CN1572912A - Method of treating metal surface and metal surface treated thereby - Google Patents
Method of treating metal surface and metal surface treated thereby Download PDFInfo
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- CN1572912A CN1572912A CNA200410046519XA CN200410046519A CN1572912A CN 1572912 A CN1572912 A CN 1572912A CN A200410046519X A CNA200410046519X A CN A200410046519XA CN 200410046519 A CN200410046519 A CN 200410046519A CN 1572912 A CN1572912 A CN 1572912A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/12—Electrolytic coating other than with metals with inorganic materials by cathodic processes on light metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
It is an object of the present invention to provide a method of metal surface treatment and a surface treated metal thereby, which has excellent corrosion resistance and can form a coat having high corrosion resistance on metal substrates such as iron, zinc, aluminum and magnesium. A method of metal surface treatment comprising the step of forming a chemical conversion coat on the surface of ametal article tobe treatedbya chemical conversion treatment reaction by a chemical conversion treatment agent containing a zirconium-containing compound and a fluorine-containing compound, wherein said chemical conversion treatment reaction is conducted through cathodic electrolysis treatment.
Description
Technical Field
The present invention relates to a metal surface treatment method and a surface-treated metal.
Background
In order to improve properties such as corrosion resistance, the surface of a metal material is usually subjected to surface treatment. One of the well-known surface treatments with a chemical conversion treatment agent containing a zirconium compound is known. This surface treatment method is carried out by a non-electrolytic reaction in which a metal to be treated undergoes a dissolution reaction by the action of a treatment solution, dissolved metal ions react with fluorine ions to produce fluoride, and the hydrogen ions are reduced to produce hydrogen gas, and the fluorine ions are replaced by hydroxide ions by hydrolysis of zirconium complex ions to raise the pH in the vicinity of the object to be treated, thereby depositing insoluble zirconium salts formed from zirconium hydroxide/fluoride and the fluoride of the metal to be treated and the metal salt of the object to be treated on the metal surface.
In the above-mentioned electroless reaction of the zirconium chemical conversion treatment agent, it is extremely difficult to cause the reaction to occur uniformly over the entire surface of the object to be treated, and therefore, it is difficult to form a uniform coating film having sufficient denseness. Further, the coating layer contains a large amount of oxide and fluoride formed by etching of the raw material, and the corrosion resistance thereof is deteriorated. In addition, in the non-electrolytic reaction, since the anode and cathode reactions proceed on the same surface, the chemical conversion coating is formed and then the chemical conversion reactivity is lowered, so that only a thin and rough chemical conversion coating of a raw material metal, an alkali metal, or the like can be obtained, and it is difficult to obtain a uniform and dense protective film.
As described above, it is difficult to impart sufficient rust inhibitive performance to a treated object with a chemical conversion coating obtained by a non-electrolytic reaction using a zirconium chemical conversion treatment agent, particularly to a treated objectsuch as an iron-based substrate or a zinc-based substrate having low reactivity with a chemical conversion treatment agent. Further, for surface treatment of aluminum-based substrates and magnesium-based substrates, it is also necessary to form a coating layer having a better chemical conversion property to achieve a higher level of corrosion resistance. Therefore, there is a need for a metal surface treatment process that can form a more uniform and dense chemical conversion coating.
Further, as a metal surface treatment method, a method of performing surface treatment by electrolytic reaction is also known. (see patent documents 1 and 2, for example). However, these methods are methods for treating phosphate compounds and titanium compounds, and are not methods for forming a uniform and dense zirconium chemical conversion coating. In particular, the chemical conversion treatment method using phosphate has a problem of increasing environmental load due to eutrophication. Further, in this treatment method, sludge is generated by reaction with metal ions in the phosphating solution. If the chemical conversion treatment is performed with a titanium-based compound, a sufficiently high level of corrosion resistance cannot be achieved.
Patent document 3 discloses a composition for surface treatment containing (a) a compound containing at least one element selected from Ti, Zr, Hf and Si and (B) a fluorine-containing compound as a Hf supply source, wherein a total molar weight of Ti, Zr, Hf and Si in the compound as the component (a) is represented by a, a molar weight of all fluorine atoms in the fluorine-containing compound as the component (B) in terms of Hf is represented by B, and a ratio K/B of the two is in a range of 0.06. ltoreq. k.ltoreq.0.18, and a method for surface treatment of a metal by bringing the composition into contact with a metal surface.
However, in this method, whena surface treatment composition in which a fluorine-containing element and a zirconium-containing compound are dissolved is used for electrolytic treatment, and chemical conversion treatment is performed by such electrolytic treatment, since a large excess of fluorine and alkali metal is present in the solution, it is difficult to obtain the effect of protecting the cathode even when an electrolytic voltage is applied to the material to be treated, and the formed chemical conversion coating contains a large amount of fluoride and an alkali metal compound, and thus the requirement of corrosion resistance cannot be sufficiently satisfied. In addition to this, a problem of corrosion of the equipment by a large amount of fluorine occurs.
[ patent document 1]Japanese patent application laid-open No. 2000-234200
[ patent document 2]Japanese laid-open patent application publication No. 2002-
[ patent document 3]International publication No. 02/103080
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a metal surface treatment method which can form a coating layer excellent in corrosion resistance and can form a coating layer excellent in corrosion resistance for a metal substrate of iron, zinc, aluminum, magnesium, or the like, and a surface-treated metal treated by such a method.
The present invention relates to a metal surface treatment method for forming a chemical conversion coating on the surface of a metal object by a chemical conversion treatment reaction using a chemical conversion treatment agent containing a zirconium-containing compound and a fluorine-containing compound, wherein the chemical conversion treatment reaction is performed by cathodic electrolysis.
Preferably, the cathodic electrolysis treatment is performed after adjustment in a chemical conversion treatment agent, and after adjustment, the chemical conversion treatment agent has a zirconium-containing compound concentration of 10 to 100000ppm in terms of zirconium metal concentration, a ratio of the total mass of zirconium metal to the total mass of fluorine elements (amount of zirconium/amount of fluorine) of 0.2 to 1.0, and a pH of 1 to 6.
Preferably, the cathodic electrolysis treatment is carried out at a voltage of 0.1-40V and a current density of 0.1-30A/dm2Under the conditions of (1).
Preferably, the metal object to be treated is at least one substrate selected from the group consisting of an aluminum-based substrate, a zinc-based substrate, and a magnesium-based substrate.
The present invention also relates to a surface-treated metal characterized by having a chemical conversion treatment coating obtained by the above method.
Detailed Description
The following is a detailed description of the present invention.
The metal surface treatment method of the present invention is a method of forming a chemical conversion coating by subjecting a metal surface to cathodic electrolysis treatment using a chemical conversion treatment agent containing a zirconium-containing compound and a fluorine-containing compound. A dense and uniform coating can be produced by the cathodic electrolysis treatment reaction as compared with a chemical conversion treatment coating formed by a non-electrolytic treatment. Therefore, even in the case where the coating layer is formed in the same amount as that of the chemical conversion coating layer formed by the non-electrolytic treatment, the method of the present inventioncan form the chemical conversion coating layer excellent in corrosion resistance.
When a chemical conversion treatment agent containing a zirconium-containing compound and a fluorine-containing compound is used for an electrolytic reaction, an anticorrosive chemical conversion coating having excellent corrosion resistance can be obtained, and the coating has better corrosion resistance than a chemical conversion coating obtained by an electrolytic reaction using a titanium-based or phosphate-based chemical conversion treatment agent. Therefore, this method is a method which is demanded and desirable in a wide range of uses.
When a chemical conversion coating film is formed on an aluminum-based substrate by a non-electrolytic reaction using a chemical conversion treatment agent containing a zirconium-containing compound and a fluorine-containing compound, etching of a raw material first occurs as shown in the following reaction formulae (1) and (2). Hydrolysis of the zirconyl fluoride salt mainly shown in the following reaction formulas (3) to (5) occurs next, and a zirconium-based chemical conversion coating is formed.
That is, when a coating layer is formed by electroless treatment, since the chemical conversion coating layer is formed by the reaction of the above reaction formulae (1) to (5), a zirconium-based chemical conversion coating layer containing much fluorine is formed, and the corrosion resistance of the coating layer is poor. When the cathodic electrolysis treatment is carried out using a chemical conversion treatment agent containing a zirconium-containing compound and a fluorine-containing compound, the reaction that generates hydrogen gas mainly occurs on the metal surface, and the cathodic corrosion of the base metal is prevented, so that the metal surface is not etched, and the fluoride of the metal to be treated is not generated. Therefore, a coating layer containing relatively stable zirconia is deposited in the vicinity of the metal surface by hydrolysis reaction of the zirconium complex ion, and a dense and stable protective film having a low fluorine content is formed. Further, when a chemical conversion coating is formed on an iron-based or zinc-based substrate by cathodic electrolysis using the chemical conversion treatment agent, it is also possible to form a coating layer having a reduced fluorine content, and therefore, this method is presumed to improve the corrosion resistance.
In general, when an aluminum-based substrate is surface-treated, aluminum ions are accumulated in the composition of the balance bath. In this case, if the accumulated aluminum is 500ppm or more as in the treatment by the non-electrolytic method, the chemical conversion reactivity is hindered, and it is necessary to dispose of water supply, waste, and the like. On the other hand, if cathodic electrolysis is used, the coating is carried out in a state where the amount of aluminum ion etching is small (the conversion rate of the coating is high), and the influence on the accumulated aluminum ions is small, so that water supply and waste disposal are unnecessary.
The zirconium-containing compound is not particularly limited as long as it is a zirconium-containing compound, and examples thereof include fluorozirconic acid, lithium salts thereof, sodium salts thereof, potassium salts thereof, ammonium salts thereof, zirconium fluoride, and zirconium oxide. These zirconium-containing compounds may be used alone, or 2 or more kinds may be used in combination.
The fluorine-containing compound is not particularly limited as long as it is a compound containing fluorine, and examples thereof include hydrofluoric acid, ammonium fluoride, ammonium hydrofluoride, sodium fluoride, sodium hydrofluoride and the like in addition to the above zirconium fluoride and the like. These fluorine-containing compounds may be used alone, or 2 or more kinds may be used in combination.
In the metal surface treatment method of the present invention, the cathodic electrolysis treatment is preferably performed after the chemical conversion treatment agent is adjusted, and after the adjustment, when the concentration of the zirconium-containing compound in the chemical conversion treatment agent is converted into the concentration of zirconium metal, the lower limit is 10ppm and the upper limit is 100000ppm, and the lower limit, which is the ratio of the total mass of zirconium metal to the total mass of fluorine element (amount of zirconium/amount of fluorine), is 0.2, the upper limit is 1.0, and the lower limit of the pH value is 1 and the upper limit is 6. When the cathodic electro-treatment is performed after the adjustment in this way, a chemical conversion coating containing a small amount of fluorine can be formed, and therefore, the corrosion resistance can be improved.
In the above-mentioned cathodic electrolysis treatment, the concentration of the zirconium-containing compound and the amount of zirconium/the amount of fluorine are adjusted to the above-mentioned predetermined ranges, and examples thereof include a method in which the total zirconium concentration and the total fluorine concentration in the chemical conversion treatment agent are measured by using an atomic absorption spectrometer and ion chromatography, respectively, and the zirconium-containing compound and the fluorine-containing compound are supplied to the treatment solution based on the measurement results. Examples of the method for adjusting the pH value to the predetermined range include a method in which nitric acid or ammonium hydroxide is supplied to the treatment solution while measuring the pH value with a pH meter.
In the cathodic electrolysis treatment of the present invention, the chemical conversion treatment agent in the treatment bath is preferably adjusted so that the lower limit is 10ppm and the upper limit is 100000ppm in terms of the concentration of the zirconium-containing compound in the zirconium metal. If the concentration is less than 10ppm, the zirconium compound deposited on the metal surface is insufficient, and therefore, the corrosion resistance may not be improved. If the concentration exceeds 100000ppm, the corrosion resistance cannot be further improved and waste is caused. The lower limit is more preferably 30ppm, and the upper limit is more preferably 5000 ppm.
In the cathodic electrolysis treatment of the present invention, the chemical conversion treatment agent in the treatment bath is preferably adjusted to have a lower limit of 0.2 and an upper limit of 1.0 as the ratio (amount of zirconium/amount of fluorine) of the total mass of zirconium metal (the total mass of all zirconium contained as zirconium metal in the chemical conversion treatment agent) to the total mass of fluorine (the total mass of all fluorine contained in the chemical conversion treatment agent). If the ratio is less than 0.2, the amount of fluorine becomes excessive, which may prevent the cathodic electrolysis treatment from forming a chemical conversion coating. The chemical conversion coating formed has a high fluorine content and poor corrosion resistance. If the ratio exceeds 1.0, the total amount of fluorine is insufficient, and precipitation of metal salts may be caused. The lower limit is more preferably 0.25, and the upper limit is more preferably 0.8.
In the cathodic electrolysis treatment in the present invention, the chemical conversion treatment agent in the treatment bath is preferably adjusted to a pH within a range having a lower limit of 1 and an upper limit of 6. If the pH is less than 1, the zirconium compound is hardly precipitated on the metal surface, so that a sufficient coating amount cannot be obtained, and the corrosion resistance may be lowered. If the pH exceeds 6, a sufficient coating amount cannot be obtained, which is not preferable. The lower limit is more preferably 2, and the upper limit is more preferably 5.
The chemical conversion treatment agent may contain metal ions such as titanium, manganese, silicon, zinc, cerium, iron, molybdenum, vanadium, trivalent chromium, and magnesium in addition to the above components; tannic acid, imidazoles, triazines, triazoles, guanidines, hydrazines, biguanides, phenol resins, silane coupling agents, colloidal silica, amines, phosphoric acid, and other rust inhibitors; a surfactant; a chelating agent; resins, and the like.
In the metal surface treatment method of the present invention, the electrolytic treatment is performed by using the object to be treated as a cathode.
The lower limit of the voltage for the cathodic electrolysis is preferably 0.1V and the upper limit thereof is preferably 40V. If the voltage is less than 0.1V, the amount of the coating layer formed is reduced, which may result in deterioration of the corrosion resistance. If the voltage exceeds 40V, the effect of increasing the coating amount is saturated, which may be an adverse factor in energy. The lower limit is more preferably 1V, and the upper limit is more preferably 30V.
The lower limit of the preferred current for the cathodic electrolysis is 0.1A/dm2The upper limit is 30A/dm2. E.g. current less than 0.1A/dm2In the case, the amount of the coating layer formed is reduced, which may result in deterioration of corrosion resistance. E.g. more than 30A/dm2In this case, the effect of increasing the coating amount is saturated, and this may become a negative factor in energy. The lower limit is more preferably 0.2A/dm2The upper limit is more preferably 10A/dm2。
The lower limit of the treatment time of the cathodic electrolysis treatment is preferably 3 seconds and the upper limit thereof is preferably 180 seconds. If the treatment time is less than 3 seconds, the amount of the coating layer formed is reduced, and the corrosion resistance is deteriorated. If it exceeds 180 seconds, the effect of increasing the coating amount is saturated, and this may be an energy disadvantage.
The lower limit of the treatment temperature of the electrolytic treatment is preferably 10 ℃ and the upper limit thereof is preferably 70 ℃. If the temperature is less than 10 ℃, the amount of the coating layer formed is reduced and the corrosion resistance is deteriorated. If the temperature exceeds 70 ℃, the effect of increasing the coating amount is saturated and may become a negative factor in energy. It is to be noted that the treatment may be carried out at normal temperature without particularly controlling the lower limit of the treatment temperature.
In the cathodic electrolysis treatment, the electrode used as the anode is not particularly limited as long as it is insoluble in the chemical conversion treatment agent. For example: stainless steel, platinized titanium, niobite titanium, carbon, iron, nickel, zinc, etc.
Examples of the object to be treated which is suitable for the metal surface treatment method of the present invention include iron-based substrates, aluminum-based substrates, zinc-based substrates, magnesium-based substrates, and the like. The iron, aluminum, zinc-based substrate and magnesium-based substrate are an iron-based substrate made of iron and/or an alloy thereof, an aluminum-based substrate made of aluminum and/or an alloy thereof, a zinc-based substrate made of zinc and/or an alloy thereof, and a magnesium-based substrate made of magnesium and/or an alloy thereof, respectively. In particular, the method of the present invention can form a chemical conversion coating having sufficient corrosion resistance even on iron-based and zinc-based substrates on which a conventional zirconium-based chemical conversion treatment agent cannot achieve sufficient corrosion resistance and a phosphate-based chemical conversion treatment agent is generally used. Therefore, the method of the present invention is also suitable for the purpose of dephosphorylation of a chemical conversion treatment agent for iron-based and zinc-based substrates. The method for treating a metal surface of the present invention is used for chemical conversion treatment of an object to be treated comprising a plurality of metal substrates among an iron-based substrate, an aluminum-based substrate, a zinc-based substrate, and a magnesium-based substrate, and can impart excellent corrosion resistance to various objects to be treated.
The iron-based base material is not particularly limited, and examples thereof include cold-rolled steel sheets and hot-rolled steel sheets. The aluminum base material is not particularly limited, and examples thereof include 5000 # aluminum alloy and 6000 # aluminum alloy.
The zinc-based base material is not particularly limited, and examples thereof include galvanized steel sheets such as galvanized steel sheets, zinc nickel-plated steel sheets, galvanized iron steel sheets, zinc chromium-plated steel sheets, zinc aluminum-plated steel sheets, zinc titanium-plated steel sheets, zinc magnesium-plated steel sheets, and zinc manganese-plated steel sheets, and galvanized steel sheets such as zinc-based steel sheets, and zinc alloy-plated steel sheets.
The magnesium-based base material is not particularly limited, and examples thereof include magnesium metal and magnesium alloy produced by rolling, die casting, fusion casting, or the like. The magnesium alloy is not particularly limited, and examples thereof include AZ31, AZ91, AZ91D, AM60, AM50, and AZ 31B. By using the above metal surface treatment method, the chemical conversion treatment can be simultaneously performed on the iron, aluminum, zinc and magnesium base materials.
Preferably, the above-mentioned metal watch is usedThe lower limit of the amount of zirconium in the chemical conversion coating formed by the surface treatment method is 10mg/m2With an upper limit of 300mg/m2. This can impart excellent corrosion resistance to the substrate. If the amount of zirconium in the chemical conversion coating is less than 10mg/m2The corrosion resistance may be insufficient. Even if the amount of zirconium in the chemical conversion coating is more than 300mg/m2The effect is not improved and waste is not caused. The lower limit is more preferably 20mg/m2The upper limit is more preferably 150mg/m2。
Preferably, the surface of the metal base material is subjected to degreasing treatment, degreasing post-washing treatment, pickling post-washing treatment, and the like, before cathodic electrolysis treatment using the chemical conversion treatment agent.
The degreasing treatment is performed to remove oil and dirt adhering to the surface of the substrate. The method is to use degreasing washing liquid without phosphorus and nitrogen, and the degreasing washing liquid is usually soaked for a plurality of minutes at the temperature of 30-55 ℃. If necessary, a preliminary degreasing treatment may be performed before the degreasing treatment.
The post-degreasing water-washing treatment is carried out to wash out the degreaser after the degreasing treatment with water. The method is to perform spray washing treatment 1 time or more than 1 time with a large amount of washing water.
The acid washing treatment is carried out by immersing the substrate in an acid washing agent such as sulfuric acid containing an oxidizing agent or a mixed acid washing solution of sulfuric acid and nitric acid at a temperature of 30 to 60 ℃ for several minutes. The washing treatment after the acid washing can be carried out by a conventionally known method. Alternatively, the cathodic electrolysis treatment may be followed by a water washing treatment.
The present invention also relates to a surface-treated metal having a chemical conversion treatment coating obtained by the above metal surface treatment method. When a corrosion resistant primer such as cationic plating, powder coating, thermosetting resin, or the like is further formed on the chemical conversion coating, the surface-treated metal of the present invention has excellent corrosion resistance. The surface-treated metal of the present invention may be coated with, but not limited to, cationic plating, powder coating, roll coating, and the like. The cationic plating is not particularly limited, and a known cationic plating coating material composed of an aminated epoxy resin, an aminated acrylic resin, a vulcanized epoxy resin, or the like can be applied.
The metal surface treatment method of the present invention is a method for obtaining a chemical conversion coating by subjecting a chemical conversion treatment agent containing a zirconium-containing compound and a fluorine-containing compound to cathodic electrolysis, and thus a treatment material having excellent corrosion resistance can be obtained. Further, the present invention can impart excellent corrosion resistance to iron, zinc, aluminum, or magnesium-based substrates without using a metal such as hexavalent chromium, which is a preferable method from the environmental point of view.
Particularly, when the concentration of the zirconium-containing compound in the chemical conversion agent is adjusted to a value of 10 to 100000ppm in terms of zirconium metal, the ratio of the mass of the total zirconium metal to the mass of the total fluorine (amount of zirconium/amount of fluorine) is adjusted to a range of 0.2 to 1.0, and the cathode electrode treatment is performed after the pH is adjusted to a range of 1 to 6, a chemical conversion coating having a small fluorine content can be formed, thereby improving the corrosion resistance.
Since the chemical conversion treatment agent used in the present invention can impart excellent corrosion resistance to the treated object without containing phosphate ions, this method does not cause environmental problems such as eutrophication, and can suppress the amount of sludge.
The metal surface treatment method of the present invention is constituted by the above-mentioned parts, and the corrosion resistance of the object to be treated can be improved as compared with a method of performing electrolytic treatment by electroless treatment or using a titanium-based or phosphoric-acid-based treating agent. Further, since this method is a method capable of imparting excellent corrosion resistance to all materials of iron-based, aluminum-based, zinc-based, and magnesium-based substrates, it is extremely suitable for use in an object to be treated composed of a plurality of substrates such as iron-based, aluminum-based, zinc-based, and magnesium-based substrates, for example, automobile bodies and parts. It is also a method which has a small environmental load and can suppress the generation of sludge.
[ examples]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "part" and "%" mean "part by mass" and "% by mass", unless otherwise specified.
Examples 1 to 13 and comparative examples 1 to 7
Preparation of chemical conversion treatment agent
Zirconium hydrofluoric acid, zirconium ammonium fluoride, titanium hydrofluoric acid, phytic acid, aluminum nitrate, hydrofluoric acid, phosphoric acid, water-soluble phenol, and tannic acid, which were zirconium-containing compounds and fluorine-containing compounds, were mixed, and ion-exchanged water was added to prepare chemical conversion treatment agents shown in table 1.
Production of test plate
A70 mm X150 mm X0.8 mm A1100 plate (manufactured by NIPPON TEST BOARD Co., Ltd.) was degreased by dipping it in an aqueous solution of 3% alkaline degreaser (SURFCCLEANER 322N8, manufactured by NIPPON PAINT Co., Ltd.) at 70 ℃ for 30 seconds. After the spray treatment for 30 seconds, the plate was washed with tap water, and then immersed in an aqueous solution of 25% acid pickling agent (NP Conditioner2000, manufactured by Nippon paint Co., Ltd.) at a temperature of 70 ℃ for 30 seconds. The resultant was sprayed with tap water for 30 seconds to wash with water. Next, cathode electrolytic treatment was performed using SUS304 as an anode and the prepared chemical conversion treatment agent under the conditions shown in table 1. Further, the amount of zirconium (mg/m) in the coating was measured using "XRF 1700" (fluorescence X-ray analysis apparatus manufactured by Shimadzucorporation)2) And F/Zr mass ratio.
In the cathodic electrolysis treatment, the concentration of zirconium metal, the zirconium/fluorine mass ratio and the pH value in the chemical conversion agent in the treatment bath were adjusted as shown in Table 1.
The total zirconium concentration and the total fluorine concentration of the chemical conversion treatment agent in the treatment bath were measured by an atomic absorption analyzer NOVA a330 manufactured by science corporation and an ion chromatograph DX-120 manufactured by Dionex corporation, respectively, and based on the measurement results, zirconium fluoride and hydrofluoric acid were supplied to the treatment solution to adjust the total zirconium concentration and the total fluorine concentration. Further, the pH value of the chemical conversion treatment agent in the treatment liquid was measured by using a pH meter D-24 manufactured by Higherkinson Seisakusho, and nitric acid or hydroxylammonium was supplied to the treatment liquid to adjust the pH value based on the measurement result.
Evaluation of physical Properties of test sheet
The corrosion resistance of the test plate was evaluated as follows according to the following methods.
<resist Property>
A Salt Spray Test (SST) was performed at 5% (2000 hours) in accordance with JIS Z2371, and then the rust percentage of the treated plate was examined. The rust area of the surface of the treated plate was visually evaluated according to the following evaluation criteria.
10: no occurrence of rust
9: the area of rust spots is less than 10%
8: the area of rust spots is less than 20%
7: the area of rust spots is less than 30%
6: the area of rust spots is less than 40%
5: the area of rust spots is less than 50%
4: the area of rust spots is less than 60%
3: the rusty spot occurrence area is less than 70 percent
2: the area of rust spots is less than 80%
1: the area of rust spots is less than 90 percent
[ Table 1]
| Item | Examples | Comparative example | ||||||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | |||
| Test board | A1100 | A1100 | ||||||||||||||||||||
| To Theory of things Agent for treating cancer | Zirconium fluoacid (mass% of Zr) | 0.01 | - | - | - | 0.01 | - | - | - | - | - | - | - | 0.01 | 0.01 | 0.01 | 0.01 | - | - | - | Phosphate ion 2.1 | |
| Zirconium ammonium fluoride (mass% of Zr) | - | 0.1 | 0.1 | 0.1 | - | 0.2 | 0.01 | 1.00 | 0.01 | 0.01 | 0.01 | 0.01 | - | - | - | - | 0.01 | - | - | Nitrate ion 2 | ||
| Fluotitanic acid (mass% of Ti) | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | 0.3 | Nickel ion 0.025 | ||
| Phytic acid (mass%) | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | 0.2 | Zinc ion 1.7 | ||
| Aluminium nitrate (mass% of Al) | - | 0.1 | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | ||
| Zr/F mass ratio in treating agent | 0.71 | 0.78 | 0.75 | 0.77 | 0.81 | 0.65 | 0.73 | 0.71 | 0.79 | 0.71 | 0.69 | 0.78 | 0.66 | 0.11 | 0.18 | 0.12 | 0.14 | - | 0.17(Ti/F) | - | ||
| Phosphoric acid (% by mass) | - | - | 0.001 | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | ||
| Water-soluble phenol (% by mass) | - | - | - | 0.05 | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | - | ||
| Tannic acid (% by mass) | - | - | - | - | 0.05 | - | - | - | - | 0.05 | - | - | - | - | - | 0.05 | - | 0.05 | - | - | ||
| Treatment of Condition | PH | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 4.5 | 3.5 | 3.5 | 3.5 | 2.0 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 2 | 3 | 3.5 | 3.5 | 2.2 | |
| Temperature (. degree.C.) | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | RT | 50 | 50 | 50 | 50 | 50 | RT | 50 | 50 | 40 | ||
| Time (seconds) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 5 | 30 | 15 | 30 | 180 | 30 | 20 | 180 | 30 | 30 | 120 | ||
| Electrolysis conditions (voltage: V) | -10 | -10 | -10 | -10 | -10 | -10 | -10 | -10 | -5 | -20 | -20 | -20 | -10 | - | - | - | - | -10 | -10 | -10 | ||
| Conditions of electrolysis (Current Density: A/dm)2)* | -0.5 | -0.5 | -0.5 | -0.5 | -0.5 | -0.5 | -0.5 | -0.5 | -0.3 | -1.0 | -1.0 | -1.0 | -0.5 | - | - | - | - | -0.5 | -0.5 | -0.5 | ||
| Coating layer Characteristics of | Zr amount (mg/m) in the coating2) | 60 | 72 | 57 | 49 | 55 | 62 | 62 | 73 | 41 | 35 | 36 | 51 | 70 | 58 | 37 | 39 | 35 | 0 | 70(Ti) | - | |
| Mass ratio of F/Zr in coating | 0.62 | 0.65 | 0.66 | 0.60 | 0.64 | 0.70 | 0.63 | 0.60 | 0.56 | 0.58 | 0.63 | 0.63 | 0.61 | 0.87 | 0.91 | 0.86 | 0.82 | - | - | - | ||
| SST score (SST2000h) | 8 | 9 | 8 | 8 | 9 | 7 | 8 | 8 | 7 | 7.5 | 7 | 9 | 8.5 | 3 | 2 | 2 | 2 | 1 | 3 | 1 | ||
Represents cathodic electrolysis treatment
Zr/F mass ratio by fluorescent X-ray measurement
As can be seen from Table 1, the materials obtained by the non-electrolytic treatment (comparative examples 1 to 5) had inferior corrosion resistance to those obtained by the cathodic electrolysis. Thus, the coating layer formed by the cathodic electrolysis treatment can improve the corrosion resistance. Further, when fluorinated titanic acid (comparative example 6) was used as the chemical conversion treatment agent, the corrosion resistance was inferior to that when the zirconium-containing chemical conversion treatment agent was used.
Examples 14 to 21 and comparative examples 8 to 11
Preparation of chemical conversion treatment agent
Zirconium hydrofluoric acid as a zirconium-containing compound and a fluorine-containing compound was mixed with a nitrate as another metal-containing compound, and ion-exchanged water was added to prepare a chemical conversion treatment agent as shown in table 2.
Production of test plate
SPCC-SDsheets (manufactured by Nippon test plate Co., Ltd.) of 70mm X150 mm X0.8 mm, galvanized steel sheets (GA steel sheets, manufactured by Nippon test plate Co., Ltd.) of 70mm X150 mm X0.8 mm, and 5182-series aluminum sheets (manufactured by Nippon test plate Co., Ltd.) of 70mm X150 mm X0.8 mm were degreased by spraying an aqueous solution of 2% alkaline degreaser (SURFCCLEANER 53, manufactured by Nippon paint Co., Ltd.) at a temperature of 40 ℃ for 2 minutes. After the treatment by spraying with tap water for 30 seconds, the prepared chemical conversion treatment agent was subjected to cathodic electrolysis under the conditions shown in Table 2 using SUS304 as an anode. Subsequently, the mixture was sprayed with tap water for 30 seconds and then washed with purified water for 30 seconds. Then, it was plated using electroplating POWERNICS110 (electroplating paint manufactured by Nippon paint Co., Ltd.) to a dry film thickness of 20 μm, washed with water and then burned at a temperature of 170 ℃ for 20 minutes to prepare a test plate.
The total zirconium concentration and the total fluorine concentration in the chemical conversion treatment agent in the treatment solution were measured by using an atomic absorption analyzer NOVAA330 manufactured by chemical corporation and an ion chromatograph DX-120 manufactured by Dionex gmbh of japan, and according to the measurement results, zirconium fluoride and hydrofluoric acid were supplied to the treatment solution, and the total zirconium concentration and the total fluorine concentration were adjusted to values shown in table 2. Further, the pH of the chemical conversion treatment agent in the treatment solution was measured by using a pH meter D-24 manufactured by Higherkinson Seisakusho, and according to the measurement results, nitric acid or hydroxylammonium was supplied to the treatment solution, and the pH was adjusted to the values shown in Table 2.
Comparative example 12
Production of test plate
An SPCC-SD sheet of 70 mm. times.150 mm. times.0.8 mm was degreased by spray treatment with an aqueous solution of 2% alkaline degreaser (SURFCCLEANER 53, manufactured by Nippon paint Co., Ltd.) at a temperature of 40 ℃ for 2 minutes. After the water washing by spraying it with tap water for 30 seconds, surface conditioning was carried out at normal temperature for 30 seconds using SURFFINE 5N-8M (a surface conditioner manufactured by Nippon paint Co., Ltd.), followed by cathodic electrolysis under conditions shown in Table 2 using SUS304 as an anode and SURFFINE SD6350 (a zinc phosphate treating agent manufactured by Nippon paint Co., Ltd.). Then, the mixture was sprayed with tap water for 30 seconds and washed with water, and then sprayed with purified water for 30 seconds and washed with water. Further, the plate was plated with the plating POWERNICS110 (plating coating produced by Nippon paint Co., Ltd.) so that the dry film thickness was 20 μm, washed with water and then fired at a temperature of 170 ℃ for 20 minutes to prepare a test plate.
Comparative example 13
A test plate was prepared in the same manner as in comparative example 12 except that the cathodic electrolysis was replaced with a non-electrolytic treatment.
Evaluation of physical Properties of test sheet
The secondary adhesion of the test plate was evaluated by the following method.
<Secondary Adhesivity (SDT)>
On the resulting test plate, 2 slits as deep as the base material were longitudinally scribed in parallel, and immersed in a 5% NaCl aqueous solution at a temperature of 50 ℃ for 480 hours. After that, the slit portion was peeled off with an adhesive tape, and the peeling of the paint was observed. Theevaluation results are shown in table 2.
○ peeling width less than 3mm
X: peeling width of 3mm or more
<sludge>
1m per 1L of chemical conversion treatment agent2The cold-rolled steel sheet (SPCC-SD), galvanized steel sheet, and 5182-series aluminum (Al) of (1), and the haze in the chemical conversion treatment agent was visually observed.
○ no turbidity
X: with turbidity
[ Table 2]]
| Examples | Comparative example | ||||||||||||||
| 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 8 | 9 | 10 | 11 | 12 | 13 | ||
| Test board | SPC | SPC | SPC | SPC | SPC | SPC | GA | 5182 | SPC | SPC | GA | 5182 | SPC | SPC | |
| To Theory of things Agent for treating cancer | Zirconium fluoacid (of Zr) Mass%) | 0.010 | 0.010 | 0.010 | 0.050 | 0.100 | 0.200 | 0.010 | 0.010 | 0.010 | 0.010 | 0.010 | 0.010 | S U R F D I N E S D 6 3 5 0 | S U R F D I N E S D 6 3 5 0 |
| Treating agent Medium Zr/F Mass ratio of | 0.769 | 0.769 | 0.769 | 0.794 | 0.769 | 0.769 | 0.769 | 0.769 | 0.167 | 0.067 | 0.063 | 0.111 | |||
| Magnesium nitrate (of Mg) Mass%) | - | 0.01 | 0.01 | 0.01 | 0.01 | 0.01 | - | - | - | - | - | - | |||
| Zinc nitrate (of Zn) Mass%) | - | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | - | - | - | - | - | - | |||
| Resin: water solubility Epoxy resin Fat (substance) Measuring) | - | - | 0.01 | - | 0.01 | - | - | - | - | - | - | - | |||
| To Theory of things Strip for packaging articles Piece | pH | 3.5 | 4.0 | 4.0 | 4.3 | 4.1 | 3.9 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | - | - |
| Temperature of (℃) | 40 | RT | 30 | 30 | 30 | 30 | 40 | 40 | 40 | 60 | 60 | 60 | - | - | |
| Time of day (second) | 30 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 300 | 60 | 60 | 60 | - | - | |
| Electrolytic strip Piece (electric power) Pressing: v) | -10 | -20 | -15 | -25 | -20 | -10 | -10 | -10 | - | - | - | - | -10 | - | |
| Electrolytic strip Piece (electric current) Density: A/dm2) | -0.5 | -0.8 | -0.5 | -1.1 | -1.0 | -0.6 | -0.5 | -0.5 | - | - | - | - | -0.5 | - | |
| coating composition Layer(s) Specially for treating diabetes Property of (2) | In the coating Amount of Zr (mg/ m2) | 60 | 124 | 122 | 128 | 135 | 121 | 133 | 70 | 65 | 29 | 25 | 31 | - | - |
| In the coating F/Zr mass Ratio of measurement | 0.70 | 0.66 | 0.64 | 0.59 | 0.69 | 0.62 | 0.65 | 0.60 | 0.82 | 0.88 | 0.81 | 0.80 | - | - | |
| SDT | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | × | × | ○ | ○ | |
| Sludge | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | |
Represents cathodic electrolysis treatment
ZR/F Mass ratio determined by fluorescent X-ray
As can be seen from Table 2, the materials obtained by the non-electrolytic treatment (comparative examples 8 to 13) had inferior secondary adhesion to the materials obtained by the cathodic electrolysis (examples 14 to 21). Thus, the coating layer formed by the cathodic electrolysis treatment can improve the secondary adhesion. Furthermore, examples 14 to 18 suppressed the generation of sludge as compared with the electrolytic treatment (comparative example 12) and the non-electrolytic treatment (comparative example 13) using a zinc phosphate treatment agent.
Examples 22 to 23
Preparation of chemical conversion treatment agent
Zirconium-containing compounds, fluorine-containing compounds, zirconium hydrofluoric acid, zirconium ammonium fluoride, and γ -aminopropyltriethoxysilane were mixed, and ion-exchanged water was added to prepare chemical conversion treatment agents shown in table 3.
Production of test plate
A magnesium alloy AZ91D plate of 70 mm. times.150 mm. times.2.0 mm produced by a thixotropy molding method was degreased by spray-treating it with an aqueous solution of 1% alkaline degreasing agent (SURF MAGDINE SF120 CLEANER, manufactured by Japan paint) at a temperature of 50 ℃ for 2 minutes. After spray-treating it with tap water for 30 seconds, it was spray-treated with an aqueous solution of 1% acid pickling agent (SURFMAGDING SF400, manufactured by Japan paint) at 50 ℃ for 2 minutes to be acid-pickled. The resultant was sprayed with tap water for 30 seconds to carry out water washing. Then, it was spray-treated with a 10% aqueous solution of a detergent (SURF MAGDINE SF300, manufactured by Japan paint) at 60 ℃ for 5 minutes for acid washing. Subsequently, the resultant was sprayed with tap water for 30 seconds and then washed with water, and the prepared chemical conversion agent was subjected to cathodic electrolysis under the conditions shown in Table 3 using SUS304 as an anode. Subsequently, the mixture was sprayed with tap water for 30 seconds and then washed with purified water for 30 seconds.
The total zirconium concentration and the total fluorine concentration in the chemical conversion treatment agent in the treatment bath were measured by an atomic absorption analyzer NOVA a330 manufactured by chemical corporation and an ion chromatograph DX-120 manufactured by Dionex corporation, respectively,and according to the measurement results, zirconium fluoride and hydrofluoric acid were supplied to the treatment solution to adjust the concentrations to the values shown in table 3. Further, the pH of the chemical conversion treatment agent in the treatment bath was measured by using a pH meter D-24 manufactured by Higherkinson Seiki, and according to the measurement results, nitric acid or hydroxylammonium was supplied to the treatment solution to adjust the pH to the value shown in Table 3.
Comparative example 14
The chemical conversion treatment of the cathodic electrolysis treatment was replaced with an aqueous solution of 5% of a commercially available manganese phosphate treating agent SF572 (manufactured by Nippon paint), and the immersion treatment was carried out at 50 ℃ for 2 minutes. In addition, a test plate was prepared in the same manner as in example 22.
Comparative example 15
The chemical conversion treatment of the cathodic electrolysis treatment was replaced with an aqueous solution of 5% of a commercially available zirconium phosphate treating agent ALSURF 440 (manufactured by Japan paint), and immersion treatment was carried out at 50 ℃ for 2 minutes. In addition, a test plate was prepared in the same manner as in example 22.
The test plates obtained in examples 22 to 23 and comparative examples 14 to 15 were evaluated for corrosion resistance as follows.
The corrosion resistance was evaluated in the same manner as in example 1, except that the evaluation time of<corrosion resistance>in the evaluation of example 1 was changed from 2000 hours to 48 hours.
[ Table 3]]
| Chemical conversion treatment of Mg | Examples | Comparative example | |||
| 22 | 23 | 14 | 15 | ||
| Test board | AZ91D | ||||
| Treating agent | Zirconium fluoacid (mass% of Zr) | 1 | SF572 | ALSURF440 | |
| Zirconium ammonium fluoride (mass% of Zr) | 0.5 | ||||
| Zr/F mass ratio in treating agent | 0.77 | 0.83 | |||
| Gamma-aminopropyldiethoxysilane | 100 | 100 | |||
| Conditions of treatment | pH | 3.5 | 3.5 | - | - |
| Temperature (. degree.C.) | 30 | 30 | 50℃ | 50℃ | |
| Time (seconds) | 30 | 30 | 120 | 120 | |
| Electrolysis conditions (voltage: V) | -10 | -10 | - | - | |
| Electrolysis conditions (current density: A/dm3)* | 1.2 | 1.0 | - | - | |
| coating characteristics | Coating resistance (omega) | 0.1 | 0.1 | 0.1 | 0.1 |
| SST score (SST48h) | 10 | 9 | 2 | 2 | |
Represents cathodic electrolysis treatment
As is apparent from Table 3, the test plates obtained in examples 22 to 23 are more excellent in corrosion resistance than those of comparative examples 14 and 15.
Industrial applicability
The method for treating a metal surface of the present invention can be suitably applied to an object to be treated such as an iron-based substrate, a zinc-based substrate, an aluminum-based substrate, or a magnesium-based substrate.
Claims (5)
1. A metal surface treatment method comprising a step of forming a chemical conversion coating on the surface of a metal object by a chemical conversion treatment reaction of a chemical conversion treatment agent containing a zirconium-containing compound and a fluorine-containing compound, characterized in that the chemical conversion treatment reaction is carried out by cathodic electrolysis treatment.
2. The metal surface treatment method according to claim 1, wherein the cathodic electrolysis is performed after the chemical conversion treatment agent is adjusted, and after the adjustment, the concentration of the zirconium-containing compound in the chemical conversion treatment agent is 10 to 100000ppm in terms of the zirconium metal concentration, the ratio of the total mass of zirconium metal to the total mass of fluorine, that is, the amount of zirconium/the amount of fluorine is 0.2 to 1.0, and the pH is 1 to 6.
3. The metal surface treatment method according to claim 1 or 2, wherein the cathodic electrolysis treatment is carried out at a voltage of 0.1 to 40V and a current density of 0.1 to 30A/dm2Under the conditions of (1).
4. The metal surface treatment method according to claim 1, 2 or 3, wherein the metal object to be treated is at least one substrate selected from the group consisting of aluminum-based, zinc-based, iron-based and magnesium-based substrates.
5. A surface-treated metal characterized by having a chemical conversion treatment coating obtained by the metal surface treatment method as recited in claim 1, 2, 3 or 4.
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|---|---|---|---|---|
| JPS5794575A (en) * | 1980-12-05 | 1982-06-12 | Rasa Kogyo Kk | Surface treating method for aluminum or its alloy |
| JP3105322B2 (en) * | 1991-12-27 | 2000-10-30 | 日産自動車株式会社 | Method for forming colorless chromate film on glittering aluminum wheels |
| DE19508126A1 (en) * | 1995-03-08 | 1996-09-12 | Henkel Kgaa | Chrome-free process for improving paint adhesion after thin-layer anodization |
| JP3302684B2 (en) * | 2000-10-16 | 2002-07-15 | 日新製鋼株式会社 | Chemical treated steel sheet with excellent corrosion resistance |
| JP4019723B2 (en) * | 2001-02-23 | 2007-12-12 | 株式会社デンソー | Electrolytic phosphate chemical treatment method |
| TWI268965B (en) * | 2001-06-15 | 2006-12-21 | Nihon Parkerizing | Treating solution for surface treatment of metal and surface treatment method |
-
2004
- 2004-05-13 JP JP2004143688A patent/JP2005023422A/en active Pending
- 2004-06-08 CN CNA200410046519XA patent/CN1572912A/en active Pending
- 2004-06-08 CA CA002470445A patent/CA2470445A1/en not_active Abandoned
- 2004-06-08 EP EP04013487A patent/EP1486585B1/en not_active Expired - Lifetime
- 2004-06-08 KR KR1020040041813A patent/KR20040105617A/en not_active Application Discontinuation
- 2004-06-08 AU AU2004202524A patent/AU2004202524A1/en not_active Abandoned
- 2004-06-08 DE DE602004002519T patent/DE602004002519T2/en not_active Expired - Fee Related
- 2004-06-08 US US10/863,482 patent/US20040244875A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102812156A (en) * | 2010-03-25 | 2012-12-05 | 杰富意钢铁株式会社 | Surface treated steel plate, manufacturing method therefor, and resin-coated steel plate using same |
| CN105667007A (en) * | 2010-03-25 | 2016-06-15 | 杰富意钢铁株式会社 | Surface treated steel plate, manufacturing method therefor, and resin-coated steel plate using same |
| CN105667007B (en) * | 2010-03-25 | 2018-02-06 | 杰富意钢铁株式会社 | Surface treated steel plate and its manufacture method and the resin-coated steel sheet using the surface treated steel plate |
| CN102634832A (en) * | 2012-05-10 | 2012-08-15 | 中国兵器工业第五九研究所 | Method for preparing aluminum alloy element surface coating and system thereof |
| CN102634832B (en) * | 2012-05-10 | 2015-04-22 | 中国兵器工业第五九研究所 | Method for preparing aluminum alloy element surface coating and system thereof |
| CN102899702A (en) * | 2012-08-31 | 2013-01-30 | 华南理工大学 | Magnesium alloy surface composite treatment method |
| CN102899702B (en) * | 2012-08-31 | 2015-10-28 | 华南理工大学 | Magnesium alloy surface composite treatment method |
| CN105874107A (en) * | 2013-12-18 | 2016-08-17 | 东洋制罐株式会社 | Surface-treated steel sheet, organic-resin-coated metal container, and method for producing surface-treated steel sheet |
| CN105874107B (en) * | 2013-12-18 | 2018-11-16 | 东洋制罐株式会社 | The manufacturing method of surface treated steel plate, the canister of organic resin covering and surface treated steel plate |
| CN109415834A (en) * | 2016-07-21 | 2019-03-01 | 日本帕卡濑精株式会社 | Metal conditioner is used in electrolysis processing |
| CN109415834B (en) * | 2016-07-21 | 2021-05-18 | 日本帕卡濑精株式会社 | Metal surface treatment agent for electrolytic treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1486585A1 (en) | 2004-12-15 |
| CA2470445A1 (en) | 2004-12-09 |
| JP2005023422A (en) | 2005-01-27 |
| US20040244875A1 (en) | 2004-12-09 |
| EP1486585B1 (en) | 2006-09-27 |
| DE602004002519T2 (en) | 2007-05-31 |
| KR20040105617A (en) | 2004-12-16 |
| DE602004002519D1 (en) | 2006-11-09 |
| AU2004202524A1 (en) | 2004-12-23 |
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