WO2017138530A1 - Procédé de réapprovisionnement de bain de conversion chimique - Google Patents

Procédé de réapprovisionnement de bain de conversion chimique Download PDF

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Publication number
WO2017138530A1
WO2017138530A1 PCT/JP2017/004414 JP2017004414W WO2017138530A1 WO 2017138530 A1 WO2017138530 A1 WO 2017138530A1 JP 2017004414 W JP2017004414 W JP 2017004414W WO 2017138530 A1 WO2017138530 A1 WO 2017138530A1
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WIPO (PCT)
Prior art keywords
chemical conversion
aluminum
conversion treatment
treatment bath
bath
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PCT/JP2017/004414
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English (en)
Japanese (ja)
Inventor
雅之 神村
真彦 松川
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日本ペイント・サーフケミカルズ株式会社
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Application filed by 日本ペイント・サーフケミカルズ株式会社 filed Critical 日本ペイント・サーフケミカルズ株式会社
Priority to CN201780010530.6A priority Critical patent/CN108603293A/zh
Priority to US16/076,180 priority patent/US20190136385A1/en
Priority to KR1020187022919A priority patent/KR20180100220A/ko
Priority to EP17750252.3A priority patent/EP3415660A4/fr
Publication of WO2017138530A1 publication Critical patent/WO2017138530A1/fr

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Classifications

    • 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
    • C23C22/05—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
    • C23C22/361—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 containing titanium, zirconium or hafnium compounds
    • 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

  • This invention relates to the replenishment method to a chemical conversion treatment bath.
  • the chemical conversion treatment of aluminum and their alloys by the treatment bath and treatment method described in Patent Document 1 usually includes a step of continuously conveying an object to be treated to the treatment bath and immersing or spraying the treatment bath in the treatment bath. .
  • the active ingredient in the treatment bath is consumed and the composition of the ingredient in the treatment bath changes.
  • aluminum is etched from the substrate surface by fluorine, so that the relative concentration of aluminum in the treatment bath gradually increases and causes aluminum sludge.
  • the present inventors have found that the ratio between the aluminum ion concentration and the fluorine ion concentration in the chemical conversion treatment bath is within a certain range.
  • the present inventors have found that a chemical conversion film having both corrosion resistance and coating film adhesion can be formed.
  • the present invention maintains the ratio of the aluminum ion concentration and the fluorine ion concentration in the chemical conversion treatment bath within a certain range, so that the corrosion resistance of the chemical conversion film formed even if the aluminum-based metal chemical conversion treatment bath is continuously used. And it aims at providing the replenishment method to the aluminum type metal chemical conversion treatment bath which can maintain coating-film adhesiveness.
  • the present invention is a method for supplying a replenisher to an aluminum-based metal chemical treatment bath, wherein the replenisher includes at least one of a zirconium salt and a titanium salt, and an effective fluoride.
  • the replenisher is replenished so that the ratio of the fluorine ion concentration (mg / L) to the aluminum ion concentration (mg / L) in the aluminum-based metal chemical conversion treatment bath is F / Al of 1.8 to 4.5.
  • a replenishing method for an aluminum-based metal chemical conversion treatment bath is provided.
  • the replenisher further contains at least one selected from the group consisting of phosphoric acid, phosphorous acid, and hydrogen peroxide.
  • the aluminum-based metal chemical conversion treatment bath includes at least one selected from the group consisting of at least one of a zirconium salt and a titanium salt, an effective fluoride, phosphoric acid, condensed phosphoric acid, and a salt thereof, It is preferable to include at least one selected from the group consisting of phosphoric acid, hypophosphorous acid, and salts thereof.
  • replenish the replenisher so that the F / Al is 1.8 to 4.5 by replenishing the replenisher so that the pH of the chemical conversion bath is within a predetermined range. .
  • the replenisher is replenished so that the F / Al is 1.8 to 4.5 by replenishing the replenisher so that the electrical conductivity of the chemical conversion bath is within a predetermined range. Is preferred.
  • the aluminum-based metal chemical conversion treatment bath is an aluminum beverage can.
  • the present invention it is possible to provide a replenishment method for an aluminum-based metal chemical conversion treatment bath that can maintain the corrosion resistance and coating film adhesion of the formed chemical conversion coating even if the aluminum-based metal chemical conversion treatment bath is continuously used.
  • the aluminum-based metal chemical conversion treatment bath to which the replenishment method according to the present embodiment is applied is used to form a protective film having good appearance, corrosion resistance, coating film adhesion, and the like on an aluminum substrate made of an aluminum-based metal. .
  • An aluminum-based metal chemical conversion treatment bath (hereinafter sometimes referred to as “chemical conversion treatment bath”) to which the replenishment method according to the present embodiment is applied includes at least one of a zirconium salt and a titanium salt, an effective fluoride, and phosphoric acid. , At least one selected from the group consisting of condensed phosphoric acid and salts thereof (hereinafter sometimes referred to as “phosphoric acid etc.”), and a group consisting of phosphorous acid, hypophosphorous acid, and salts thereof It is obtained by diluting a chemical conversion treatment composition containing at least one selected (hereinafter sometimes referred to as “phosphorous acid etc.”) with an appropriate amount of water.
  • a chemical conversion film having excellent corrosion resistance and the like can be formed on the surface of the aluminum substrate.
  • the effective fluoride contained in the chemical conversion bath etches and separates the oxide film formed on the surface of the aluminum substrate.
  • Phosphorous acid or the like functions as a reducing agent that prevents oxidation of the etched aluminum substrate surface.
  • a double salt is formed by at least one of zirconium salt and titanium salt, effective fluoride, phosphoric acid, etc., phosphorous acid, etc., and a strong chemical conversion film is formed on the surface of the aluminum substrate.
  • zirconium salt No particular limitation is imposed on the zirconium salt contained in the chemical conversion treatment bath according to the present embodiment, for example, zirconium hydrofluoric acid (H 2 ZrF 6) and lithium fluoro zirconate, sodium, potassium, ammonium salts (Li 2 ZrF 6 , Na 2 ZrF 6 , K 2 ZrF 6 , (NH 4 ) 2 ZrF 6 ), zirconium sulfate (Zr (SO 4 ) 2 ), zirconyl sulfate (ZrO (SO 4 )), zirconium nitrate (Zr (NO 3) 4 ), zirconyl nitrate (ZrO (NO 3 ) 2 ), zirconium acetate, zirconium fluoride (ZrF 4 ) and the like. These may be used alone or in combination of two or more.
  • titanium salt No particular limitation is imposed on the titanium salt contained in the chemical conversion treatment bath according to the present embodiment, for example, lithium titanium hydrofluoric acid and fluorotitanic acid, sodium, potassium, ammonium salts (Li 2 TiF 6, Na 2 TiF 6 , K 2 TiF 6 , (NH 4 ) 2 TiF 6 ), titanium sulfate (Ti (SO 4 ) 2 ), titanyl sulfate (TiO (SO 4 )), titanium nitrate (Ti (NO 3 ) 4 ), titanine nitrate ( Examples thereof include TiO (NO 3 ) 2 ) and titanium fluoride (TiF 3 ⁇ TiF 4 ). These may be used alone or in combination of two or more.
  • At least one of the zirconium salt and the titanium salt is preferably contained in the chemical conversion treatment bath according to this embodiment in an amount of 10 ppm or more in terms of metal, more preferably 10 to 500 ppm, and still more preferably 10 to 100 ppm.
  • concentration of at least one of the zirconium salt and the titanium salt in the chemical conversion bath is less than 10 ppm in terms of metal, almost no chemical conversion film is formed.
  • the concentration of at least one of the zirconium salt and the titanium salt is within 500 ppm in terms of the metal. Preferably there is.
  • Effective fluoride refers to fluoride that liberates fluorine ions in the chemical conversion treatment bath. No particular limitation is imposed on the effective fluoride contained in the chemical conversion treatment bath according to the present embodiment, for example, hydrofluoric acid (HF), ammonium fluoride (NH 4 F), ammonium hydrogen fluoride (NH 4 HF 2 ), Sodium fluoride (NaF), sodium hydrogen fluoride (NaHF 2 ) and the like. These may be used alone or in combination of two or more.
  • HF hydrofluoric acid
  • NH 4 F ammonium fluoride
  • NH 4 HF 2 ammonium hydrogen fluoride
  • NaF sodium fluoride
  • NaHF 2 sodium hydrogen fluoride
  • fluorine ions are liberated from the effective fluoride.
  • the fluorine ion has a function of suppressing precipitation of zirconium phosphate generated in the chemical conversion bath. Furthermore, it has the function to suppress the generation
  • the fluorine ion concentration (mg / L) in the chemical conversion bath according to this embodiment is the ratio of the concentration of aluminum ions (mg / L) eluted in the chemical conversion bath by the chemical conversion reaction, F / Al. Is preferably in the range of 1.8 to 4.5.
  • F / Al is 1.8 or more, the uniformity of the chemical conversion film formed on the surface of the aluminum substrate is improved by sufficiently solubilizing aluminum ions in the chemical conversion treatment bath.
  • F / Al is preferably 1.8 to 2.2.
  • the concentration of aluminum ions can be measured by ICP (inductively coupled plasma emission spectrometer), and the concentration of fluorine ions can be measured by ion chromatography.
  • [Phosphoric acid, etc.] It is not particularly restricted but may be phosphoric acid and its salts contained in the chemical conversion treatment bath according to the present embodiment, for example, H 3 PO 4, (NH 4) H 2 PO 4, NaH 2 PO 4, KH 2 PO 4 , etc. And alkaline earth metal phosphates such as calcium phosphate and magnesium phosphate.
  • alkaline earth metal phosphates such as calcium phosphate and magnesium phosphate.
  • condensed phosphoric acid and its salt contained in the chemical conversion treatment bath which concerns on this embodiment, For example, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, ultraphosphoric acid etc. are mentioned.
  • the salt of condensed phosphoric acid include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, and ammonium salts. These may be used alone or in combination of two or more.
  • Phosphoric acid and the like are preferably contained in the chemical conversion bath according to the present embodiment in an amount of 10 ppm or more, more preferably 10 to 500 ppm, and even more preferably 10 to 100 ppm in terms of phosphoric acid.
  • concentration in the chemical conversion treatment bath of phosphoric acid or the like according to this embodiment is less than 10 ppm in terms of phosphoric acid, boiling water blackening occurs.
  • concentration of phosphoric acid or the like in the chemical conversion bath exceeds 500 ppm in terms of phosphoric acid, boiling water blacking resistance is caused and coating film adhesion is deteriorated.
  • [Phosphorous acid, etc.] Although it does not specifically limit as phosphorous acid, hypophosphorous acid, and these salts contained in the chemical conversion treatment bath which concerns on this embodiment, for example, in addition to phosphorous acid and hypophosphorous acid, as these salts, sodium, examples include alkali metal salts such as potassium, alkaline earth metal salts such as calcium and magnesium, and ammonium salts. These may be used alone or in combination of two or more.
  • Phosphorous acid or the like is preferably contained in the chemical conversion bath according to this embodiment in an amount of 10 ppm or more in terms of phosphorous acid, more preferably 10 to 5000 ppm, and even more preferably 50 to 500 ppm.
  • concentration in the chemical conversion treatment bath such as phosphorous acid according to the present embodiment is less than 10 ppm in terms of phosphorous acid, the uniformity of the chemical conversion film becomes insufficient.
  • concentration of phosphorous acid or the like in the chemical conversion treatment bath is 5000 ppm or more in terms of phosphorous acid, the coating film adhesion is lowered.
  • an antibacterial agent such as ethanol and isopropanol
  • guanidine group-containing compounds such as polyhexamethylenebiguanidine hydrochloride
  • benzimidazoles such as 2- (4-thiazolyl) -benzimidazole and methyl-2-benzimidazole carbamate.
  • Antibacterial agents phenolic antibacterial agents such as p-chloro-m-xylenol and p-chloro-m-cresol, 2,4,5,6-tetrachloroisophthalonitrile, 1,2-dibromo-2,4- Nitryl antibacterial agents such as dicyanobutane, pyridine antibacterial agents such as (2-pyridylthio-1-oxide) sodium and bis (2-pyridylthio-1-oxide) zinc, 2-methyl-4-isothiazolin-3-one , 5-chloro-2-methyl-4-isothiazolin-3-one, etc.
  • isothiazolone antibacterial Benzalkonium chloride, quaternary ammonium salts such as benzethonium chloride, benzoic acid, p- oxyethyl benzoate, sorbic acid, potassium sorbate, sodium dehydroacetate, sodium propionate.
  • surfactants include nonionic surfactants, cationic surfactants, and anionic surfactants.
  • rust inhibitors include tannic acid, imidazoles, triazines, guanines, and hydrazines. , Biguanides and the like.
  • a silane coupling agent, colloidal silica, amines, a phenol-based water-soluble organic compound containing a phenol resin, and the like may be added to the chemical conversion bath.
  • the pH at 25 ° C. of the chemical conversion treatment bath according to the present embodiment is preferably 2 to 4, and more preferably 2.5 to 3.5.
  • the pH of the chemical conversion treatment bath is less than 2, not only etching becomes excessive and it becomes difficult to form a chemical conversion film, but boiling water blackening resistance and coating film adhesion deteriorate.
  • the pH of the chemical conversion bath exceeds 4, the chemical conversion bath becomes cloudy and sludge is generated, and it is difficult to form a chemical conversion film, resulting in a decrease in resistance to boiling water blackening.
  • the treatment target of the chemical conversion treatment bath according to the present embodiment is an aluminum base
  • the aluminum-based metal that is the material of the aluminum base is not particularly limited, but aluminum, aluminum-copper alloy, aluminum-manganese alloy, aluminum-silicon An alloy, an aluminum-magnesium alloy, an aluminum-magnesium-silicon alloy, an aluminum-zinc alloy, an aluminum-zinc-magnesium alloy, and the like can be given.
  • it does not restrict
  • the aluminum-based metal chemical conversion treatment bath according to the present embodiment can preferably chemically convert an aluminum beverage can made of a 3000-based alloy.
  • the chemical conversion treatment bath according to this embodiment a uniform chemical conversion film can be formed on the surface of the aluminum substrate. Therefore, since the corrosion resistance can be maintained even if the chemical conversion film is thinned, the adhesion of the chemical conversion film can be improved. For example, since an aluminum beverage can is subjected to severe drawing after the formation of a chemical conversion film, adhesion of the chemical conversion film is required in addition to corrosion resistance, but the chemical conversion treatment bath according to this embodiment is for such an aluminum beverage can etc. Are also preferably used.
  • the replenisher used in the replenishment method for the aluminum-based metal chemical conversion treatment bath according to the present embodiment includes at least one of a zirconium salt and a titanium salt, and an effective fluoride, and includes phosphoric acid, phosphorous acid, hydrogen peroxide It is preferable to further include at least one selected from the group consisting of:
  • At least one of zirconium salt and titanium salt, effective fluoride, phosphoric acid, and phosphorous acid are components that form a chemical conversion film by forming a double salt. Is consumed.
  • fluorine ions are liberated from the effective fluoride, but fluorine ions are consumed by forming aluminum ions and fluoroaluminum eluted in the chemical conversion bath.
  • phosphorous acid functions as a reducing agent which prevents the oxidation of the surface of the aluminum base material etched by fluorine, it loses its function as a reducing agent when it is oxidized. Therefore, it is necessary for the chemical conversion treatment bath to be used by continuously adding these components to the chemical conversion treatment bath.
  • the zirconium salt contained in the replenisher according to the present embodiment is not particularly limited, and examples thereof include a zirconium salt contained in the chemical conversion treatment bath according to the present embodiment.
  • examples of the titanium salt, effective fluoride, phosphoric acid, and phosphorous acid include effective fluoride, phosphoric acid, phosphorous acid, and the like included in the chemical conversion treatment bath according to the present embodiment.
  • the replenisher according to the present embodiment may contain a pH adjuster. It does not specifically limit as a pH adjuster, General acids and alkalis, such as nitric acid and ammonia, are mentioned.
  • the replenisher according to the present embodiment may contain an antibacterial agent, a surfactant, a rust preventive agent, and the like as necessary, as in the case of the chemical conversion treatment bath.
  • ⁇ Replenishment method> a replenishment method for the aluminum-based metal chemical conversion treatment bath performed using the replenisher according to the present embodiment will be described.
  • the above replenisher is replenished so that the ratio of F / Al is 1.8 to 4.5.
  • the aluminum ion concentration in the chemical conversion treatment bath is increased by etching the aluminum-based metal with fluorine in the chemical conversion treatment bath.
  • An increase in the aluminum ion concentration causes aluminum sludge.
  • aluminum ions are combined with fluorine ions to become fluoroaluminum and are solubilized, aluminum sludge can be prevented by the presence of a sufficient amount of fluorine ions relative to the aluminum ions.
  • fluorine ion concentration in the chemical conversion bath increases, etching with fluorine ions becomes excessive, and formation of the chemical conversion film is hindered.
  • etching by fluorine ions is suppressed by combining aluminum ions and fluorine ions to form fluoroaluminum.
  • the presence of a sufficient amount of aluminum ions relative to fluorine ions suppresses excessive etching by fluorine ions. Therefore, it is important to maintain the ratio between the aluminum ion concentration and the fluorine ion concentration in the chemical conversion bath within the above range.
  • F / Al is 1.8 or more
  • the aluminum ion is sufficiently solubilized in the chemical conversion treatment bath to improve the uniformity of the chemical conversion film formed on the surface of the aluminum substrate, and is preferably 4.5 or less.
  • F / Al is preferably 1.9 to 2.1.
  • the replenisher is replenished so that the pH at 25 ° C. in the chemical conversion bath is 2 to 4.
  • the pH of the chemical conversion bath at 25 ° C. is less than 2, the amount of etching with respect to the aluminum base increases as described above, and the aluminum ion concentration increases.
  • the pH exceeds 4 the permissible dissolved concentration of aluminum ions decreases, so the aluminum ion concentration decreases. Therefore, by maintaining the pH within the above range, the aluminum ion concentration in the chemical conversion bath can be maintained within a certain value, and F / Al can be easily maintained within a preferred range.
  • the measuring method of pH is not specifically limited, A commercially available pH electrode etc. are used.
  • the replenisher according to the present embodiment when added so that the pH is maintained within the above range, the replenisher is consequently maintained so that F / Al is maintained within the range of 1.8 to 4.5. It is preferable to adjust the content and pH of components such as effective fluoride contained.
  • the replenisher is replenished so that the electrical conductivity of the chemical conversion bath at 25 ° C. is 0.5 to 5 mS / cm.
  • the continuous use of the chemical conversion treatment bath consumes zirconium salt, titanium salt, effective fluoride, phosphoric acid, phosphorous acid, etc., which are film forming components in the chemical conversion treatment agent, Ion concentration decreases.
  • the electrical conductivity of the chemical conversion bath decreases. Therefore, by maintaining the electric conductivity within the above range, the concentration of the film forming component in the chemical conversion treatment bath can be maintained within a certain value.
  • the measuring method of electrical conductivity is not specifically limited, A commercially available EC electrode etc. are used.
  • the replenisher according to the present embodiment when added so that the electric conductivity is maintained within the above range, the replenishment is performed so that F / Al is maintained within the range of 1.8 to 4.5 as a result. It is preferable to adjust the content of components such as effective fluoride contained in the agent.
  • the method of replenishing the replenisher according to the present embodiment is not particularly limited, but it is preferable that a small amount is replenished as needed so that the composition of each component in the chemical conversion bath does not change greatly.
  • the pH and electrical conductivity are automatically managed so as to be maintained within a certain value in accordance with the detected value of the pH electrode or EC electrode.
  • the chemical conversion treatment bath to which the replenishment method of the present embodiment is applied can preferably carry out chemical conversion treatment of aluminum beverage cans and the like that require adhesion as well as corrosion resistance of the chemical conversion coating.
  • ⁇ Chemical conversion treatment method> a chemical conversion treatment method for an aluminum-based metal performed using the chemical conversion treatment bath according to the present embodiment will be described.
  • pretreatment of the aluminum substrate is performed.
  • aluminum cans such as beverage cans are manufactured by drawing and so-called drawing and ironing processing (hereinafter referred to as “DI processing”), and aluminum powder or lubricating oil called smut generated in the process is on the surface.
  • DI processing drawing and ironing processing
  • an oxide film is usually formed on the surface of the aluminum base and is passivated. Therefore, it is preferable to remove these smuts and lubricating oil by alkali treatment, acid treatment, etc., and to appropriately etch the surface of the aluminum base.
  • alkali treatment or acid treatment as a pretreatment, a strong chemical conversion film can be formed on the surface of the aluminum substrate.
  • the method of chemical conversion treatment of the aluminum-based metal is not particularly limited, but is performed by immersing an aluminum product or the like to be treated in the chemical conversion treatment bath, or spraying or coating the chemical conversion treatment agent composition in the chemical conversion treatment bath. Is called.
  • the time required for the chemical conversion treatment varies depending on the chemical conversion treatment agent composition, the treatment temperature, and the treatment method for the chemical conversion treatment bath, but is usually 5 to 60 seconds.
  • the temperature of the chemical conversion treatment bath is preferably room temperature to 60 ° C., and more preferably 30 to 50 ° C. If the temperature of the chemical conversion bath is below room temperature (for example, 25 ° C.), the formation rate of the chemical conversion film is slow, and in order to increase the formation rate, the concentration of each component in the treatment bath must be increased. Even economically disadvantageous. On the other hand, when the temperature of the chemical conversion treatment bath exceeds 60 ° C., the treatment bath becomes cloudy and sludge tends to be generated. Moreover, since a great deal of energy is required to maintain the temperature of the chemical conversion bath, it is economically disadvantageous.
  • Example 1 Each component was prepared so that the concentration of zirconium ions, aluminum ions, and fluorine ions was an aqueous solution having the concentrations shown in Table 1, and used as a chemical conversion treatment bath of Example 1.
  • (NH 4 ) 2 ZrF 6 was used as the zirconium ion source, and HF was used as the fluorine ion source.
  • an aluminum can body without a lid obtained by DI processing of an aluminum alloy (A3004) plate is used, and the chemical conversion treatment is performed under the conditions shown in Table 1 for the pH of the chemical conversion treatment bath, the treatment temperature, and the treatment time. Went.
  • pH in Table 1 means pH at 25 ° C.
  • Examples 3, 5, 7, 9> In addition to zirconium ion, aluminum ion, and fluorine ion, each component was prepared so that the concentration of each component of phosphoric acid, phosphorous acid, and hydrogen peroxide (H 2 O 2 ) was the concentration shown in Table 1, Example 3 Chemical conversion treatment baths 5, 7, 9 were used. The chemical conversion treatment was performed under the same conditions as in Example 1 except that the treatment conditions were as shown in Table 1.
  • Example 2 The chemical conversion treatment bath of Example 1 was supplemented with 0.1% of replenisher A containing 20 g / L of zirconium ions, 20 g / L of fluorine ions, and 20 g / L of nitric acid to obtain a chemical conversion treatment bath of Example 2.
  • replenisher A containing 20 g / L of zirconium ions, 20 g / L of fluorine ions, and 20 g / L of nitric acid to obtain a chemical conversion treatment bath of Example 2.
  • the amount of each component in the chemical conversion bath was as shown in Table 1 by the above replenishment.
  • the chemical conversion treatment was performed under the same conditions as in Example 1 except that the treatment conditions were as shown in Table 1.
  • Example 4 The chemical conversion treatment bath of Example 3 was supplemented with 0.1% of supplementary agent B containing 10 g / L of zirconium ions, 10 g / L of fluorine ions, 10 g / L of phosphoric acid, and 20 g / L of nitric acid. A treatment bath was used. In addition, the same thing as Example 1 was used as each component source. The amount of each component in the chemical conversion bath was as shown in Table 1 by the above replenishment. The chemical conversion treatment was performed under the same conditions as in Example 1 except that the treatment conditions were as shown in Table 1.
  • Example 6 Replenishment agent C containing 0.1 g of zirconium ions, 10 g / L of fluorine ions, 10 g / L of phosphoric acid, 10 g / L of phosphorous acid, and 20 g / L of nitric acid is replenished to the chemical conversion treatment bath of Example 5.
  • the chemical conversion treatment bath of Example 6 was obtained.
  • the same thing as Example 1 was used as each component source.
  • the amount of each component in the chemical conversion bath was as shown in Table 1 by the above replenishment.
  • the chemical conversion treatment was performed under the same conditions as in Example 1 except that the treatment conditions were as shown in Table 1.
  • Example 8 Replenishment agent D containing 10 g / L of zirconium ions, 10 g / L of fluorine ions, 10 g / L of phosphoric acid, 10 g / L of hydrogen peroxide, and 20 g / L of nitric acid is replenished to the chemical conversion treatment bath of Example 7 by 0.1%. Thus, the chemical conversion treatment bath of Example 8 was obtained. In addition, the same thing as Example 1 was used as each component source. The amount of each component in the chemical conversion bath was as shown in Table 1 by the above replenishment. The chemical conversion treatment was performed under the same conditions as in Example 1 except that the treatment conditions were as shown in Table 1.
  • Example 10 Replenisher containing zirconium ion 10 g / L, fluorine ion 10 g / L, phosphoric acid 10 g / L, phosphorous acid 10 g / L, hydrogen peroxide 10 g / L, nitric acid 20 g / L with respect to the chemical conversion treatment bath of Example 9. E was replenished by 0.1% to obtain a chemical conversion treatment bath of Example 10. In addition, the same thing as Example 1 was used as each component source. The amount of each component in the chemical conversion bath was as shown in Table 1 by the above replenishment. The chemical conversion treatment was performed under the same conditions as in Example 1 except that the treatment conditions were as shown in Table 1.
  • the aluminum can body which is a to-be-processed object of the chemical conversion treatment bath of an Example and a comparative example was pre-processed with the following method.
  • First, the lubricating oil and smut were removed by spraying at 75 ° C. for 60 seconds using a commercially available acidic cleaning agent (Surf Cleaner NHC260 manufactured by Nippon Paint Surf Chemicals Co., Ltd.).
  • spray water washing was performed for 15 seconds with tap water.
  • the chemical conversion treatment agent composition which concerns on the chemical conversion treatment bath of an Example and a comparative example was sprayed on the aluminum can body which is a to-be-processed object on the conditions shown in Table 1, respectively.
  • spray water was washed with tap water for 15 seconds and deionized water for 5 seconds, and then dried at 200 ° C. for 3 minutes to obtain treatment containers for Examples and Comparative Examples used in the following evaluation tests.
  • a 1 mm cross-cut test was performed as a primary adhesion test with reference to the former JIS K 5400.
  • 100 squares having a width of 1 mm were formed on a coating film using a cutter knife, and after sticking an adhesive tape, it was peeled off and the number of squares on which the coating film remained was counted. .
  • Those having a number of squares having a coating film of 100 were evaluated as acceptable, and the others were evaluated as unacceptable. The results are shown in Table 1.

Abstract

L'objet de la présente invention est de fournir un procédé de réapprovisionnement d'un bain de conversion chimique de métal d'aluminium, le procédé permettant de maintenir la résistance à la corrosion et l'adhésivité de film de revêtement du revêtement de conversion chimique formé, même quand le bain de conversion chimique de métal d'aluminium est utilisé en continu. L'invention porte sur un procédé de réapprovisionnement d'un bain de conversion chimique de métal d'aluminium avec un agent de réapprovisionnement, l'agent de réapprovisionnement comprenant un sel de zirconium et/ou un sel de titane et un fluorure efficace, et l'agent de réapprovisionnement étant fourni de sorte que le rapport F/Al de la concentration en ions fluor (mg /L) rapporté à la concentration d'ions aluminium (mg/L) dans le bain de conversion chimique de métal d'aluminium soit de 1,8 à 4,5.
PCT/JP2017/004414 2016-02-10 2017-02-07 Procédé de réapprovisionnement de bain de conversion chimique WO2017138530A1 (fr)

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CN201780010530.6A CN108603293A (zh) 2016-02-10 2017-02-07 对于化成处理浴的补给方法
US16/076,180 US20190136385A1 (en) 2016-02-10 2017-02-07 Chemical conversion bath replenishment method
KR1020187022919A KR20180100220A (ko) 2016-02-10 2017-02-07 화성처리욕에의 보급방법
EP17750252.3A EP3415660A4 (fr) 2016-02-10 2017-02-07 Procédé de réapprovisionnement de bain de conversion chimique

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EP3415660A1 (fr) 2018-12-19
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JP2017141495A (ja) 2017-08-17
CN108603293A (zh) 2018-09-28
US20190136385A1 (en) 2019-05-09

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