WO2014192082A1 - Supplément, matériau métallique traité en surface, et son procédé de production - Google Patents

Supplément, matériau métallique traité en surface, et son procédé de production Download PDF

Info

Publication number
WO2014192082A1
WO2014192082A1 PCT/JP2013/064801 JP2013064801W WO2014192082A1 WO 2014192082 A1 WO2014192082 A1 WO 2014192082A1 JP 2013064801 W JP2013064801 W JP 2013064801W WO 2014192082 A1 WO2014192082 A1 WO 2014192082A1
Authority
WO
WIPO (PCT)
Prior art keywords
zirconium
fluorine
metal material
ions
replenisher
Prior art date
Application number
PCT/JP2013/064801
Other languages
English (en)
Japanese (ja)
Inventor
川井　智
慶幸 川出
Original Assignee
日本パーカライジング株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本パーカライジング株式会社 filed Critical 日本パーカライジング株式会社
Priority to CN201380076902.7A priority Critical patent/CN105378144B/zh
Priority to EP13886009.3A priority patent/EP3006600B1/fr
Priority to PCT/JP2013/064801 priority patent/WO2014192082A1/fr
Priority to US14/894,488 priority patent/US20160186351A1/en
Priority to KR1020157033718A priority patent/KR101726536B1/ko
Priority to JP2015519528A priority patent/JP6055915B2/ja
Publication of WO2014192082A1 publication Critical patent/WO2014192082A1/fr
Priority to PH12015502678A priority patent/PH12015502678A1/en

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • 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
    • 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
    • C23C22/86—Regeneration of coating baths

Definitions

  • the present invention relates to a replenisher, a surface-treated metal material, and a method for producing the same.
  • Patent Document 1 Patent Document 2
  • a chemical conversion treatment and / or an electrolytic treatment for example, a cathode of a metal material in a surface treatment solution for a metal material containing zirconium (hereinafter also referred to as Zr) ions and fluorine (hereinafter also referred to as F) ions.
  • Zr zirconium
  • F fluorine
  • zirconium ions in the surface treatment liquid for metal materials become oxides and adhere as a film and are consumed.
  • Zirconium ion concentration of the steel decreases.
  • fluorine ions are less taken into the film than zirconium ions, and the amount of decrease in fluorine ion concentration per unit area in the surface treatment liquid for metal materials is less than that of zirconium ions.
  • H 2 ZrF 6 is often used as the surface treatment liquid for metal material containing zirconium ions, and the reaction formula thereof is as follows.
  • the pH in the vicinity of the metal material rises due to the consumption of acid by etching, the reduction of hydrogen ions in the vicinity of the cathode electrode, etc., and as shown in Equation (1) 2 ZrF 6 is hydrolyzed, and a zirconium-based film such as zirconium oxide is formed on the surface of the metal material.
  • Patent Document 3 uses a zirconium compound containing fluorine and a replenisher containing a zirconium compound not containing fluorine, and an amount of zirconium ions in consideration of the balance with the replenishment amount of fluorine ions to the surface treatment liquid for metal materials. It is proposed that the above problem can be solved by replenishing. More specifically, in paragraph 0033 of Patent Document 3, a Zr ion concentration of 17 g / L of a Zr fluoride hydrofluoric acid and Zr nitrate mixed solution (fluorinated Zr hydroacid: Zr nitrate 55:45 by weight) is used. It is disclosed that Zr ions have been replenished.
  • replenishers used for replenishing zirconium ions to the surface treatment liquid for metal materials are usually used while being stored in a warehouse for a long time after purchase. For this reason, it is required to be usable even after being stored for a long period of time.
  • the replenisher is stored for a long period of time in a high temperature environment, it is necessary that no precipitation or the like occurs in the replenisher.
  • the present inventors examined the storage stability of the replenisher specifically described in Patent Document 3, and as a result, the storage stability did not meet the recent required level, and further improvements were necessary. It was.
  • the cumulative treatment load is the result of continuous operation of the coating treatment, and the cumulative treatment area (Sm 2 ) of the metal material divided by the surface treatment liquid volume for metal material (VL) (S / V (m 2 / L)), as a coating treatment technology for metal materials, it is necessary that the change in the component balance of the surface treatment liquid for metal materials is small and the processability does not deteriorate for a larger cumulative processing load. It is said.
  • the surface treatment liquid for metal materials is partially or completely updated to ensure stable treatment. It is necessary to ensure sex. In that case, it is not preferable from the viewpoint of production efficiency, cost, and environment.
  • the inventors conducted continuous operation of the film treatment using the replenisher specifically described in Patent Document 3, and verified the film treatment property at the time of a larger cumulative treatment load. It has been found that the amount of the coating on the surface is reduced.
  • the present invention avoids an increase in the HF concentration in the surface treatment liquid for metal material so that chemical conversion treatment and / or electrolytic treatment can be continuously performed on the metal material.
  • An object of the present invention is to provide a replenisher that can replenish the surface treatment solution for metal material with higher concentration of zirconium ions and has excellent long-term storage stability.
  • Another object of the present invention is to provide a method for producing a surface-treated metal material using the replenisher.
  • the present inventors have found that the above problem can be solved by using a replenisher having a high zirconium ion concentration obtained by using a predetermined compound. That is, the configuration of the present invention for solving the above problems is as follows.
  • the total concentration (g / L) of zirconium ions derived from the fluorine-free zirconium compound (A) and the fluorine-containing product (B) is 25 or more.
  • Total molar amount (M F ) of fluorine ions derived from fluorine-containing material (B) and total molar amount of zirconium ions derived from fluorine-free zirconium compound (A) and fluorine-containing material (B) (M Zr ) (M F / M Zr ) is less than 2.00 and less than 6.00.
  • a chemical conversion treatment and / or an electrolytic treatment is continuously performed on the metal material in a surface treatment solution for the metal material containing zirconium ions and fluorine ions to form a chemical conversion treatment film containing zirconium on the metal material.
  • a method of manufacturing a surface-treated metal material (1) A method for producing a surface-treated metal material, wherein the replenisher according to any one of (1) to (3) is added to a surface treatment solution for a metal material to replenish zirconium ions.
  • the chemical conversion treatment and / or the electrolytic treatment can be continuously performed on the metal material, while avoiding an increase in the HF concentration in the surface treatment liquid for the metal material.
  • Zirconium ions can be replenished to the surface treatment liquid at a higher concentration, and a replenisher that is superior in long-term storage stability can be provided.
  • the manufacturing method of the surface treatment metal material which uses this replenisher can be provided.
  • the replenisher of the present invention contains a predetermined fluorine-free zirconium compound (A), a predetermined fluorine-containing material (B), and a predetermined acid component (C), and contains zirconium ions (Zr ions) at a high concentration. contains. Further, the replenisher of the present invention is a ratio (M AC / M F ) between the total molar amount (M AC ) of the anion derived from the acid component (C) and the total molar amount (M F ) of the fluorine ion (F ion).
  • the ratio (M F / M Zr ) of the total molar amount (M Zr ) of zirconium ions and the total molar amount (M F ) of fluorine ions is within a predetermined range.
  • the replenisher contains zirconium ions at a higher concentration than fluorine ions. Therefore, in continuous chemical conversion coating production, when the replenisher is continuously replenished to the surface treatment liquid for metal material, a large amount of zirconium ions can be continuously supplied while avoiding an increase in HF. As a result, the chemical conversion treatment and / or the electrolytic treatment of the metal material can be continuously performed while suppressing the amount of auto drain.
  • the replenisher is more excellent in long-term storage stability and can be continuously subjected to chemical conversion treatment and / or electrolytic treatment of metal materials.
  • An agent can be provided.
  • the replenisher of the present invention is a surface treatment for a metal material containing zirconium ions and fluorine ions, which is used for forming a chemical conversion treatment film containing zirconium as a main component on the surface of the metal material by chemical conversion treatment and / or electrolytic treatment. It is mainly used to supply zirconium ions to the liquid. In addition, in continuous chemical conversion treatment film manufacture, implementation of an auto drain is not refused. First, various materials contained in the replenisher will be described in detail, and then a method for producing the replenisher will be described in detail.
  • the fluorine-free zirconium compound (A) contained in the replenisher of the present invention is a compound containing no Z atom and no fluorine atom.
  • the fluorine-free zirconium compound (A) include at least one selected from the group consisting of basic zirconium carbonate, zirconium carbonate, zirconium hydroxide, and ammonium zirconium carbonate.
  • basic zirconium carbonate or carbonic acid is preferred in that the storage stability of the replenisher is superior and the surface treatment can be carried out more continuously (hereinafter also referred to simply as “the effect of the present invention is more excellent”).
  • Zirconium is more preferred.
  • the fluorine-containing material (B) contained in the replenisher of the present invention is a compound containing a fluorine atom, and F ions are supplied into the replenisher by the compound.
  • Zr ion is also supplied in a replenisher.
  • the fluorine-containing material (B) include at least one selected from the group consisting of hydrofluoric acid, a hydrofluoric acid salt, zirconium hydrofluoric acid, and a zirconium hydrofluoric acid salt.
  • hydrofluoric acid or zirconium hydrofluoric acid is more preferable in that the effect of the present invention is more excellent.
  • the salt of hydrofluoric acid include a salt of hydrofluoric acid and a base (for example, an amine compound), preferably a base containing no metal such as an ammonium salt.
  • the salt of zirconium hydrofluoric acid include metal acid salts such as K 2 ZrF 6 (for example, sodium salt, potassium salt, lithium salt, ammonium salt, etc.).
  • K 2 ZrF 6 for example, sodium salt, potassium salt, lithium salt, ammonium salt, etc.
  • the acid component (C) contained in the replenisher of the present invention plays a role in adjusting the pH of the replenisher and other components (fluorine-free zirconium compound (A) and / or fluorine-containing material (B)). It plays a role in helping solubility.
  • the acid component (C) include at least one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid. Among these, nitric acid or sulfuric acid is more preferable in that the effect of the present invention is more excellent.
  • an acid component (C) you may mix and use the said acid component 2 or more types.
  • Total molar amount (M F ) of fluorine ions derived from fluorine-containing material (B) and total molar amount of zirconium ions derived from fluorine-free zirconium compound (A) and fluorine-containing material (B) (M Zr ) (M F / M Zr ) is less than 2.00 and less than 6.00. Below, each relationship is demonstrated.
  • the ratio (M AC / M F ) is preferably more than 0.40 and less than 2.00, more preferably more than 0.50 and less than 2.00, and more than 0.50. .60 or less is more preferable, and 1.00 or more and 1.60 or less is particularly preferable.
  • the ratio (M AC / M F ) is less than 0.35, the long-term storage stability of the replenisher is poor.
  • the ratio (M AC / M F) is 2.00 or more, the amount of deposition of the film continued use of the replenisher is reduced, it is no longer possible to create the desired coating.
  • the anion derived from the acid component (C) intends NO 3 ⁇ , Cl ⁇ , SO 4 2 ⁇ , and CH 3 COO ⁇ .
  • the total concentration (g / L) of zirconium ions derived from the fluorine-free zirconium compound (A) and the fluorine-containing material (B) in the replenisher of the present invention is 25 or more. If it is in the said range, a more economical chemical conversion treatment film can be manufactured.
  • the total concentration (g / L) of zirconium ions is preferably 30 or more, and more preferably 35 or more, from the viewpoint that the amount of the replenisher used is small and the operation economy is more excellent.
  • the upper limit is not particularly limited, but it is often 70 or less from the viewpoint of the solubility of the fluorine-free zirconium compound (A) and the fluorine-containing product (B).
  • the concentration of the replenisher is dilute, so that a large amount of the replenisher must be replenished to the surface treatment liquid for metal material, and supercharged water is accordingly added As a result, the volume of the surface treatment liquid for metal materials has increased, and as a result, it is necessary to increase the amount of auto drain of the surface treatment liquid for metal materials in order to perform continuous film treatment. Is not preferable. Further, when zirconium hydrofluoric acid or a salt thereof is used as the fluorine-containing material (B), zirconium ions derived from the fluorine-containing material (B) are supplied.
  • the ratio (M F / M Zr ) to the total molar amount (M F ) is 2.00 or more and less than 6.00. If it is in the said range, HF of the surface treatment liquid for metal materials will not accumulate
  • the ratio (M F / M Zr ) is preferably 2.50 to 5.50, more preferably 3.00 to 5.00, in which the effect of the present invention is more excellent.
  • the ratio (M F / M Zr ) is less than 2.00, it is difficult to dissolve zirconium ions in the replenisher.
  • the ratio (M F / M Zr ) is 6.00 or more, if the replenisher is continuously used, accumulation of HF in the surface treatment liquid for metal material cannot be avoided. In the case of producing a treated film, it is necessary to increase the amount of auto drain, which is not preferable from an environmental and economic point of view.
  • the measurement of various ions described above can be performed using a known measuring instrument, atomic absorption, ICP, ion chromatography, or a fluorine ion meter.
  • the content of the fluorine-free zirconium compound (A) in the replenisher of the present invention is not particularly limited as long as the relations (I) to (III) are satisfied, but the deposition efficiency of the chemical conversion film is more excellent.
  • the amount is preferably from 0.1 to 500 parts by weight, more preferably from 10 to 300 parts by weight, based on 100 parts by weight of the fluorine-containing material (B).
  • the pH of the replenisher of the present invention is not particularly limited, but is preferably less than 4.0 and more preferably more than 0 and 1.5 or less in terms of excellent stability of the replenisher.
  • an alkali component can also be used.
  • Alkali components include alkali metal oxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, organic substances such as ammonia, monoethanolamine, diethanolamine, and triethanolamine. Examples include amines. Among them, it is preferable to use ammonia from the viewpoint that there is no metal contamination and no organic solvent is contained.
  • the replenisher of the present invention may contain a solvent, if necessary.
  • the kind in particular of solvent used is not restrict
  • the organic solvent include alcohol solvents.
  • Regarding the content of the organic solvent it may be in a range that does not impair the stability of the replenisher and the stability of the surface treatment liquid for metal material replenished with the replenisher, but it should not be used from the viewpoint of the working environment. preferable.
  • the replenisher contains a solvent
  • the total mass of the fluorine-free zirconium compound (A), the fluorine-containing material (B), and the acid component (C) is the replenisher in that the deposition efficiency of the chemical conversion coating is more excellent. 2 to 90% by mass is preferable with respect to the total amount, and 4 to 80% by mass is more preferable.
  • the manufacturing method of the replenisher of the present invention is not particularly limited, and a known method is adopted.
  • a method in which a fluorine-free zirconium compound (A), a fluorine-containing material (B), and an acid component (C) are added and mixed in a solvent can be mentioned.
  • the above-described replenisher is replenished into the surface treatment liquid for metal material.
  • the replenisher it is preferable to add the replenisher so that the zirconium ion concentration does not decrease by 20% or more in order to obtain a predetermined chemical conversion coating on the metal material continuously and stably.
  • the total fluorine ion amount replenished simultaneously with zirconium is determined from the total amount of total fluorine ions contained in the chemical treatment film and the total amount of fluorine ions contained in the surface treatment solution for metal materials taken out of the metal material. It is preferable to replenish the amount obtained by subtracting the amount of fluorine ions of HF produced as a by-product in the surface treatment solution for metal material when a zirconium compound film is formed.
  • the method of adding the replenisher of the present invention to the surface treatment solution for metal material is not particularly limited, and a method of adding the replenisher in small portions (Method A) or a predetermined amount of replenisher in a lump. (Method B).
  • Method A is preferable from the point that the component fluctuation
  • the method of adding the replenisher to the surface treatment liquid for metal material may be employed.
  • the surface for metal materials during the manufacturing method of surface-treated metal materials is superior in that it is excellent in production efficiency especially at high-speed operation, and can continuously and stably produce the surface-treated metal materials.
  • a method of adding a replenisher to the treatment liquid is preferred.
  • the surface treatment liquid for metal material used in the method for producing a surface-treated metal material of the present invention will be described.
  • the surface treatment liquid for metal material used in the method for producing a surface-treated metal material of the present invention described above contains Zr ions and fluorine ions.
  • Examples of the supply source of zirconium ions in the surface treatment liquid for metal materials include the above-described fluorine-free zirconium compound (A), zirconium hydrofluoric acid, or a salt thereof.
  • Zr ions in the surface treatment liquid for metal materials as shown in (1) ZrF n (4-n) , complex fluorination in which 1 to 6 mol of fluorine is coordinated to 1 mol of zirconium.
  • zirconium ions and (2) zirconium or zirconyl inorganic acids such as zirconium nitrate or zirconium sulfate, or zirconium or zirconyl ions generated from organic acid zirconium or zirconyl such as zirconium acetate or zirconyl acetate.
  • the content of zirconium ions in the surface treatment liquid for metal material is not particularly limited, but is 0.05 to 10.5 in that it is more excellent in stability of the surface treatment liquid for metal material and more excellent in deposition efficiency of the chemical conversion film. 00 g / L is preferable, and 0.10 to 2.00 g / L is more preferable.
  • fluorine-containing compound a known fluorine-containing compound (fluorine-containing compound) is used as a supply source of fluorine ions in the surface treatment liquid for metal materials.
  • fluorine-containing compound those having at least one element selected from the group consisting of Ti, Zr, Hf, Si, Al and B are preferably used. Specifically, for example, (TiF 6 ) 2 ⁇ , (ZrF 6 ) 2 ⁇ , (HfF 6 ) 2 ⁇ , (SiF 6 ) 2 ⁇ , (AlF 6 ) 3 ⁇ , (BF 4 OH) ⁇ , etc.
  • fluorine-containing compound examples include hydrofluoric acid, its ammonium salt, its alkali metal salt, and metal fluoride (for example, aluminum fluoride, zinc fluoride, vanadium fluoride, tin fluoride, fluorine fluoride).
  • metal fluoride for example, aluminum fluoride, zinc fluoride, vanadium fluoride, tin fluoride, fluorine fluoride.
  • oxyfluorides eg, fluorine oxide, acetyl fluoride, benzoyl fluoride, etc.
  • Fluorine ions in the surface treatment liquid for metal materials are HF-derived fluorine ions (F ⁇ ) present in the surface treatment liquid for metal materials and fluorine-containing complex ions such as the above complex zirconium fluoride ions. It refers to both fluorine ions, and the total fluorine ion concentration described above and below refers to the total concentration of both.
  • the free fluorine concentration refers to the concentration of fluorine ions (F ⁇ ) derived from HF.
  • the content of total fluorine ions in the surface treatment liquid for metal materials is not particularly limited, but the total fluorine ion concentration is superior in terms of the stability of the surface treatment liquid for metal materials and the deposition efficiency of the chemical conversion coating.
  • the free fluorine ion concentration is preferably 5 mg / L to 400 mg / L, more preferably 10 to 250 mg / L.
  • the content (concentration) of Zr ions, total fluorine ions, and free fluorine ions in the surface treatment solution for metal materials can be quantified using atomic absorption, ICP, ion chromatography, or a fluorine ion meter.
  • the pH of the surface treatment solution for metal materials is adjusted as appropriate according to the target metal material and the conditions of chemical conversion treatment or electrolytic treatment, but it is superior in stability of the surface treatment solution for metal materials and deposits of the chemical conversion treatment film. From the viewpoint of more excellent properties, it is preferably about 2.5 to 5.0, more preferably 3.0 to 5.0. In addition, pH of the surface treatment liquid for metal materials can be measured using a pH meter.
  • Metal material The kind in particular of metal material to be used is not restrict
  • the shape of the metal material is not particularly limited, and may be a plate shape or another shape. Other shapes include, for example, the body and parts of transportation equipment such as automobiles, agricultural equipment and parts, steel furniture, building materials, and the like.
  • the chemical conversion treatment using the above-described surface treatment solution for metal material can be carried out under known conditions using a known treatment facility.
  • the chemical conversion treatment is a treatment for forming a film on the surface of the metal material by bringing a predetermined surface treatment liquid for the metal material into contact with the metal material at room temperature or warming (immersion, coating, or spraying). .
  • the time for contacting the metal material with the surface treatment liquid for the metal material is appropriately adjusted according to the material, shape, treatment method, application, and target coating amount of the target metal material. Usually, it is often about 0.1 to 600 seconds in terms of more excellent characteristics.
  • the electrolytic treatment (anodic electrolytic treatment, cathodic electrolytic treatment) using the surface treatment liquid for metal material
  • it can be carried out under known conditions using a known electrolytic treatment facility.
  • the current density is preferably from 0.1 to 20.0 A / dm 2 and more preferably from 0.5 to 10.0 A / dm 2 from the viewpoint of more excellent deposition efficiency of the chemical conversion coating.
  • the amount of zirconium deposited on the formed chemical conversion coating is appropriately adjusted according to the material and application of the target metal material.
  • either the chemical conversion treatment or the electrolytic treatment can be used because the properties as the chemical conversion coating are more excellent. In many cases, the amount is usually about 1 to 70 mg / m 2 .
  • Test plate The following (1) to (3) were used as test plates used in Examples and Comparative Examples.
  • Aluminum alloy plate (6000 series aluminum alloy plate thickness: 0.8mm)
  • Cold rolled steel plate (SPC, plate thickness: 0.8 mm)
  • Alloyed hot-dip galvanized steel sheet (GA, thickness: 0.8 mm)
  • Continuous processing test method As the chemical conversion treatment, any one of the following continuous treatment methods 1 to 3 was performed.
  • ⁇ Continuous processing method 1> A treatment solution having the following component concentrations was bathed for 10 L, adjusted to pH 4.0, and heated to 40 ° C. to obtain a surface treatment solution for metal materials. The treatment liquid was stirred, and the test plate (1) was immersed for 180 seconds to perform a surface treatment with a target Zr adhesion amount of 13 mg / m 2 . This was treated as a single treatment, and thereafter a surface treatment (continuous treatment test) was repeatedly performed using a new test plate (1).
  • the test was performed until the treatment load reached 13.3 m 2 / L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount during the 13.3 m 2 / L treatment were measured.
  • the Zr adhesion amount on the treatment material surface was quantified using XRF (fluorescence X-ray analysis method).
  • ⁇ Continuous processing method 2> A treatment solution having the following component concentrations was bathed for 10 L, adjusted to pH 4.0, and heated to 40 ° C. to obtain a surface treatment solution for metal materials. This treatment liquid was stirred, and the test plate (2) was immersed for 120 seconds to perform a surface treatment with a target Zr deposition amount of 20 mg / m 2 . This was treated as one time, and then a new surface treatment (continuous treatment test) was performed using a new test plate (2).
  • the test was performed until the treatment load reached 16.7 m 2 / L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount at the time of 16.7 m 2 / L treatment were measured.
  • the Zr adhesion amount on the treatment material surface was quantified using XRF (fluorescence X-ray analysis method).
  • the concentrations of the various components were Zr ions: 500 mg / L, total F ions: 680 mg / L, free F ions: 36 mg / L, NO 3 ions: 750 mg / L.
  • a treatment solution having the following component concentrations was bathed for 10 L, adjusted to pH 3.7, and heated to 40 ° C. as a surface treatment solution for metal materials.
  • the treatment liquid was stirred, and the test plate (3) was immersed for 30 seconds to perform a surface treatment with a target Zr deposition amount of 10 mg / m 2 .
  • This was treated as a single treatment, and thereafter a surface treatment (continuous treatment test) was repeatedly performed using a new test plate (3).
  • the amount of the treatment liquid (take-out liquid) adhering to the test plate (3) and taken out was 22 mL / m 2 , so the liquid level and the amount of the treatment liquid in the treatment liquid were increased every 0.5 m 2 / L.
  • Replenishment of the Zr concentration drop was performed with water and the replenisher shown in Table 1, and the Zr concentration was adjusted simultaneously with the liquid level.
  • the pH of the treatment liquid was also adjusted with ammonia water as necessary every 0.5 m 2 / L.
  • the above-mentioned continuous test was performed until 10 L of the total amount of the processing solution was replaced with 100% by the carry-out solution. That is, the test was performed until the treatment load reached 45.5 m 2 / L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount at the time of 45.5 m 2 / L treatment were measured.
  • the Zr adhesion amount on the treatment material surface was quantified using XRF (fluorescence X-ray analysis method).
  • Zr carbonate represents zirconium carbonate
  • basic carbonate Zr represents basic zirconium carbonate
  • Zr concentration represents zirconium ion concentration (g / L).
  • the ratio (M AC / M F) is in the predetermined range is smaller than Comparative Example 1-3, was inferior storage stability of the replenisher.
  • Comparative Examples 4 to 6 it is presumed that the ratio of the anion derived from the acid component (C) is higher than the fluorine derived from the fluorine-containing material (B) as an anion for stabilizing zirconium in the replenisher.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'objet de la présente invention est de décrire un supplément qui évite une augmentation de la concentration de HF dans un liquide de traitement de surface pour des matériaux métalliques, qui est capable de fournir des ions de zirconium à concentration élevée en utilisant le liquide de traitement de surface de matériaux métalliques, et a une excellente stabilité au stockage à long terme, afin de convertir chimiquement en continu et/ou traiter électrolytiquement un matériau métallique. Ce supplément contient des quantités prescrites d'un composé de zirconium (A) ne contenant pas de fluor et comprenant au moins un type choisi dans un groupe comprenant le carbonate basique de zirconium, le carbonate de zirconium, l'hydroxyde de zirconium, et le carbonate d'ammonium–zirconium ; une matière contenant du fluor (B) comprenant au moins un type choisi dans un groupe comprenant l'acide fluorhydrique, un sel d'acide fluorhydrique, l'acide fluorozirconique et un sel d'acide fluorozirconique ; et un composant acide (C) comprenant au moins un type choisi dans un groupe comprenant l'acide nitrique, l'acide chlorhydrique, l'acide sulfurique, et l'acide acétique.
PCT/JP2013/064801 2013-05-28 2013-05-28 Supplément, matériau métallique traité en surface, et son procédé de production WO2014192082A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
CN201380076902.7A CN105378144B (zh) 2013-05-28 2013-05-28 补给剂、表面处理金属材料及其制备方法
EP13886009.3A EP3006600B1 (fr) 2013-05-28 2013-05-28 Supplément et procédé de production d'un matériau métallique traité en surface
PCT/JP2013/064801 WO2014192082A1 (fr) 2013-05-28 2013-05-28 Supplément, matériau métallique traité en surface, et son procédé de production
US14/894,488 US20160186351A1 (en) 2013-05-28 2013-05-28 Replenisher, surface-treated metallic material, and production method thereof
KR1020157033718A KR101726536B1 (ko) 2013-05-28 2013-05-28 보급제, 표면처리 금속재료 및 그의 제조방법
JP2015519528A JP6055915B2 (ja) 2013-05-28 2013-05-28 補給剤、表面処理金属材料の製造方法
PH12015502678A PH12015502678A1 (en) 2013-05-28 2015-11-27 Supplement, surface -treated metal material, and production method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/064801 WO2014192082A1 (fr) 2013-05-28 2013-05-28 Supplément, matériau métallique traité en surface, et son procédé de production

Publications (1)

Publication Number Publication Date
WO2014192082A1 true WO2014192082A1 (fr) 2014-12-04

Family

ID=51988157

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/064801 WO2014192082A1 (fr) 2013-05-28 2013-05-28 Supplément, matériau métallique traité en surface, et son procédé de production

Country Status (7)

Country Link
US (1) US20160186351A1 (fr)
EP (1) EP3006600B1 (fr)
JP (1) JP6055915B2 (fr)
KR (1) KR101726536B1 (fr)
CN (1) CN105378144B (fr)
PH (1) PH12015502678A1 (fr)
WO (1) WO2014192082A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017138530A1 (fr) * 2016-02-10 2017-08-17 日本ペイント・サーフケミカルズ株式会社 Procédé de réapprovisionnement de bain de conversion chimique
JP2017537229A (ja) * 2014-12-12 2017-12-14 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ フッ化物含有浴に基づく腐食防止金属前処理におけるプロセス制御の最適化

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115074715B (zh) * 2022-06-30 2024-01-30 东风商用车有限公司 一种用于耐高温涂层的前处理锆化剂及前处理方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07197273A (ja) * 1993-11-29 1995-08-01 Nippon Parkerizing Co Ltd 金属処理用組成物および処理方法
JP2006509909A (ja) * 2002-12-11 2006-03-23 日本パーカライジング株式会社 缶端部用原料アルミニウムの高性能非クロム前処理
JP2008202149A (ja) 2008-06-02 2008-09-04 Nippon Parkerizing Co Ltd 金属の表面処理用処理液及び表面処理方法
JP2010090407A (ja) 2008-10-03 2010-04-22 Nippon Parkerizing Co Ltd 金属表面処理液、および金属表面処理方法
JP2012017524A (ja) * 2010-06-09 2012-01-26 Nippon Paint Co Ltd 無機系クロムフリー金属表面処理剤
JP4996409B2 (ja) 2007-09-28 2012-08-08 新日本製鐵株式会社 化成処理被覆鋼板の製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5316565B2 (fr) 1973-01-20 1978-06-02
US6916414B2 (en) * 2001-10-02 2005-07-12 Henkel Kommanditgesellschaft Auf Aktien Light metal anodization
TW567242B (en) * 2002-03-05 2003-12-21 Nihon Parkerizing Treating liquid for surface treatment of aluminum or magnesium based metal and method of surface treatment
JP2008240045A (ja) * 2007-03-27 2008-10-09 Nippon Paint Co Ltd 鋼製ドラム缶の製造方法
US8951362B2 (en) * 2009-10-08 2015-02-10 Ppg Industries Ohio, Inc. Replenishing compositions and methods of replenishing pretreatment compositions
US9157165B2 (en) * 2010-04-22 2015-10-13 Nippon Steel & Sumitomo Metal Corporation Method of production of chemically treated steel sheet
WO2013080325A1 (fr) * 2011-11-30 2013-06-06 日本パーカライジング株式会社 Supplément et procédé de production de tôle en acier traitée en surface

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07197273A (ja) * 1993-11-29 1995-08-01 Nippon Parkerizing Co Ltd 金属処理用組成物および処理方法
JP2006509909A (ja) * 2002-12-11 2006-03-23 日本パーカライジング株式会社 缶端部用原料アルミニウムの高性能非クロム前処理
JP4996409B2 (ja) 2007-09-28 2012-08-08 新日本製鐵株式会社 化成処理被覆鋼板の製造方法
JP2008202149A (ja) 2008-06-02 2008-09-04 Nippon Parkerizing Co Ltd 金属の表面処理用処理液及び表面処理方法
JP2010090407A (ja) 2008-10-03 2010-04-22 Nippon Parkerizing Co Ltd 金属表面処理液、および金属表面処理方法
JP2012017524A (ja) * 2010-06-09 2012-01-26 Nippon Paint Co Ltd 無機系クロムフリー金属表面処理剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3006600A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017537229A (ja) * 2014-12-12 2017-12-14 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ フッ化物含有浴に基づく腐食防止金属前処理におけるプロセス制御の最適化
WO2017138530A1 (fr) * 2016-02-10 2017-08-17 日本ペイント・サーフケミカルズ株式会社 Procédé de réapprovisionnement de bain de conversion chimique

Also Published As

Publication number Publication date
KR20160003134A (ko) 2016-01-08
KR101726536B1 (ko) 2017-04-12
CN105378144B (zh) 2017-05-31
CN105378144A (zh) 2016-03-02
EP3006600A1 (fr) 2016-04-13
JPWO2014192082A1 (ja) 2017-02-23
EP3006600B1 (fr) 2018-12-19
JP6055915B2 (ja) 2016-12-27
PH12015502678A1 (en) 2016-03-07
EP3006600A4 (fr) 2017-01-18
US20160186351A1 (en) 2016-06-30

Similar Documents

Publication Publication Date Title
CN100537845C (zh) 金属表面处理用处理液和表面处理方法
JP5571277B2 (ja) 亜鉛系金属材料用表面処理液および亜鉛系金属材料の表面処理方法
JPWO2002103080A1 (ja) 金属の表面処理用処理液及び表面処理方法
AU2004202524A1 (en) Method of surface treating metal and metal surface treated thereby
JP6281990B2 (ja) アルミニウムおよびアルミニウム合金のための改善された三価クロム含有組成物
WO2010050131A1 (fr) Solution de traitement par conversion chimique d’un matériau métallique et procédé de traitement
JP6055915B2 (ja) 補給剤、表面処理金属材料の製造方法
TWI452172B (zh) 補給劑、表面處理鋼板之製造方法
JP2006241579A (ja) 化成処理剤及び表面処理金属
WO2018042980A1 (fr) Tôle d'acier traitée en surface, tôle d'acier revêtue de résine organique et récipient l'utilisant
JP6545191B2 (ja) 亜鉛又は亜鉛合金基材用３価クロム化成処理液及び化成皮膜
JP5447218B2 (ja) 表面処理めっき鋼板および表面処理液
JP6594678B2 (ja) 表面処理剤、表面処理方法及び表面処理済み金属材料
TWI602951B (zh) 補給劑、表面處理金屬材料及其製造方法
CA2881081A1 (fr) Liquide de traitement de surface metallique, procede de traitement de surface des bases metalliques et base metallique obtenue par un procede de traitement de surface des bases metalliques
JP2011127141A (ja) 電着塗装用表面処理金属材料、および化成処理方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13886009

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20157033718

Country of ref document: KR

Kind code of ref document: A

Ref document number: 2015519528

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 12015502678

Country of ref document: PH

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2013886009

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: IDP00201508774

Country of ref document: ID

WWE Wipo information: entry into national phase

Ref document number: 14894488

Country of ref document: US