of the film constituting the chemical conversion treatment layer may be crystalline or amorphous (non-crystalline). In general, since only a magnetite film formed by black dyeing treatment has poor corrosion resistance, it has been necessary to apply anti-rust oil to iron-based metal materials after black dyeing treatment. However, in the present invention, since the chemical conversion treatment film is formed on the magnetite layer, a temporary rust prevention effect can be obtained, so that the application of rust preventive oil becomes unnecessary.

  As a specific method for forming a crystalline film as a chemical conversion treatment layer, a phosphate using an acidic aqueous solution containing a phosphate ion as an anion and containing at least one selected from zinc, calcium and manganese as a cation Processing. For the purpose of increasing the reaction rate, it is preferable that an etching component such as transition metal ions such as nickel and cobalt, oxidizing agents such as nitric acid and nitrous acid, fluorine ions and complex fluorine ions are further added to the acidic aqueous solution. As the acidic aqueous solution for phosphating treatment in which the types and contents of the above anions and cations are appropriately combined, commercially available ones can be used as they are, for example, “Palbond 860” manufactured by Nihon Parkerizing Co., Ltd. "Palbond L3020", "Palphos M1A", "Palphos M5", "Palbond 880", "Palbond SX35", "Palbond L47", "Felicoat 7" and the like.

Usually, the crystalline film formed in this way contains at least one compound as shown below.
・ Zinc phosphate (Hopite: Zn ₃ (PO ₄ ) ₂ · 4H ₂ O)
・ Zinc iron phosphate (phosphophyllite: Zn ₂ Fe (PO ₄ ) ₂ · 4H ₂ O)
-Manganese phosphate (Huluilite: Mn ₅ (PO ₃ (OH)) ₂ (PO ₄ ) ₂ · 4H ₂ O)
・ Manganese iron phosphate ((Mn _1-x Fe _x ) ₅ H ₂ (PO ₄ ) ₄ · 4H ₂ O, where x is an iron-based metal material etched during chemical conversion, and its iron component is coated (Indicating that it is contained in 0 <x <1.)
・ Zinc calcium phosphate (Scholzite: CaZn ₂ (PO ₄ ) ₂ · 2H ₂ O)
Among these, a crystalline film containing manganese iron phosphate is particularly preferable because it has a property of improving slidability.

  The method of bringing the acidic aqueous solution for phosphating into contact with the magnetite layer as the first layer is not particularly limited. For example, a spray treatment in which the acidic aqueous solution for phosphating is sprayed on the surface of the magnetite layer, a magnetite layer is formed. Examples include immersion treatment in which an iron-based metal material is immersed in an acidic aqueous solution for phosphate treatment, steam treatment using steam, and a pouring treatment in which an acidic aqueous solution for phosphate treatment is poured onto the surface of the magnetite layer.

  The formation temperature of the crystalline 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 film may be insufficient. On the other hand, if the formation temperature exceeds 120 ° C, the effect may be saturated and economically disadvantageous. Etching at the time becomes excessive, and adhesion may be inferior.

  Since the crystalline film as the chemical conversion treatment layer has irregularities due to crystals, it is not appropriate to discuss the thickness, and it is important to pay attention to the crystal size. The crystal size of the crystalline phosphate is preferably 5 μm or less, more preferably 4 μm or less, and most preferably 3 μm or less. If the crystal size exceeds 5 μm, good corrosion resistance and slidability may not be obtained.

  Thus, by bringing an acidic aqueous solution containing a phosphate ion as an anion and containing at least one selected from zinc, calcium and manganese as a cation with the magnetite layer, zinc phosphate, zinc iron phosphate, phosphorus When a chemical conversion treatment layer comprising at least one crystalline phosphate selected from manganese oxide, manganese iron phosphate, and zinc calcium phosphate is formed on the magnetite layer formed by chemical conversion treatment, The crystal size is miniaturized and the corrosion resistance and slidability can be dramatically improved. Furthermore, in the present invention, it was also found that sludge generated during the phosphate treatment is remarkably small. This is presumably because the chemical reactivity in film formation is controlled by the magnetite layer. Therefore, the present invention has an advantage that the number of complicated sludge removal operations and the amount of sludge discharged as industrial waste can be reduced.

  As a specific method for forming an amorphous film as a chemical conversion treatment layer, an acidic aqueous solution containing phosphate ions as anions and at least one selected from iron, tin, zirconium, titanium and hafnium as cations Phosphate treatment using For the purpose of increasing the reaction rate, it is preferable that an etching component such as transition metal ions such as nickel and cobalt, oxidizing agents such as nitric acid and nitrous acid, fluorine ions and complex fluorine ions are further added to the acidic aqueous solution. As the acidic aqueous solution for phosphating treatment in which the types and contents of the anions and cations described above are appropriately combined, commercially available ones can be used as they are, for example, “Parphos 1077” manufactured by Nihon Parkerizing Co., Ltd. , “Palphos 525T”, “Palphos K5100” and the like.

Usually, the amorphous film thus formed contains at least one compound as shown below.
・ Iron phosphate ・ Tin phosphate ・ Zirconium phosphate ・ Titanium phosphate ・ Hafnium phosphate

  Further, as another method for forming an amorphous film as a chemical conversion treatment layer, it contains at least one selected from nitrate ion, sulfate ion, fluorine ion, complex fluorine ion and carbonate ion as an anion, and iron, titanium , Zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum, and a method using an acidic aqueous solution containing at least one selected from tungsten and tungsten as cations. Such an acidic aqueous solution can be prepared by appropriately combining the types and contents of the compounds corresponding to the above-mentioned anions and cations, or those commercially available can be used as they are.

The compounds contained in the amorphous film thus formed are oxides, sulfides and / or fluorides, and typical ones are exemplified below.
-Titanium oxide-Zirconium oxide-Hafnium oxide-Indium oxide-Tin oxide-Bismuth oxide-Vanadium oxide-Nickel oxide-Cerium oxide-Molybdenum oxide-Tungsten oxide-Zirconium fluoride-Zirconium fluoride-Titanium fluoride-Hafnium fluoride-Fluorine Indium phosphide

  Among the above-mentioned compounds, an amorphous material containing zirconium hydroxide and any one of titanium hydroxide, zirconium fluoride, titanium fluoride, zirconium oxide, and titanium oxide from the viewpoint of particularly improving the corrosion resistance. A film is preferred. Further, the amorphous film has at least one selected from titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum, and tungsten within a range that does not adversely affect the characteristics of the film. A hydroxide containing an element, for example, zirconium hydroxide, titanium hydroxide, hafnium hydroxide, indium hydroxide, or the like may be partially contained.

  The method for bringing the acidic aqueous solution into contact with the magnetite layer as the first layer is not particularly limited. For example, spray treatment in which the acidic aqueous solution is sprayed on the surface of the magnetite layer; Examples include immersion treatment in which the substrate is immersed, steam treatment using steam, and pouring treatment in which an acidic aqueous solution is poured onto the surface of the magnetite layer.

  The formation temperature of the amorphous film as the chemical conversion treatment layer is usually 10 ° C to 100 ° C, preferably 15 ° C to 80 ° C, and more preferably 20 ° C to 60 ° C. If the formation temperature is less than 10 ° C, the formation of the film may be insufficient. On the other hand, if the formation temperature exceeds 100 ° C, the effect may be saturated and economically disadvantageous. , Etching during the chemical conversion reaction becomes excessive, and the adhesion may be inferior.

  The thickness of the amorphous 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 slidability may not be obtained. On the other hand, if the thickness exceeds 3 μm, the effect is saturated and economically disadvantageous. In addition, the black appearance may be impaired.

Thus, an acidic aqueous solution containing a phosphate ion as an anion and at least one selected from zinc, calcium and manganese as a cation, or selected from a nitrate ion, a sulfate ion, a fluoride ion, a complex fluoride ion and a carbonate ion An acidic aqueous solution containing at least one selected from the group consisting of iron, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten as a cation. The chemical conversion treatment layer which consists of an amorphous membrane | film | coat can be formed on a magnetite layer by making it contact with. The chemical conversion treatment layer made of this amorphous film can improve the corrosion resistance and the slidability as well as the chemical conversion treatment layer made of crystalline phosphate, and the magnetite layer and the third layer as the first layer. Excellent adhesion to the solid lubricating layer as a layer. In addition, the chemical conversion treatment layer made of this amorphous film exhibits the effect of improving the corrosion resistance and slidability even if it is an extremely thin film, and therefore has an advantage that the dimensional change accompanying the film formation can be remarkably reduced. . Furthermore, in the formation of this amorphous film, sludge adhesion to the film, which is a problem when forming a chemical conversion treatment layer made of crystalline phosphate, can be greatly reduced, and etching of the material accompanying chemical conversion treatment can be performed. It was found that the film can be formed without roughening the surface because the reaction is extremely small.

  The solid lubricant layer as the third layer can be formed by applying a known solid lubricant and baking as required. The solid lubricant is generally obtained by dispersing a large amount of solid lubricant fine particles in a binder solution obtained by dissolving a binder resin in a solvent. Examples of the 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) Mineral), fullerene (nanocarbon), copper powder, nickel powder, lead powder, tin powder, silver powder, gold powder, zinc powder, indium powder, polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether Polymer (PFA), melamine annulate (MCA: almost 1: 1 organic adduct of melamine and isocyanuric acid), polyimide powder, nylon, high density polyethylene powder, organic molybdenum compound, fat, soap, waxes (tallow, Lithium stearate, beeswax etc.), fatty acids, phthalocyanine . Among these, good sliding properties and stable molybdenum disulfide terms obtained, graphite and PTFE are preferred. Examples of the binder resin include polyamide imide, polyimide, epoxy, furan, melamine, acrylic, urethane, and the like. Examples of the solvent include xylene, toluene, butanol, isobutyl alcohol, isopropyl alcohol, dioxane, methyl ethyl ketone, n-methyl-2-pyrrolidone and the like. As such a solid lubricant, a commercially available one can be used as it is, for example, “HMB-2” manufactured by Kawamata Laboratories Co., Ltd. as containing molybdenum disulfide, and containing graphite. “HMB-18” manufactured by Kawamata Laboratories Co., Ltd. “HMB-34” manufactured by Kawamata Laboratories Co., Ltd. as a product containing molybdenum disulfide and graphite, manufactured by Daikin Industries, Ltd. as a product containing PTFE and graphite "TC-7109BK" etc. are mentioned.

  As a method for applying the solid lubricant, a known method can be adopted. For example, an iron-based metal in which a spray, brush coating, tumbling, a magnetite layer as a first layer, and a chemical conversion treatment layer as a second layer are formed. Examples include a method of immersing the material in a solid lubricant. After application of the solid lubricant, the solid lubricant layer can be formed by baking at an appropriate temperature and time as necessary.

  The thickness of the solid lubricant layer is preferably 0.2 μm to 50 μm, more preferably 0.5 μm to 30 μm, and most preferably 0.7 μm to 15 μm. If the thickness of the solid lubricating layer is less than 0.2 μm, good slidability may not be obtained. On the other hand, if the thickness exceeds 50 μm, the effect may be saturated and economically disadvantageous. Further, the generation of a large amount of wear powder may adversely affect the slidability.

  In addition, known additives such as a dispersant, an antifoaming agent, a stabilizer, a flame retardant, a curing accelerator, and a pigment may be appropriately added to the solid lubricant as long as the effects of the present invention are not impaired. However, since the black surface-treated iron-based metal material of the present invention is characterized by exhibiting a good black color, these additives are limited to those in which the solid lubricant is black or colorless and transparent.

  Thus, a solid lubricant layer can be formed by applying a solid lubricant on the chemical conversion treatment layer and baking it as necessary. This solid lubricating layer can impart excellent slidability to the ferrous metal material.

Between the steps of forming the first layer to the third layer of the present invention, washing with water, drying, antirust oil coating, degreasing and the like may be performed as necessary. A preferred production process in the present invention is degreasing of iron-based metal material → washing → first layer formation → water washing → second layer formation → water washing → drying → third layer formation.
Furthermore, prior to the formation of the first layer and / or the second layer, surface adjustment may be performed for the purpose of promoting film formation. In particular, when forming a crystalline phosphate as the second layer, prior to the formation of the second layer, surface adjustment is performed using a commonly used surface conditioner, which facilitates film formation and increases the crystal size. The effect of miniaturization can be obtained. Examples of the surface conditioner include “Preparene X”, “Preparene 55”, “Preparene Z”, “Preparene VM”, “Preparene XG”, and “Preparene 35” manufactured by Nippon Parkerizing Co., Ltd.

In order to improve corrosion resistance, slidability, etc., an intermediate coating layer may be provided between the second layer and the third layer described above. The intermediate coating layer may be, for example, a metal silicate such as sodium silicate, lithium silicate, potassium silicate, calcium silicate, aluminum silicate, silicon oxide such as silicon monoxide or colloidal silica (silicon dioxide), chlorotri C _1-2 alkoxysilane, glycidyloxyalkyl-tri C _1-2 alkoxysilane, di (glycidyloxyalkyl) di C _1-2 alkoxysilane, 3-aminopropyldiethoxymethylsilane, aminoalkyl-tri C _1-2 Alkoxysilane, di (aminoalkyl) di C _1-2 alkoxysilane, vinyl tri C _1-2 alkoxysilane, vinyl tri C _1-2 alkoxysilane, methyltrimethoxysilane, (meth) acryloyloxyalkyl-tri C _1-2 alkoxy Silane, tetraethyl silicate, di ((meth) acryloyloxy Alkyl) - di C _1-2 alkoxysilane such as silane coupling agent, ethyl polysilicate, propyl polysilicate, silicate compounds such as butyl polysilicate, silicone resins, isopropyl trioctanoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate , Titanium-i-propoxyoctylene glycolate, isopropyl (N-aminoethylaminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) Phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyl dimethacrylic Sostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphate) titanate, titanium tetra (monoethyl ethoxide), titanium tetra (monobutyl ethoxide) ), Titanium tetrakis (acetylacetonate), titanate coupling agents such as tetranormal butyl titanate and organic titanium compounds, organic vanadium compounds such as vanadyl acetylacetonate, organic nickel compounds such as nickel acetylacetonate, cerium acetylacetonate, etc. An aqueous solution, dispersion or solvent system containing at least one selected from organic cerium compounds Hereinafter, it may be formed by a method of coating a chemical conversion treatment layer as a second layer and drying it as necessary. Further, two or more intermediate coating layers may be formed.

  The method for applying the coating type treatment liquid onto the chemical conversion treatment layer is not particularly limited, and examples thereof include bar coating, curtain coating, extrusion coating, roll coating, dip coating, spray coating, spin coating, gravure coating, and die coating. Known methods such as coating may be mentioned.

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

  Moreover, you may add an acrylic resin, a urethane resin, an epoxy resin, a phenol resin, a polyester resin, a polyimide resin etc. to a process liquid as an arbitrary component. The ionicity of each resin is not particularly limited, and may be any of anionic, cationic and nonionic.

  When the above intermediate coating layer is formed instead of the chemical conversion treatment layer, that is, the magnetite layer formed by chemical conversion treatment, the intermediate coating layer, and the solid lubricating layer are provided in this order on the surface of the iron-based metal material. The black surface-treated iron-based metal material that exhibits a good black appearance and can withstand practical use in terms of corrosion resistance and slidability, although the corrosion resistance and slidability of the black surface-treated iron-based metal material of the present invention cannot be obtained. It can be.

The black surface-treated iron-based metal material of the present invention has a very good black appearance, is excellent in corrosion resistance and slidability, and has a chromium-free coating formed thereon. Optical machine parts, measuring machine parts, firearms, telecommunication parts, automatic motorcycle machine parts, automatic four wheel machine parts, ornaments, etc. It is extremely useful as a member constituting a linear motion device or the like of equipment devices represented by semiconductor manufacturing equipment and food manufacturing equipment.
In addition, the present invention can form a black multilayer film having the above-described excellent performance at a low cost by a relatively simple process without using a power supply facility for electrolysis. It can be applied for use.

  Below, an Example is given with a comparative example and the effect of the black surface treatment iron-type metal material of this invention is demonstrated concretely. The iron-based metal materials, degreasing agents, black dyeing agents used for film formation, chemical conversion liquids and solid lubricating paints used in the examples are arbitrarily selected from commercially available materials and reagents. The present invention is not limited in any way.

<Outline of manufacturing process>
Examples 1 to 10 and 17 to 20 and Comparative Examples 6 to 7 were carried out in the following steps.
Alkaline degreasing → Washing → First layer formation → Water washing → Second layer formation → Washing → Drying → Third layer formation → Baking Examples 11 to 16 were carried out in the following steps.
Alkaline degreasing → Washing → First layer formation → Washing → Second layer formation → Washing → Drying → Intermediate coating layer formation → Drying / baking → Third layer formation → Baking Reference Examples 1 to 4 were carried out in the following steps.
Alkaline degreasing → Washing → First layer formation → Water washing → Drying → Intermediate coating layer formation → Drying / baking → Third layer formation → Baking Comparative Examples 1 to 5 were carried out in the following steps.
Alkaline degreasing → Washing → Film formation → Washing → Drying → Solid lubricating coating (third layer) formation → Baking For Comparative Example 8, after alkaline degreasing, washing with water and drying steps, solid lubricating coating (third layer) Formed.

  About each material obtained by the Example and the comparative example, the blackness evaluation of external appearance, corrosion resistance, and sliding property were evaluated by the following method. In addition, after forming to the 3rd layer, the thickness of the layer measured the thickness of each layer by observing a film cross section using a metal microscope. Moreover, about the Example and comparative example which formed the crystalline membrane | film | coat in the 2nd layer, the crystal size was measured using the scanning electron microscope after 2nd layer formation.

<Appearance (blackness) evaluation>
A cold-rolled steel sheet (abbreviation SPC: JIS G 3141, 70 × 150 × 0.8 tmm) was used as the iron-based metal material, and alkaline degreasing was performed prior to film formation. For alkaline degreasing, an aqueous solution obtained by diluting Fine Cleaner (registered trademark) 4360 manufactured by Nippon Parkerizing Co., Ltd. to 2% with tap water is heated to 60 ° C., and the cold-rolled steel sheet is immersed in this solution for 10 minutes, and then washed with water. It was done by doing.
The appearance (blackness) evaluation was visually performed on the layers formed on each cold-rolled steel sheet in Examples 1 to 20, Comparative Examples 1 to 7, and Reference Examples 1 to 4. In addition, about an Example, it evaluates about each of a 1st layer-3rd layer, About Comparative Examples 1-5, it evaluates only after forming a solid-lubrication layer, About Comparative Examples 6 and 7, The evaluation for the second layer and the third layer was performed.
The appearance (blackness) was evaluated according to the following criteria.
(Evaluation criteria)
○: Uniform black △: Black with unevenness and scumming ×: Not black

<Corrosion resistance evaluation>
A cold-rolled steel sheet (abbreviation SPC: JIS G 3141, 70 × 150 × 0.8 tmm) was used as the iron-based metal material, and alkaline degreasing was performed prior to film formation. For alkaline degreasing, an aqueous solution obtained by diluting Fine Cleaner (registered trademark) 4360 manufactured by Nippon Parkerizing Co., Ltd. to 2% with tap water is heated to 60 ° C., and the cold-rolled steel sheet is immersed in this solution for 10 minutes, and then washed with water. It was done by doing.
After cross-cutting with a sharp cutter on the surface of each cold-rolled steel sheet obtained in Examples and Comparative Examples, 5 mass% salt water was sprayed for 240 hours. After the spraying was completed, the cross cut portion and the general surface without the cross cut were evaluated according to the following criteria.
(Evaluation criteria)
◎: No occurrence of red rust on the general surface, swelling in the cross-cut part, no peeling, etc. ○: No occurrence of red rust on the general surface, swelling in the cross-cut part, slight peeling, etc. △: General surface Spot-like red rust occurs, swells in the crosscut part, peels off, etc. ×: Red rust occurs on the entire surface of the general surface and the crosscut part

<Slidability evaluation>
As the iron-based metal material, a carbon steel material for mechanical structure (abbreviation S45C: JIS G 4051, φ22 × 8 mm, buffed and Ra10 nm, Ry50 nm finished) was used, and alkaline degreasing was performed prior to film formation. For alkaline degreasing, an aqueous solution obtained by diluting Fine Cleaner (registered trademark) 4360 manufactured by Nippon Parkerizing Co., Ltd. to 2% with tap water was heated to 60 ° C., and carbon steel for machine structure was immersed in this solution for 10 minutes. Thereafter, washing was performed with water.
About each carbon steel material for mechanical structures obtained by the Example and the comparative example, slidability was evaluated using the SRV test machine by Optimol Instruments. The evaluation was a non-lubricated evaluation in which no lubricating oil was used. A sliding test was performed under the following sliding test conditions, and the friction coefficient, the counterpart material aggression, and the appearance of the sliding trace after the sliding test were evaluated.
(Sliding test conditions)
Mating material: SUJ2 steel ball (10mmφ)
Load: 15N (Hertz surface pressure: 116Kg / mm ² )
Stroke: 2mm
Speed: 5Hz
Test time: 15 minutes Test temperature: Room temperature (in air)

The friction coefficient is obtained by calculating an average value of measured friction coefficients (measurement upper limit value: 0.64). The mating material aggression is calculated by calculating the mating material sliding trace area after the sliding test. Further, the observation of the appearance of the sliding marks after the sliding test was evaluated according to the following criteria.
(Evaluation criteria)
◎: Uniform dark black ○: Uniform thin black △: Black but partially metallic luster ×: Metallic luster (exposed material)

Example 1
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 148 ° C. as a black dyeing agent. Then, it was immersed for 60 minutes, and the 1st layer which has a magnetite as a main component was formed.
Using a titanium hydrofluoric acid reagent, a nitric acid reagent, and a hydrofluoric acid reagent, the titanium concentration is 2000 mg / L, the nitric acid concentration is 10,000 mg / L, and the fluorine concentration is 7 mg / L as free fluorine. A chemical conversion solution was prepared. Next, the chemical conversion treatment liquid is heated to 50 ° C., and the iron-based metal material after the first layer is formed is immersed in the chemical conversion treatment solution adjusted to pH 3.0 with an ammonia water reagent for 300 seconds, and titanium oxide is mainly used. A second layer as a component was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second layer of iron-based metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 2)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 145 ° C. as a black dyeing agent. Then, it was immersed for 50 minutes, and the 1st layer which has a magnetite as a main component was formed.
Using a zircon hydrofluoric acid reagent, a nitric acid reagent and a hydrofluoric acid reagent, an acidic chemical composition having a zirconium concentration of 300 mg / L, a nitric acid concentration of 7000 mg / L, and a fluorine concentration of 10 mg / L as free fluorine. A treatment solution was prepared. Next, the chemical conversion treatment liquid is heated to 40 ° C., and the iron-based metal material after the first layer is formed is immersed in the chemical conversion treatment solution adjusted to pH 4.2 with an ammonia water reagent for 180 seconds. A second layer as a component was formed.
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 (low pressure spray gun "MGB40" manufactured by Asahi Sunac Co., Ltd.) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 3)
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 150 ° C. as a black dyeing agent. Then, it was immersed for 60 minutes, and the 1st layer which has a magnetite as a main component was formed.
Using an hafnium oxide reagent, a nitric acid reagent and a hydrofluoric acid reagent, an acidic chemical conversion treatment solution having 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 Was prepared. Next, the chemical conversion treatment liquid is heated to 45 ° C., and the iron-based metal material after the first layer is formed is immersed in the chemical conversion treatment solution adjusted to pH 4.5 with an ammonia water reagent for 600 seconds, and hafnium oxide is mainly used. A second layer as a component was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-2” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second layer of iron-based metal material. After that, baking was performed at 200 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

Example 4
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 147 ° C. as a black dyeing agent. Then, it immersed for 30 minutes and formed the 1st layer which has a magnetite as a main component.
Using an indium oxide reagent, a nitric acid reagent and hydrofluoric acid, an acidic chemical conversion treatment solution having 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. Prepared. Next, the chemical conversion treatment liquid is heated to 45 ° C., and the iron-based metal material forming the first layer is immersed in the chemical conversion treatment liquid adjusted to pH 3.5 with an aqueous ammonia reagent for 300 seconds, and indium oxide is mainly used. A second layer as a component was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second layer of iron-based metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 5)
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water from “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 135 ° C. as a black dyeing agent. Then, it immersed for 20 minutes and formed the 1st layer which has a magnetite as a main component.
Calcium phosphate-based chemical conversion treatment solution (“Palbond 860” manufactured by Nihon Parkerizing Co., Ltd.) is diluted to 6% by mass with tap water, adjusted to a total acidity of 21 points, and further heated to 70 ° C. Then, the iron-based metal material after the formation of the first layer was immersed for 300 seconds to form a second layer mainly composed of calcium calcium phosphate (scholzite) and zinc phosphate (hopeite).
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 (low pressure spray gun "MGB40" manufactured by Asahi Sunac Co., Ltd.) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 6)
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water from “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 135 ° C. as a black dyeing agent. Thereafter, it was immersed for 3 minutes to form a first layer mainly composed of magnetite.
In the surface conditioner in which the surface conditioner for zinc phosphate treatment ("preparene X" manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 0.3% by mass, the iron-based metal material after the first layer is formed It was immersed for 30 seconds. Next, a zinc phosphate chemical conversion treatment solution (“Palbond L3020” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 4.8% by mass, and 0.5% by mass of additive 4813 manufactured by Nihon Parkerizing Co., Ltd. is used. % And additive 4856 made by Nihon Parkerizing Co., Ltd. were added respectively, and the total acidity was adjusted to 23 points, the free acidity was adjusted to 0.9 points, and further heated to 45 ° C. 0.042% by mass of accelerator 131 manufactured by Nippon Parkerizing Co., Ltd. was added, and the surface-adjusted iron-based metal material was immersed for 90 seconds, zinc phosphate (hopeite) and zinc iron phosphate (phosphophyllite) Was formed as a main component.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-2” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second layer of iron-based metal material. After that, baking was performed at 200 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 7)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 147 ° C. as a black dyeing agent. Then, it was immersed for 90 minutes, and the 1st layer which has a magnetite as a main component was formed.
Iron phosphate chemical treatment solution (“Parphos 1077” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 5% by mass, the total acidity is adjusted to 10 points, and the acid consumption point is adjusted to 0.4 points. In the chemical conversion treatment liquid heated to 50 ° C., the iron-based metal material after the formation of the first layer was immersed for 90 seconds to form a second layer mainly composed of iron phosphate.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second layer of iron-based metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 8)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 145 ° C. as a black dyeing agent. Then, it immersed for 30 minutes and formed the 1st layer which has a magnetite as a main component.
In a surface conditioner obtained by diluting a surface conditioner for treating manganese phosphate ("preparene 55" manufactured by Nihon Parkerizing Co., Ltd.) with tap water to a concentration of 0.3% by mass, the iron-based metal material after the first layer is formed. It was immersed for 30 seconds. Next, a manganese phosphate surface treatment agent (“Palphos M1A” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 14% by mass to give a total acidity of 50 points, a free acidity of 8.6 points, and an acid ratio. (Total acidity / free acidity) was adjusted to 5.8, the iron concentration was adjusted to 1.5 g / L, and the surface-adjusted iron-based metal material was immersed in a chemical conversion treatment solution heated to 97 ° C. for 900 seconds. Then, a second layer mainly composed of manganese phosphate (huriolite) and manganese iron phosphate was formed.
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 (low pressure spray gun "MGB40" manufactured by Asahi Sunac Co., Ltd.) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

Example 9
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water from “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 142 ° C. as a black dyeing agent. Then, it was immersed for 40 minutes, and the 1st layer which has a magnetite as a main component was formed.
An acidic chemical conversion treatment solution having a tin concentration of 300 mg / L and a chlorine concentration of 1000 mg / L was prepared using a tin chloride reagent and a hydrochloric acid reagent. Next, the chemical conversion treatment liquid is heated to 40 ° C., and the iron-based metal material after the first layer is formed is immersed in the chemical conversion treatment solution adjusted to pH 4.2 with an aqueous ammonia reagent for 300 seconds. A second layer as a component was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second layer of iron-based metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 10)
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 148 ° C. as a black dyeing agent. Then, it was immersed for 60 minutes, and the 1st layer which has a magnetite as a main component was formed.
An acidic chemical conversion treatment solution having a bismuth concentration of 300 mg / L and a nitric acid concentration of 6000 mg / L was prepared using a bismuth nitrate reagent and a nitric acid reagent. Next, the chemical conversion treatment liquid is heated to 50 ° C., and the iron-based metal material after the first layer is formed is immersed in the chemical conversion treatment liquid adjusted to pH 4.8 with an aqueous ammonia reagent for 180 seconds, and bismuth oxide is mainly used. A second layer as a component was formed.
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 (low pressure spray gun "MGB40" manufactured by Asahi Sunac Co., Ltd.) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 11)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water of “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 132 ° C. as a black dyeing agent. Then, it immersed for 30 minutes and formed the 1st layer which has a magnetite as a main component.
Using a zircon hydrofluoric acid reagent, a nitric acid reagent and a hydrofluoric acid reagent, an acidic chemical composition having a zirconium concentration of 150 mg / L, a nitric acid concentration of 9000 mg / L, and a fluorine concentration of 6 mg / L as free fluorine. A treatment solution was prepared. Next, the chemical conversion treatment liquid was heated to 45 ° C., and the iron-based metal material after the first layer was formed was immersed for 90 seconds in the chemical conversion treatment liquid adjusted to pH 3.5 with an ammonia water reagent. A second layer as a component was formed.
Using 3-aminopropyldiethoxymethylsilane (“D1980” manufactured by Tokyo Chemical Industry Co., Ltd.), a coating type treatment liquid having a silicon oxide equivalent concentration of 2 mass% was prepared. Next, after apply | coating the coating-type process liquid on the 2nd layer of an iron-type metallic material with normal temperature, it hold | maintained at 150 degreeC for 30 minute (s), and formed the intermediate | middle application layer.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-2” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the intermediate coating layer of ferrous metal material. After that, baking was performed at 200 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 12)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 145 ° C. as a black dyeing agent. Then, it was immersed for 75 minutes, and the 1st layer which has a magnetite as a main component was formed.
Calcium phosphate-based chemical conversion treatment solution (“Palbond 860” manufactured by Nihon Parkerizing Co., Ltd.) is diluted to 6% by mass with tap water, adjusted to a total acidity of 21 points, and further heated to 70 ° C. Then, the iron-based metal material after the formation of the first layer was immersed for 300 seconds to form a second layer mainly composed of calcium calcium phosphate (scholzite) and zinc phosphate (hopeite).
Colloidal silica (“Snowtex (registered trademark) N” manufactured by Nissan Chemical Industries, Ltd.) was diluted to prepare a coating type treatment liquid having a silicon oxide equivalent concentration of 5 mass%. Next, after apply | coating the coating type process liquid on the 2nd layer of an iron-type metallic material with normal temperature, it hold | maintained at 120 degreeC for 20 minute (s), and formed the intermediate | middle application layer.
Using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the intermediate coating layer of ferrous metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 13)
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water of “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 140 ° C. as a black dyeing agent. Then, it was immersed for 40 minutes, and the 1st layer which has a magnetite as a main component was formed.
In a surface conditioner obtained by diluting a surface conditioner for treating manganese phosphate ("preparene 55" manufactured by Nihon Parkerizing Co., Ltd.) with tap water to a concentration of 0.3% by mass, the iron-based metal material after the first layer is formed. It was immersed for 30 seconds. Next, a manganese phosphate chemical conversion treatment solution (“Parphos M1A” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 14% by mass to give a total acidity of 50 points, a free acidity of 8.6 points, and an acid ratio. (Total acidity / free acidity) was adjusted to 5.8, the iron concentration was adjusted to 1.5 g / L, and the surface-adjusted iron-based metal material was immersed in a chemical conversion treatment solution heated to 98 ° C. for 600 seconds. Then, a second layer mainly composed of manganese phosphate (huriolite) and manganese iron phosphate was formed.
Using ethyl polysilicate, methyltrimethoxysilane, and tetraethylsilicate ("SB-4611" manufactured by Tama Chemical Industry Co., Ltd.), a coating type treatment liquid having a silicon oxide equivalent concentration of 2 mass% was prepared. After applying the mold treatment liquid on the second layer of the iron-based metal material at room temperature, the mold treatment liquid was held at 110 ° C. for 15 minutes to form an intermediate coating layer.
After applying solid lubricant paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) on the intermediate coating layer of iron-based metal material using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Corporation) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 14)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 147 ° C. as a black dyeing agent. Then, it immersed for 30 minutes and formed the 1st layer which has a magnetite as a main component.
Iron phosphate chemical treatment solution (“Parphos 1077” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 5% by mass, the total acidity is adjusted to 10 points, and the acid consumption point is adjusted to 0.4 points. The iron-based metal material after the first layer was formed was immersed in a chemical conversion treatment solution heated to 55 ° C. for 75 seconds to form a second layer containing iron phosphate as a main component.
Using titanium-i-propoxyoctylene glycolate (“TOG” manufactured by Nippon Soda Co., Ltd.), a coating type treatment liquid having a titanium oxide equivalent concentration of 2 mass% was prepared. Next, after apply | coating the coating type process liquid on the 2nd layer of an iron-type metallic material with normal temperature, it hold | maintained at 180 degreeC for 30 minute (s), and formed the intermediate | middle application layer.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-2” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the intermediate coating layer of ferrous metal material. After that, baking was performed at 200 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 15)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 147 ° C. as a black dyeing agent. Then, it immersed for 45 minutes and formed the 1st layer which has a magnetite as a main component.
Using a zircon hydrofluoric acid reagent, a nitric acid reagent and a hydrofluoric acid reagent, an acidic chemical composition having a zirconium concentration of 200 mg / L, a nitric acid concentration of 9000 mg / L, and a fluorine concentration of 13 mg / L as free fluorine. A treatment solution was prepared. Next, the chemical conversion treatment liquid is heated to 43 ° C., and the iron-based metal material after the first layer is formed is immersed in the chemical conversion treatment solution adjusted to pH 4.0 with an ammonia water reagent for 120 seconds. A second layer as a component was formed.
Using ethyl polysilicate, methyltrimethoxysilane, and tetraethylsilicate (“SB-4611” manufactured by Tama Chemical Industry Co., Ltd.), a coating type treatment liquid having a silicon oxide equivalent concentration of 3 mass% was prepared. Next, after apply | coating the coating type process liquid on the 2nd layer of an iron-type metallic material with normal temperature, it hold | maintained at 130 degreeC for 30 minute (s), and formed the intermediate | middle application layer.
After applying solid lubricant paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) on the intermediate coating layer of iron-based metal material using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Corporation) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 16)
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water from “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 143 ° C. as a black dyeing agent. Then, it was immersed for 35 minutes, and the 1st layer which has a magnetite as a main component was formed.
In a surface conditioner in which a surface conditioner for zinc phosphate treatment ("preparene Z" manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 0.1% by mass, the iron-based metal material after the first layer is formed It was immersed for 30 seconds. Next, a zinc phosphate chemical conversion treatment solution (“Palbond L3020” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 4.8% by mass, and 0.5% by mass of additive 4813 manufactured by Nihon Parkerizing Co., Ltd. is used. % And additive 4856 made by Nihon Parkerizing Co., Ltd. were added respectively, and the total acidity was adjusted to 23 points, the free acidity was adjusted to 0.9 points, and further heated to 40 ° C. 0.042% by mass of accelerator 131 manufactured by Nippon Parkerizing Co., Ltd. was added, and the surface-adjusted iron-based metal material was immersed for 120 seconds, zinc phosphate (hopeite) and zinc iron phosphate (phosphophyllite) Was formed as a main component.
Colloidal silica (“Snowtex (registered trademark) N” manufactured by Nissan Chemical Industries, Ltd.) was diluted to prepare a coating type treatment liquid having a SiO ₂ concentration of 3% by mass. Next, after apply | coating the coating type processing liquid on the 2nd layer of an iron-type metal material with normal temperature, it hold | maintained at 120 degreeC for 20 minute (s), and formed the 1st intermediate coating layer.
Using 3-aminopropyldiethoxymethylsilane (“D1980” manufactured by Tokyo Chemical Industry Co., Ltd.), a coating type treatment liquid having a silicon oxide equivalent concentration of 1 mass% was prepared. Next, after apply | coating the coating type processing liquid on the 1st intermediate application layer of iron-type metal material with normal temperature, it hold | maintained at 150 degreeC for 30 minute (s), and formed the 2nd intermediate application layer.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), a solid lubricant paint (“HMB-2” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second intermediate coating layer of the iron-based metal material. ) And then baked at 200 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 17)
15g of lithium hydroxide monohydrate is obtained by diluting "Pal Black A" manufactured by Nihon Parkerizing Co., Ltd. with tap water to a concentration of 80.5% by mass on the surface of the ferrous metal material after the alkali degreasing treatment. / L was added, and the mixture was sufficiently stirred and dissolved as a black dyeing agent, heated to 147 ° C. and then immersed for 60 minutes to form a first layer mainly composed of magnetite.
Using a zircon hydrofluoric acid reagent, a nitric acid reagent and a hydrofluoric acid reagent, an acidic chemical composition having a zirconium concentration of 120 mg / L, a nitric acid concentration of 8000 mg / L, and a fluorine concentration of 10 mg / L as free fluorine. A treatment solution was prepared. Next, the chemical conversion treatment liquid is heated to 52 ° C., and the iron-based metal material after the first layer is formed is immersed in the chemical conversion treatment solution adjusted to pH 3.9 with an aqueous ammonia reagent for 900 seconds. A second layer as a component was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second layer of iron-based metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 18)
To the surface of the ferrous metal material after alkaline degreasing treatment, “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. diluted to 80.5% by mass with tap water, and 12 g of lithium hydroxide monohydrate. / L added, and sufficiently stirred and dissolved as a black dyeing agent, heated to 147 ° C. and then immersed for 40 minutes to form a first layer mainly composed of magnetite.
In a surface conditioner obtained by diluting a surface conditioner for treating manganese phosphate ("preparene VM" manufactured by Nihon Parkerizing Co., Ltd.) with tap water to a concentration of 0.5% by mass, the iron-based metal material after the first layer is formed. It was immersed for 45 seconds. Next, a manganese phosphate chemical conversion treatment solution (“Parphos M5” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 11% by mass, the total acidity is 8 points, the free acidity is 1.3 points, and the acid ratio (Total acidity / free acidity) is 6.2, the concentration of the accelerator is adjusted to 2.5 points using the accelerator 131 manufactured by Nippon Parkerizing Co., Ltd., and further heated to 85 ° C. The adjusted iron-based metal material was immersed for 600 seconds to form a second layer mainly composed of manganese phosphate (huriolite) and manganese iron 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 (low pressure spray gun "MGB40" manufactured by Asahi Sunac Co., Ltd.) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 19)
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 150 ° C. as a black dyeing agent. Then, it immersed for 70 minutes and formed the 1st layer which has a magnetite as a main component.
An acidic chemical conversion treatment solution having a molybdenum concentration of 8000 mg / L and a sulfuric acid concentration of 10,000 mg / L was prepared using a sodium molybdate reagent and a sulfuric acid reagent. Next, the chemical conversion treatment liquid is heated to 60 ° C., and the iron-based metal material after the first layer is formed is immersed in a chemical conversion treatment solution adjusted to pH 2.9 with an aqueous ammonia reagent for 180 seconds. A second layer as a component was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the second layer of iron-based metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Example 20)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 147 ° C. as a black dyeing agent. Then, it immersed for 30 minutes and formed the 1st layer which has a magnetite as a main component.
Using a sodium tungstate reagent, a phosphoric acid reagent, and a sulfuric acid reagent, an acidic chemical conversion treatment solution having a tungsten concentration of 15000 mg / L, a phosphoric acid concentration of 10,000 mg / L, and a sulfuric acid concentration of 1000 mg / L was prepared. . Next, the iron-based metal material after the formation of the first layer is immersed for 100 seconds in a chemical conversion treatment solution adjusted to pH 1.0 with a sodium hydroxide reagent to form a second layer mainly composed of tungsten oxide. did.
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 (low pressure spray gun "MGB40" manufactured by Asahi Sunac Co., Ltd.) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Reference Example 1)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 145 ° C. as a black dyeing agent. Then, it was immersed for 75 minutes, and the 1st layer which has a magnetite as a main component was formed.
Using a vanadyl acetylacetonate reagent, the vanadium concentration was set to 5000 mg / L, and 300 parts by mass of deionized water and 2 parts by mass of an anionic reactive surfactant were added to the reactor and stirred with a homomixer. A mixture of 50 parts by weight of deionized water and 1 part by weight of potassium persulfate, 287 parts by weight of deionized water, 4 parts by weight of reactive emulsifier, 60 parts by weight of methyl methacrylate, 158 parts by weight of styrene, 18 parts by weight of 2-ethylhexyl acrylate, Coating type treatment in which a water-dispersible acrylic resin obtained by blending a mixture of 4.5 parts by weight of methacrylic acid, 4.5 parts by weight of 2-hydroxyethyl methacrylate and 45 parts by weight of glycidyl methacrylate little by little at the same time is 2000 mg / L. A liquid was prepared. Next, after apply | coating the coating type processing liquid on the 1st layer of an iron-type metallic material with normal temperature, it was made to dry for 15 minutes at 100 degreeC, and the intermediate coating layer was formed.
Using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the intermediate coating layer of ferrous metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Reference Example 2)
The surface of the iron-based metal material after the alkaline degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 150 ° C. as a black dyeing agent. Then, it was immersed for 65 minutes, and the 1st layer which has a magnetite as a main component was formed.
Using a nickel acetylacetonate reagent, a nickel concentration of 7000 mg / L, and 100 parts by mass of a polyester polyol having a number average molecular weight of 5000 obtained from 1,6-hexanediol and adipic acid in a reactor, 2, 2 -Reaction was performed by adding 5 parts by mass of dimethyl-1,3-propanediol, 20 parts by mass of 2,2-dimethylolpropionic acid, 100 parts by mass of 4,4-dicyclohexylmethane diisocyanate, and 100 parts by mass of N-methyl-2-pyrrolidone. Thus, a urethane prepolymer having a free isocyanate group content of 5% based on the nonvolatile content was obtained. Next, 16 parts by mass of tetramethylene diamine and 10 parts by mass of triethylamine are added to 500 parts by mass of deionized water and stirred with a homomixer. The urethane prepolymer is added and emulsified and dispersed, and finally deionized water is added. A coating type treatment liquid in which the obtained water-dispersible urethane resin having a nonvolatile content of 25% by mass was 3000 mg / L was prepared. Next, after apply | coating the coating type processing liquid on the 1st layer of an iron-type metal material with normal temperature, it was dried at 150 degreeC for 20 minute (s), and the intermediate | middle application layer was formed.
After applying solid lubricant paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) on the intermediate coating layer of iron-based metal material using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Corporation) , Held at 100 ° C. for 15 minutes, and further baked at 280 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Reference Example 3)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 145 ° C. as a black dyeing agent. Then, it immersed for 70 minutes and formed the 1st layer which has a magnetite as a main component.
Using a cerium acetylacetonate reagent, the cerium concentration was adjusted to 8500 mg / L, and 300 parts by mass of deionized water and 2 parts by mass of an anionic reactive surfactant were added to the reactor and stirred with a homomixer. A mixture of 50 parts by weight of deionized water and 1 part by weight of potassium persulfate, 287 parts by weight of deionized water, 4 parts by weight of reactive emulsifier, 60 parts by weight of methyl methacrylate, 158 parts by weight of styrene, 18 parts by weight of 2-ethylhexyl acrylate, Coating type treatment in which the water-dispersible acrylic resin obtained by blending a mixture of 4.5 parts by weight of methacrylic acid, 4.5 parts by weight of 2-hydroxyethyl methacrylate and 45 parts by weight of glycidyl methacrylate little by little simultaneously is 3000 mg / L. A liquid was prepared. Next, after apply | coating the coating type processing liquid on the 1st layer of an iron-type metallic material with normal temperature, it was made to dry at 130 degreeC for 30 minute (s), and the intermediate coating layer was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-2” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the intermediate coating layer of ferrous metal material. After that, baking was performed at 200 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Reference Example 4)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 147 ° C. as a black dyeing agent. Then, it immersed for 30 minutes and formed the 1st layer which has a magnetite as a main component.
Using ethyl polysilicate, methyltrimethoxysilane, and tetraethylsilicate (“SB-4611” manufactured by Tama Chemical Industry Co., Ltd.), a coating type treatment liquid having a silicon oxide equivalent concentration of 4 mass% was prepared. The mold treatment solution was applied on the first layer of the iron-based metal material at room temperature, and then held at 110 ° C. for 15 minutes to form an intermediate coating layer.
Using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“HMB-18” manufactured by Kawamata Laboratories Co., Ltd.) is applied onto the intermediate coating layer of ferrous metal material. After that, baking was performed at 130 ° C. for 1 hour to form a third layer. The main components and layer thicknesses of each layer are shown in Table 1, and the evaluation results are shown in Table 2.

(Comparative Example 1)
A black chromium plating film was formed on the surface of the iron-based metal material after the alkaline degreasing treatment by a method according to the example of Patent Document 2 (Japanese Patent Laid-Open No. 2007-119826).
Using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Corporation), a solid lubricating paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) was coated on the black chromium plating film of an iron-based metal material. Then, it hold | maintained at 100 degreeC for 15 minute (s), and also baked at 280 degreeC for 1 hour, and formed the solid lubricating layer. The main components and layer thickness of each layer are shown in Table 3, and the evaluation results are shown in Table 4.

(Comparative Example 2)
The iron-based metal material after the alkali degreasing treatment was subjected to a low-temperature electrolytic chromium plating treatment called a Raydent (registered trademark) treatment to form a black chromium film on the surface.
After painting a solid lubricant paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) on the black chromium film of iron-based metal material using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.) , Held at 100 ° C. for 15 minutes, and further baked 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 3, and the evaluation results are shown in Table 4.

(Comparative Example 3)
The surface of the iron-based metal material after the alkali degreasing treatment is diluted to 80.5% by mass with tap water using “Pal Black A” manufactured by Nihon Parkerizing Co., Ltd. and heated to 147 ° C. as a black dyeing agent. Then, it immersed for 25 minutes and formed the 1st layer which has a magnetite as a main component.
After applying a solid lubricant paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) on the first layer of the iron-based metal material using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Corporation) , Held at 100 ° C. for 15 minutes, and further baked 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 3, and the evaluation results are shown in Table 4.

(Comparative Example 4)
Using a zircon hydrofluoric acid reagent, a nitric acid reagent and a hydrofluoric acid reagent, an acidic chemical composition having a zirconium concentration of 250 mg / L, a nitric acid concentration of 5000 mg / L, and a fluorine concentration of 7 mg / L as free fluorine. A treatment solution was prepared. Next, the chemical conversion treatment liquid is heated to 40 ° C., and the iron-based metal material after the alkaline degreasing treatment is immersed in a chemical conversion treatment solution adjusted to pH 4.3 with an ammonia water reagent for 180 seconds to contain zirconium oxide as a main component. A film was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), a solid lubricant paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) is coated on a coating containing iron oxide as a main component. ), And then kept at 100 ° C. for 15 minutes, and further baked 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 3, and the evaluation results are shown in Table 4.

(Comparative Example 5)
In a surface conditioner obtained by diluting a surface conditioner for manganese phosphate treatment ("preparene VM" manufactured by Nihon Parkerizing Co., Ltd.) with tap water to a concentration of 0.3% by mass, 30 iron-based metal materials after alkaline degreasing treatment are used. Soaked for 2 seconds. Next, a manganese phosphate chemical conversion treatment solution (“Parphos M1A” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 14% by mass to give a total acidity of 50 points, a free acidity of 8.6 points, and an acid ratio. (Total acidity / free acidity) was adjusted to 5.8, the iron concentration was adjusted to 1.5 g / L, and the surface-adjusted iron-based metal material was immersed in a chemical conversion treatment solution heated to 98 ° C. for 900 seconds. And the membrane | film | coat which has manganese phosphate (huriolite) and manganese iron phosphate as a main component was formed.
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), a solid lubricant paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) is coated on a coating containing iron oxide as a main component. ), And then kept at 100 ° C. for 15 minutes, and further baked 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 3, and the evaluation results are shown in Table 4.

(Comparative Example 6)
A black chromium plating film was formed on the surface of the iron-based metal material after the alkaline degreasing treatment by a method according to the example of Patent Document 2 (Japanese Patent Laid-Open No. 2007-119826).
Ferrous metal material after black chrome plating film formation in surface conditioner diluted with 0.3% by mass concentration of surface conditioner for manganese phosphate treatment ("preparene 55" manufactured by Nihon Parkerizing Co., Ltd.) with tap water Was immersed for 30 seconds. Next, a manganese phosphate chemical conversion treatment solution (“Parphos M1A” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 14% by mass to give a total acidity of 50 points, a free acidity of 8.6 points, and an acid ratio. (Total acidity / free acidity) was adjusted to 5.8, the iron concentration was adjusted to 1.5 g / L, and the surface-adjusted iron-based metal material was immersed in a chemical conversion treatment solution heated to 98 ° C. for 900 seconds. And the membrane | film | coat which has manganese phosphate (huriolite) and manganese iron phosphate as a main component was formed.
Using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), a solid lubricating paint (“TC-” manufactured by Daikin Industries, Ltd.) is coated on a film mainly composed of iron-based metallic iron manganese phosphate. 7109BK "), and then kept at 100 ° C for 15 minutes, and further baked 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 3, and the evaluation results are shown in Table 4.

(Comparative Example 7)
The iron-based metal material after the alkali degreasing treatment was subjected to a low-temperature electrolytic chromium plating treatment called a Raydent (registered trademark) treatment to form a black chromium film on the surface.
In a surface conditioner prepared by diluting a surface conditioner for treating manganese phosphate ("preparene 55" manufactured by Nihon Parkerizing Co., Ltd.) with tap water to a concentration of 0.3% by mass, an iron-based metal material after forming a black chromium film is added. It was immersed for 30 seconds. Next, a manganese phosphate chemical conversion treatment solution (“Parphos M1A” manufactured by Nihon Parkerizing Co., Ltd.) is diluted with tap water to a concentration of 14% by mass to give a total acidity of 50 points, a free acidity of 8.6 points, and an acid ratio. (Total acidity / free acidity) was adjusted to 5.8, the iron concentration was adjusted to 1.5 g / L, and the surface-adjusted iron-based metal material was immersed in a chemical conversion treatment solution heated to 98 ° C. for 900 seconds. Then, a film mainly composed of manganese phosphate (huriolite) and manganese iron phosphate (huriolite) was formed.
Using a coating gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), a solid lubricating paint (“TC-” manufactured by Daikin Industries, Ltd.) is coated on a film mainly composed of iron-based metallic iron manganese phosphate. 7109BK "), and then kept at 100 ° C for 15 minutes, and further baked 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 3, and the evaluation results are shown in Table 4.

(Comparative Example 8)
Using a paint gun (low pressure spray gun “MGB40” manufactured by Asahi Sunac Co., Ltd.), solid lubricant paint (“TC-7109BK” manufactured by Daikin Industries, Ltd.) is coated on the surface of the ferrous metal material after the alkaline degreasing treatment. After that, it was kept at 100 ° C. for 15 minutes, and further baked 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 3, and the evaluation results are shown in Table 4.

  As can be seen from Tables 3 and 4, the Examples have a good uniform black appearance after the first layer formation and maintain a good uniform black appearance after the second layer formation and after the third layer formation. It was. On the other hand, Comparative Examples 1 to 3 had a good black film. In Comparative Examples 4, 5 and 8, no black film was obtained. In Comparative Examples 6 and 7, the black appearance obtained as a part of the black film obtained in the first layer was peeled off due to the formation of the second layer.

  As can be seen from Tables 3 and 4, good corrosion resistance was obtained in all examples. On the other hand, good corrosion resistance was obtained for Comparative Example 1, but the other Comparative Examples were clearly inferior to the Examples.

  As can be seen from Tables 3 and 4, in the examples, good results were obtained in all items of the coefficient of friction, the opponent aggression property, and the sliding mark appearance observation. The coefficient of friction was stable from the start to the end of the test and did not fluctuate up and down. As for the opponent's aggression, the sliding trace area of the opponent material was very small, which was a good result. As for the appearance of the sliding trace, the sliding trace had a uniform black color even after the sliding test. On the other hand, the comparative example was clearly inferior to the example.

  From the above results, it is clear that the black surface-treated iron-based metal material obtained by the present invention has excellent corrosion resistance and slidability as compared with the prior art.

Claims (9)

  A magnetite layer formed by chemical conversion treatment on the surface of the iron-based metal material, a phosphate formed on the magnetite layer, and containing at least one element selected from zinc, tin, iron, manganese, and calcium, titanium, Oxides containing at least one element selected from zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum and tungsten, and titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, A chemical conversion treatment layer containing at least one selected from fluorides containing at least one element selected from molybdenum and tungsten and a solid lubricating layer formed on the chemical conversion treatment layer are provided. Black surface-treated iron-based metal material.   The black surface-treated iron-based metal material according to claim 1, wherein the magnetite layer further contains a lithium-containing iron oxide.   The said chemical conversion treatment layer contains at least 1 sort (s) of crystalline phosphate chosen from zinc phosphate, zinc iron phosphate, manganese phosphate, manganese iron phosphate, and zinc calcium phosphate. Black surface-treated iron-based metal material.   The black surface-treated iron system according to claim 1 or 2, wherein the chemical conversion treatment layer contains at least one amorphous compound selected from zirconium oxide, titanium oxide, zirconium fluoride, titanium fluoride, and iron phosphate. Metal material.   The black surface-treated iron-based metal material according to claim 1, wherein the magnetite layer has a thickness of 0.1 μm to 5 μm.   The black surface-treated iron-based metal material according to claim 3, wherein a crystal size of the crystalline phosphate contained in the chemical conversion treatment layer is 5 μm or less.   The black surface-treated iron-based metal material according to claim 4, wherein the chemical conversion treatment layer has a thickness of 0.01 μm to 3 μm. Contacting the surface of the iron-based metal material with an aqueous solution containing at least one selected from sodium hydroxide and potassium hydroxide and an oxidizing agent to form a magnetite layer on the surface of the iron-based metal material;
The magnetite layer of the iron-based metal material is a chemical composition containing at least one element selected from zinc, iron, manganese, calcium, titanium, zirconium, hafnium, indium, tin, bismuth, vanadium, nickel, cerium, molybdenum, and tungsten. A step of contacting with a treatment liquid and forming a chemical conversion treatment layer on the magnetite layer;
A method for producing a black surface-treated iron-based metal material, comprising: applying a solid lubricant on the chemical conversion treatment layer of the iron-based metal material to form a solid lubricant layer.   The method for producing a black surface-treated iron-based metal material according to claim 8, wherein the aqueous solution used for forming the magnetite layer further contains lithium hydroxide.