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 metallic material and a method for producing the same.
• a surface thereof is normally subjected to a chemical conversion treatment including phosphate treatment and chromate treatment depending on its application.
• Patent Literature 1 and Patent Literature 2 a chemical conversion coating using a zirconium compound and the like is proposed as a new coating treatment to replace the phosphate treatment or the chromate treatment.
• a zirconium-based chemical conversion coating (hereinafter, also referred to simply as coating) can be formed on/over the surface of the metallic material, thereby imparting excellent performance to the surface of the metallic material.
• zirconium ion in the metallic material surface treating solution is consumed while being converted into oxides and deposited as the coatings, whereby the zirconium ion concentration in the metallic material surface treating solution gradually decreases.
• an amount of fluorine ion that is taken into the coatings is smaller than that of zirconium ion so that a decrease in the fluorine ion concentration in the metallic material surface treating solution per unit area is smaller than that of the zirconium ion concentration.
• H 2 ZrF 6 is often used in the metallic material surface treating solution containing zirconium ion, and the reaction formula thereof is as shown below.
• a zirconium-based coating includes zirconium oxide or the like is formed on/over the surface of the metallic material.
• H 2 ZrF 6 is normally supplied, but because of this ratio between zirconium ion and fluorine ion, accumulation of HF cannot be inhibited. Accordingly, in order to inhibit accumulation of HF, the method in which part of the metallic material surface treating solution is automatically drained (auto-drained) during continuous operation to keep the HF concentration constant has been conventionally adopted in many cases. However, in the environmental and economical point of view, it is not preferable to auto-drain the solution containing a large amount of zirconium ion or HF into drainage water in spite of the fact that the coatings with reduced environmental loads have been proposed, and thus improvements are desired.
• Patent Literature 3 proposes that the above-described problem can be solved by replenishing the metallic material surface treating solution with zirconium ion in such an amount that the balance with the amount of supplied fluorine ion is taken into consideration using a replenisher containing a fluorine-containing zirconium compound and a fluorine-free zirconium compound.
• a replenisher used to replenish the metallic material surface treating solution with zirconium ion is usually stored for a long time in a storehouse or the like after purchase.
• the replenisher has to be in a usable condition after a long-term storage.
• it is required that, when the replenisher is stored in the high-temperature environment for a long period of time, precipitation or the like not occur in the replenisher.
• the inventors of the present invention studied storage stability of the replenisher specifically described in Patent Literature 3 and found that the storage stability thereof was not at the recent satisfactory level, and further improvements were necessary.
• the accumulated treatment load refers to a value (S/V(m 2 /L)) obtained by dividing the accumulated treatment area (Sm 2 ) of a metallic material by the volume (VL) of the metallic material surface treating solution as the result of continuous operation of the coating treatment.
• the present inventors performed continuous operation of coating treatment using the replenisher specifically described in Patent Literature 3, studied the coating treatment performance when the accumulated treatment load is larger, and discovered that the coating weight on/over the metallic material would have decreased.
• an object of the present invention is to provide a replenisher that can replenish the metallic material surface treating solution with zirconium ion at the higher concentration while inhibiting an increase of the HF concentration in the metallic material surface treating solution such that chemical conversion treatment and/or electrolysis treatment can be continuously performed on/over metallic materials, and that exhibits excellent long-term storage stability.
• an object of the present invention also is to provide a method for producing a surface-treated metallic material using the replenisher.
• the present inventors discovered that the above-described problem can be solved by using a replenisher with high zirconium ion concentration that is obtained by using the predetermined compound.
• a fluorine-free zirconium compound (A) containing at least one selected from a group consisting of zirconium basic carbonate, zirconium carbonate, zirconium hydroxide and ammonium zirconium carbonate; a fluorine-containing compound (B) containing at least one selected from the group consisting of hydrofluoric acid, a salt of hydrofluoric acid, hexafluorozirconic acid and a salt of hexafluorozirconic acid; and an acid component (C) containing at least one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid and acetic acid,
• a ratio (M AC /M F ) of a total molar quantity (M AC ) of anions derived from the acid component (C) with respect to a total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) is 0.35 or more and less than 2.00;
• a total concentration (g/L) of zirconium ion derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 25 or higher;
• a ratio (M F /F Zr ) of a total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) with respect to a total molar quantity (M Zr ) of zirconium ion derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 2.00 or more and less than 6.00.
• a surface-treated metallic material obtained by the method for producing a surface-treated metallic material according to (4) is a surface-treated metallic material obtained by the method for producing a surface-treated metallic material according to (4).
• the present invention can provide a replenisher having more excellent long-term storage stability and capable of replenishing the metallic material surface treating solution with zirconium ion at high concentration while the HF concentration in the metallic material surface treating solution is inhibited from increasing such that chemical conversion treatment and/or electrolysis treatment can be continuously performed on/over metallic materials.
• the method for producing a surface-treated metallic material using the replenisher can be provided.
• the replenisher of the present invention contains a predetermined fluorine-free zirconium compound (A), a predetermined fluorine-containing compound (B) and a predetermined acid component (C), and contains zirconium ion (Zr ion) at a high concentration.
• a ratio (M AC /M F ) between the total molar quantity (M AC ) of anions derived from the acid component (C) and the total molar quantity (M F ) of fluorine ion (F ion), and a ratio (M F M Zr ) between the total molar quantity (M Zr ) of zirconium ion and the total molar quantity (M F ) of fluorine ion fall within predetermined ranges.
• the metallic material surface treating solution is continuously replenished with the replenisher in continuous production of chemical conversion coatings
• increase of HF can be inhibited and a large amount of zirconium ion can be continuously supplied.
• the chemical conversion treatment and/or electrolysis treatment can be continuously performed on/over metallic materials while the amount of auto-drained solution is suppressed.
• the ratio (M AC /M F ) to fall within the predetermined range, the replenisher that has more excellent long-term storage stability and that enables the chemical conversion treatment and/or electrolysis treatment to be continuously performed on/over metallic materials can be provided.
• the replenisher of the present invention is used to mainly supply zirconium ion to a metallic material surface treating solution that contains zirconium ion and fluorine ion and that is used to form on/over a metallic material surface a chemical conversion coating containing zirconium as the main component through chemical conversion treatment and/or electrolysis treatment. Meanwhile, it should be noted that implementation of auto-drainage in the continuous production of chemical conversion coatings is not denied.
• the fluorine-free zirconium compound (A) contained in the replenisher of the present invention is a compound that does not contain fluorine atoms but contains Zr atoms.
• the fluorine-free zirconium compound (A) includes at least one compound selected from the group consisting of zirconium basic carbonate, zirconium carbonate, zirconium hydroxide and ammonium zirconium carbonate.
• zirconium basic carbonate or zirconium carbonate is more preferable in terms of improving the storage stability of the replenisher and continuously performing the surface treatment more frequently (hereinafter, simply referred to as “in terms of improving the excellent effect of the present invention”).
• the fluorine-containing compound (B) contained in the replenisher of the present invention is a compound that contains fluorine atoms and that supplies the replenisher with F ion.
• hexafluorozirconic acid or a salt thereof is used as the fluorine-containing compound (B)
• Zr ion is also supplied into the replenisher.
• the fluorine-containing compound (B) includes at least one compound selected from the group consisting of hydrofluoric acid, a salt of hydrofluoric acid, hexafluorozirconic acid and a salt of hexafluorozirconic acid.
• hydrofluoric acid or hexafluorozirconic acid is more preferable from the standpoint of improving the excellent effect of the present invention.
• Examples of the salt of hydrofluoric acid includes a salt of hydrofluoric acid with a base (such as an amine compound) and preferably a salt of hydrofluoric acid with a base that contains no metal, such as an ammonium salt.
• examples of the salt of hexafluorozirconic acid include metal acid salts (for example, sodium salt, potassium salt, lithium salt, ammonium salt and the like) such as K 2 ZrF 6 .
• the acid component (C) contained in the replenisher of the present invention performs roles as adjusting a pH of the replenisher and promoting solubility of other components (fluorine-free zirconium compound (A) and/or fluorine-containing compound (B)).
• the acid component (C) includes at least one component 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 from the standpoint of improving the excellent effect of the present invention.
• Two or more acid components described above may be used as the acid component (C).
• the ratio (M AC /M F ) of the total molar quantity (M AC ) of anions derived from the acid component (C) with respect to the total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) is 0.35 or more and less than 2.00.
• the total concentration (g/L) of zirconium ion derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 25 or higher.
• the ratio (M F /M Zr ) of the total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) with respect to the total molar quantity (M Zr ) of zirconium ion derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 2.00 or more and less than 6.00.
• the ratio (M AC /M F ) of the total molar quantity (M AC ) of anions derived from the acid component (C) with respect to the total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) is 0.35 or more and less than 2.00.
• the replenisher has excellent storage stability and enables continuous and stable production of chemical conversion coatings without accumulation of HF in the metallic material surface treating solution.
• 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, further more preferably more than 0.50 and 1.60 or less, and yet further more preferably 1.00 or more and 1.60 or less.
• the ratio (M AC /M F ) is less than 0.35, the long-term storage stability of the replenisher is inferior. If the ratio (M AC /M F ) is 2.00 or more, when the replenisher is continuously used, the coating weight would decrease, and the desired coating cannot be formed.
• Anions derived from the acid component (C) are NO 3 ⁇ , SO 4 2 ⁇ , and CH 3 COO ⁇ .
• the total concentration (g/L) of zirconium ion derived from the fluorine-free zirconium compound (A) and from the fluorine-containing compound (B) is 25 or higher.
• the concentration is within the range, chemical conversion coatings can be more economically produced.
• the total concentration (g/L) of zirconium ion is preferably 30 or higher, and more preferably 35 or higher, since the amount of replenisher used can be reduced, and the operation economy can be better.
• the upper limit of the concentration is often 70 or lower, in view of solubility of the fluorine-free zirconium compound (A) and the fluorine-containing compound (B).
• the ratio (M F /M Zr ) of the total molar quantity (M F ) of fluorine ion derived from the fluorine-containing compound (B) with respect to the total molar quantity (M Zr ) of zirconium ion derived from the fluorine-free zirconium compound (A) and the fluorine-containing compound (B) is 2.00 or more and less than 6.00.
• the ratio (M F /M Zr ) is preferably 2.50 to 5.50, and more preferably 3.00 to 5.00.
• the ratio (M F /M Zr ) is less than 2.00, it is difficult to have zirconium compounds dissolved in the replenisher.
• the ratio (M F /M Zr ) is 6.00 or more, when the replenisher is continuously used, accumulation of HF in the metallic material surface treating solution cannot be inhibited. Therefore, for stable production of chemical conversion coatings, the amount of auto-drained solution needs to be increased, which is not preferable from the environmental and economical standpoint.
• the respective ions described above can be measured using a known measurement device, atomic absorption, ICP, ion chromatography, or a fluorine ion meter.
• the fluorine-free zirconium compound (A) content is not particularly limited as long as the above-described relationships (I) to (III) are satisfied, but is preferably 0.1 to 500 parts by mass, and more preferably 10 to 300 parts by mass, with respect to 100 parts by mass of the fluorine-containing compound (B), since the deposition efficiency of the chemical conversion coating is excellent.
• 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, since the replenisher has excellent stability.
• an alkaline component can be also used.
• the alkaline component include alkali metal oxides such as sodium hydroxide, potassium hydroxide and the like; hydroxides of alkali earth metals such as calcium hydroxide, magnesium hydroxide and the like; and organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and the like. Among these, ammonia is preferably used since it has no metallic contamination and contains no organic solvent.
• the replenisher of the present invention may contain a solvent as necessary.
• the type of solvent used is not particularly limited, and water and/or an organic solvent is normally used.
• organic solvent examples include an alcohol-based solvent and the like. While the organic solvent content may be within the range in which stability of the replenisher and of the metallic material surface treating solution to be replenished with the replenisher is not impaired, no organic solvent is preferably contained from the standpoint of the working environment.
• the total mass of the above-described fluorine-free zirconium compound (A), fluorine-containing compound (B) and acid component (C) when the replenisher contains a solvent is preferably 2 mass % to 90 mass %, and more preferably 4 mass % to 80 mass %, with respect to the whole quantity of replenisher, since the deposition efficiency of the chemical conversion coating is more excellent.
• the method for producing the replenisher of the present invention is not particularly limited, and any known method is adopted. Examples thereof include the method in which the fluorine-free zirconium compound (A), the fluorine-containing compound (B) and the acid component (C) are added in the solvent(s) and mixed.
• the method for producing the surface-treated metallic materials of the present invention is a method in which chemical conversion treatment and/or electrolysis treatment is continuously performed on/over a metallic material in a metallic material surface treating solution containing zirconium ion and fluorine ion to form a chemical conversion coating containing zirconium on/over the metallic material.
• the zirconium ion concentration in the metallic material surface treating solution decreases accordingly, making it harder to form a coating containing a zirconium compound.
• the metallic material surface treating solution is replenished with the replenisher described above.
• the replenisher is preferably added to the metallic material surface treating solution in such a manner that the zirconium ion concentration does not decrease by 20% or more.
• the total amount of fluorine ion supplied together with zirconium is preferably an amount obtained by subtracting the amount of fluorine ion in HF generated in the metallic material surface treating solution as a by-product during producing the coating containing the zirconium compound from the sum of all fluorine ion that is taken into the chemical conversion coating and all fluorine ion in the metallic material surface treating solution that adheres to the metallic material having the chemical conversion coating formed on/over the surface when the metallic material is taken out from the bath.
• the method for adding the replenisher of the present invention into the metallic material surface treating solution is not particularly limited, and examples thereof include the method in which the replenisher is divided into small portions and added in several times (method A) and the method in which the replenisher in a predetermined amount is added at once (method B).
• method A the method in which the replenisher is divided into small portions and added in several times
• method B the method in which the replenisher in a predetermined amount is added at once
• the method A is preferable, since component variation in the metallic material surface treating solution is small and the surface-treated metallic materials can be continuously and stably produced.
• the replenisher of the present invention when the replenisher of the present invention is added into the metallic material surface treating solution, either of the method in which production is once suspended and the replenisher is added into the metallic material surface treating solution and the method in which production is not suspended and the replenisher is added into the metallic material surface treating solution during production method of the surface-treated metallic materials can be adopted.
• the method in which the replenisher is added into the metallic material surface treating solution during production method of the surface-treated metallic materials is preferable, since production efficiency is excellent particularly at high-speed operation, and the surface-treated metallic materials can be continuously and stably produced.
• the metallic material surface treating solution used in the method for producing the surface-treated metallic materials of the present invention described above contains Zr ion and fluorine ion.
• Examples of the supply source of zirconium ion in the metallic material surface treating solution include the above-described fluorine-free zirconium compound (A), hexafluorozirconic acid or a salt thereof.
• Zr ion in the metallic material surface treating solution refers to both (1) zirconium fluoride complex ion in which 1 to 6 moles of fluorine are coordinated to 1 mole of zirconium as expressed by ZrF n (4-n) and (2) zirconium ion or zirconyl ion generated from inorganic acid zirconium such as zirconium nitrate and zirconium sulfate or inorganic acid zirconyl, or alternatively, an organic acid zirconium or organic acid zirconyl such as zirconium acetate and zirconyl acetate.
• the amount of zirconium ion contained in the metallic material surface treating solution is not particularly limited but is preferably 0.05 g/L to 10.00 g/L, and more preferably 0.10 g/L to 2.00 g/L, since the metallic material surface treating solution has more excellent stability, and the deposition efficiency of the chemical conversion coating is also more excellent.
• Any known compound containing fluorine (fluorine-containing compound) can be used as the supply source of fluorine ion in the metallic material surface treating solution.
• a fluorine compound having at least one element selected from the group consisting of Ti, Zr, Hf, Si, Al and B is preferably used as the fluorine-containing compound.
• Specific examples thereof include complexes in which 1 to 3 hydrogen atoms are coordinated to anions such as (TiF 6 ) 2 ⁇ , (ZrF 6 ) 2 ⁇ , (HfF 6 ) 2 ⁇ , (SiF 6 ) 2 ⁇ , (AlF 6 ) 3 ⁇ and (BF 4 OH) ⁇ , and ammonium salts and metal salts of these anions.
• fluorine-containing compound examples include hydrofluoric acid and its ammonium salt and alkali metal salts; metal fluorides (such as aluminum fluoride, zinc fluoride, vanadium fluoride, tin fluoride, manganese fluoride, ferrous fluoride and ferric fluoride or the like); and acid fluorides (such as fluorine oxide, acetyl fluoride and benzoyl fluoride or the like).
• metal fluorides such as aluminum fluoride, zinc fluoride, vanadium fluoride, tin fluoride, manganese fluoride, ferrous fluoride and ferric fluoride or the like
• acid fluorides such as fluorine oxide, acetyl fluoride and benzoyl fluoride or the like.
• Fluorine ion in the metallic material surface treating solution refers to both fluorine ion (F ⁇ ) derived from HF present in the metallic material surface treating solution and fluorine ion in fluorine-containing complex ion such as the above-described zirconium fluoride complex ion, and the total fluorine ion concentration described above and later refers to the concentration of the sum of both fluorine ion.
• Free fluorine concentration refers to the concentration of HF-derived fluorine ion (F ⁇ ).
• the total amount of fluorine ion contained in the metallic material surface treating solution is not particularly limited but is preferably 0.050 g/L to 10.000 g/L, and more preferably 0.100 g/L to 3.000 g/L as the total fluorine ion concentration, since the metallic material surface treating solution has more excellent stability, and the deposition efficiency of the chemical conversion coating is also excellent.
• the free fluorine ion concentration is preferably 5 mg/L to 400 mg/L, and more preferably 10 mg/L to 250 mg/L.
• the amounts (concentrations) of Zr ion, total fluorine ion, and free fluorine ion in the metallic material surface treating solution can be measured by using atomic absorption, ICP, ion chromatography or a fluorine ion meter.
• the pH of the metallic material surface treating solution is appropriately adjusted according to the metallic material to be treated or the condition of the chemical conversion treatment or electrolysis treatment, but is preferably about 2.5 to 5.0, and more preferably 3.0 to 5.0, since the metallic material surface treating solution has more excellent stability and the deposition efficiency of the chemical conversion coating is also more excellent.
• the pH of the metallic material surface treating solution can be measured by using a pH meter.
• the type of metallic material used is not particularly limited, and any known metallic material can be used. Examples thereof include iron material, plating material, zinc material, aluminum material, magnesium material and the like.
• the shape of the metallic material is not particularly limited and can be a plate shape or any other shape.
• Examples of the other shapes include a vehicle body of a transporting device such as an automobile and its constituent component, a farm equipment and its constituent component, steel furniture, building material and the like.
• the chemical conversion treatment using the metallic material surface treating solution described above can be performed using known treatment facilities under a known condition.
• the chemical conversion treatment is a treatment in which a metallic material is brought into contact (immersion, coating or spraying) with a predetermined metallic material surface treating solution that is at normal temperature or heated, whereby a coating is formed on/over the surface of the metallic material.
• the duration of contact between the metallic material and the metallic material surface treating solution is appropriately adjusted depending on the quality or shape of the metallic material to be treated, treatment method, application thereof and the targeted coating weight, and is normally about 0.1 second to 600 seconds in many cases, since the chemical conversion coating has more excellent properties.
• the electrolysis treatment (anodic electrolysis treatment, cathodic electrolysis treatment) using the metallic material surface treating solution can be performed using known electrolysis treatment facilities under a known condition.
• the current density is preferably 0.1 A/dm 2 to 20.0 A/dm 2 , and more preferably 0.5 A/dm 2 to 10.0 A/dm 2 since the deposition efficiency of the chemical conversion coating is excellent.
• the coating weight of zirconium in the formed chemical conversion coating is appropriately adjusted depending on the quality or application of the metallic material to be treated, and is normally about 1 mg/m 2 to 70 mg/m 2 in many cases in both the chemical conversion treatment and the electrolysis treatment, since the chemical conversion coating has more excellent properties.
• test sheets (1) to (3) were used in Examples and Comparative Examples.
• Aluminum alloy sheet (6000-series aluminum alloy, thickness: 0.8 mm) (2) Cold-rolled steel sheet (SPC, thickness: 0.8 mm) (3) Alloyed hot-dip galvanized steel sheet (GA, thickness: 0.8 mm)
• the fluorine-free zirconium compound (A), the fluorine-containing compound (B) and the acid component (C) were mixed in water so as to have compositions shown in Table 1, whereby the various replenishers were prepared.
• the above degreasing process was performed using an alkaline degreasing agent, Finecleaner L4460 (2.0%; 45° C., 120 seconds, spraying) manufactured by Nihon Parkerizing Co., Ltd.
• any one of the following continuous treating methods 1 to 3 was performed.
• the treating solution was adjusted to have a pH of 4.0 and heated to 40° C. to prepare a metallic material surface treating solution.
• the metallic material surface treating solution was stirred and a test sheet (1) was immersed in the metallic material surface treating solution for 180 seconds, whereby the surface treatment was performed to achieve a target Zr coating weight of 13 mg/m 2 .
• This process was regarded as one cycle and repeated using new test sheets (1) so as to perform surface treatment (continuous treating test).
• the test was conducted until the processing load reached 13.3 m 2 /L, and the Zr coating weight at the beginning of the continuous treating test and the Zr coating weight at the time when the processing load became 13.3 m 2 /L were measured.
• the Zr coating weight on the surface of the treated material was quantitatively determined using X-ray fluorescence (XRF) analysis.
• a bath was made up of 10 L of a treating solution having the components of concentrations described below, the treating solution was adjusted to have a pH of 4.0 and heated to 40° C. to prepare a metallic material surface treating solution.
• the metallic material surface treating solution was stirred and a test sheet (2) was immersed in the metallic material surface treating solution for 120 seconds, whereby the surface treatment was performed to achieve a target Zr coating weight of 20 mg/m 2 .
• This process was regarded as one cycle and repeated using new test sheets (2) so as to perform surface treatment (continuous treating test).
• the test was conducted until the processing load reached 16.7 m 2 /L, and the Zr coating weight at the beginning of the continuous treating test and the Zr coating weight at the time when the processing load became 16.7 m 2 /L were measured.
• the Zr coating weight on the surface of the treated material was quantitatively determined using X-ray fluorescence (XRF) analysis.
• the treating solution was adjusted to have a pH of 3.7 and heated to 40° C. to prepare a metallic material surface treating solution.
• the metallic material surface treating solution was stirred and a test sheet (3) was immersed in the metallic material surface treating solution for 30 seconds, thereby the surface treatment was performed to achieve a target Zr coating weight of 10 mg/m 2 .
• This process was regarded as one cycle and repeated using new test sheets (3) so as to perform surface treatment (continuous treating test).
• the test was conducted until the processing load reached 45.5 m 2 /L, and the Zr coating weight at the beginning of the continuous treating test and the Zr coating weight at the time when the processing load became 45.5 m 2 /L were measured.
• the Zr coating weight on the surface of the treated material was quantitatively determined using X-ray fluorescence (XRF) analysis.
• the replenisher shown in Table 1 was put in a plastic container, which was sealed.
• the replenisher was stored for a maximum of 6 months at 35° C. immediately after sealed, and appearance of the solution was then evaluated.
• the evaluation standards are described below. Practically, “Good” or “Excellent” is preferable.
• “appearance does not change” means that none of precipitation, turbidness and gelation is observed, and the solution is colorless and transparent.
• the Zr coating weight after 100% replacement is 95% or more and less than 105% with respect to the Zr coating weight at the beginning of the continuous treating test.
• Poor The Zr coating weight after 100% replacement is less than 50% with respect to the Zr coating weight at the beginning of the continuous treating test.
• the replenisher made from the mixture solution of hexafluorozirconic acid and zirconium nitrate described in paragraph [0033] of Patent Literature 3 has the ratio M AC /M F of 0.33 and could not achieve the desired effect, as being apparent from Comparative Examples 1 to 3 in Table 1.

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  • 2013-05-28 EP EP13886009.3A patent/EP3006600B1/fr active Active
  • 2013-05-28 WO PCT/JP2013/064801 patent/WO2014192082A1/fr active Application Filing
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