KR20180100220A - Method of spreading to Mars treatment bath - Google Patents

Abstract

Provided is a method for supplying a chemical conversion film to an aluminum-based metallization treatment bath capable of maintaining corrosion resistance and coating film adhesion of a chemical conversion film formed even when an aluminum-based metallization treatment bath is continuously used.
A method of replenishing a supply agent to an aluminum-based metalization treatment bath, the supply agent comprising at least one of a zirconium salt and a titanium salt and an effective fluoride, wherein the aluminum ion concentration (mg / L) in the aluminum- (F / A) of 1.8 to 4.5 in terms of the fluorine ion concentration (mg / L) and the F / Al concentration (mg / L).

Description

Method of spreading to Mars treatment bath

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of supplying a chemical treatment bath (chemical treatment bath).

A variety of non-chromate treatment methods for surface treatment of aluminum and aluminum alloys have been proposed.

For example, an aluminum-based metal containing a predetermined amount of phosphoric acid or condensed phosphoric acid or at least one of these salts, at least one of a zirconium salt or a titanium salt, an effective fluoride and at least one of phosphorous acid, A surface treatment bath and a surface treatment method using the treatment bath have been proposed (for example, see Patent Document 1 described later). According to such a treatment bath and treatment method, it is possible to form a chemical conversion coating that combines corrosion resistance and film adhesion on the surfaces of aluminum and aluminum alloys.

The chemical treatment of aluminum and these alloys by the treatment bath and treatment method described in Patent Document 1 usually includes a step of continuously conveying the object to be treated to a treatment bath and then dipping or spraying the treatment bath. During the chemical conversion treatment, the active ingredient in the treatment bath is consumed and the composition of the component in the treatment bath is changed. For example, in the conversion treatment process, since aluminum is etched at the surface of the base material by fluorine, the relative concentration of aluminum in the treatment bath gradually increases and becomes the cause of aluminum sludge.

Therefore, if the treatment bath is continuously used without any countermeasures, effects such as corrosion resistance of the formed chemical conversion film may not be obtained. For this reason, it is conceivable to supply a supply agent containing an effective ingredient to the treatment bath at regular intervals. However, with this method, the concentration of the active ingredient in the treatment bath can not always be kept constant. For example, after the chemical conversion treatment of aluminum and alloys thereof, the chemical conversion treatment may be carried out again. In this case, since the reaction does not proceed at the site where the chemical treatment has been performed once, the amount of the effective ingredient consumed is relatively low. That is, the processing time and the consumed amount of the effective ingredient are not always proportional. In addition, as described above, there is also a problem of compositional change of components in the treatment bath. Therefore, in the conventional method, when a chemical conversion treatment is continuously performed using a treatment bath, a chemical conversion film having corrosion resistance and the like can not be stably formed.

[Patent Document 1] Japanese Unexamined Patent Publication No. 09-143752

The inventors of the present invention have made intensive investigations on the relationship between the proportions of respective components in the chemical conversion treatment bath and the formed chemical conversion coating film and found that when the ratio of the aluminum ion concentration to the fluorine ion concentration in the chemical conversion treatment bath is within a certain range, Can be formed at the same time.

Therefore, the present invention is to provide a process for producing an aluminum-based metalization treatment bath which can maintain the corrosion resistance of a chemical conversion film formed and the coating film adhesion property while maintaining the ratio of the aluminum ion concentration and the fluorine ion concentration in the chemical conversion treatment bath within a certain range, And to provide a method for spreading the metal on the metallization treatment bath.

In order to achieve the above object, the present invention is a method for supplying a supply agent to an aluminum-based metallization treatment bath, wherein the supply agent comprises at least one of a zirconium salt and a titanium salt and an effective fluoride, Wherein the supplying agent is replenished so that the ratio F / Al of the fluorine ion concentration (mg / L) to the aluminum ion concentration (mg / L) in the metalization treatment bath is 1.8 to 4.5. Provide a supply method.

It is also preferable that the replenishment agent further comprises at least one selected from the group consisting of phosphoric acid, phosphorous acid and hydrogen peroxide.

The aluminum-based metallization treatment bath may further comprise at least one of a zirconium salt and a titanium salt, an effective fluoride, at least one selected from the group consisting of phosphoric acid, condensed phosphoric acid, and salts thereof and at least one selected from the group consisting of phosphorous acid, And at least one member selected from the group consisting of these salts.

Further, it is preferable to replenish the replenishers so that the F / Al ratio is 1.8 to 4.5 by replenishing the replenishers so that the pH of the conversion treatment bath is within a predetermined range.

It is also preferable to replenish the supply agent so that the F / Al ratio is 1.8 to 4.5 by supplying the supply agent so that the chemical conversion efficiency of the chemical conversion treatment solution is within a predetermined range.

Further, it is preferable that the aluminum-based metallization treatment bath is to be treated with an aluminum beverage can.

According to the present invention, it is possible to provide a method of supplying the chemical conversion film to an aluminum-based metallization treatment bath capable of maintaining the corrosion resistance and coating film adhesion of the chemical conversion film formed even when the aluminum-based metallization treatment bath is continuously used.

Hereinafter, an embodiment of the present invention will be described. However, the present invention is not limited to the following embodiments.

The aluminum-based metallization treatment bath to which the supply method according to the present embodiment is applied is used for forming a protective film having good appearance, corrosion resistance, coating film adhesion, etc. on an aluminum base made of an aluminum-base metal.

≪ Chemical treatment bath &

The aluminum-based metallization treatment bath (hereinafter, also referred to as a " chemical treatment bath ") to which the supply method according to the present embodiment is applied comprises at least one of a zirconium salt and a titanium salt, an effective fluoride, (Hereinafter also referred to as " phosphoric acid and the like ") selected from the group consisting of phosphoric acid and salts thereof (hereinafter also referred to as " phosphoric acid and the like ") and at least one member selected from the group consisting of phosphorous acid, hypophosphoric acid, By diluting with an appropriate amount of water.

According to the chemical conversion treatment bath of the present embodiment, a chemical conversion coating excellent in corrosion resistance and the like can be formed on the surface of the aluminum base.

Specifically, first, the effective fluoride contained in the chemical conversion treatment bath etches away the oxide film formed on the surface of the aluminum base material. Further, the phosphorous acid or the like functions as a reducing agent for preventing the oxidation of the surface of the etched aluminum substrate. Then, a double salt is formed by at least one of a zirconium salt and a titanium salt, an effective fluoride, phosphoric acid and the like, phosphorous acid, etc., and a strong chemical film is formed on the surface of the aluminum base.

[Zirconium salt]

The zirconium salt contained in the chemical conversion treatment bath according to the present embodiment is not particularly limited and examples thereof include zirconium hydrofluoric acid (H ₂ ZrF ₆ ) and lithium, sodium, potassium, ammonium salts of fluorozirconic acid (Li ₂ ZrF ₆ , _{Na 2 ZrF 6, K 2 ZrF} 6, (NH 4) 2 ZrF 6), sulfuric acid, zirconium _{(Zr (SO 4) 2)} , sulfate, zirconyl (ZrO (SO _4)), zirconium nitrate (Zr (NO _{3) 4} ), Zirconyl nitrate (ZrO (NO ₃ ) ₂ ), zirconium acetate, and zirconium fluoride (ZrF ₄ ). These may be used alone, or two or more of them may be used in combination.

[Titanium salt]

Examples of the titanium salt contained in the chemical conversion treatment bath according to the present embodiment include, but are not limited to, lithium, sodium, potassium, ammonium salts of titanium hydrofluoric acid and fluorotitanic acid (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 ) TiO (NO ₃ ) ₂ ), titanium fluoride (TiF ₃ .TiF ₄ ), and the like. These may be used alone, or two or more of them may be used in combination.

It is preferable that at least one of the zirconium salt and the titanium salt is contained in an amount of 10 ppm or more, more preferably 10 to 500 ppm, and still more preferably 10 to 100 ppm in terms of metals in the chemical conversion treatment bath according to the present embodiment. When the concentration of at least one of the zirconium salt and the titanium salt in the chemical conversion treatment bath is less than 10 ppm in terms of the metal, the chemical conversion film is hardly formed. On the other hand, even when 500 ppm or more of at least one of the zirconium salt and the titanium salt is added in the treatment bath, the effect is not increased, so that the concentration of at least one of the zirconium salt and the titanium salt is preferably 500 ppm or less in terms of the metal.

[Effective Fluoride]

The term " effective fluoride " refers to a fluoride which liberates fluorine ions in a chemical treatment bath.

The effective fluoride contained in the chemical treatment bath according to the present embodiment is not particularly limited and examples thereof include 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 two or more of them may be used in combination.

In the chemical treatment bath according to the present embodiment, fluorine ions (F < ^- >) are released from the effective fluoride. The fluorine ion has a function of suppressing precipitation of zirconium phosphate generated in the chemical conversion treatment bath, in addition to etching the oxide film on the surface of the aluminum base. Further, it has a function of dissolving aluminum eluted in the chemical conversion treatment bath during chemical conversion treatment of the aluminum base as fluoroaluminum in the chemical conversion treatment bath to suppress generation of aluminum sludge.

The concentration (mg / L) of fluorine ions in the chemical treatment bath according to the present embodiment is a ratio of the concentration (mg / L) of aluminum ions eluted into the chemical treatment bath by the chemical treatment reaction, To 4.5. When F / Al is 1.8 or more, aluminum ions are sufficiently solubilized in the chemical conversion treatment bath to improve the uniformity of the chemical conversion film formed on the surface of the aluminum base. On the other hand, if it is 4.5 or less, excessive etching due to fluorine ions can be suppressed, and a chemical conversion film having sufficient corrosion resistance can be formed on the surface of the aluminum substrate. F / Al is preferably 1.8 to 2.2. The concentration of aluminum ions can be measured by ICP (inductively coupled plasma emission spectrometry) and the concentration of fluorine ions can be measured by ion chromatography.

[Phosphoric acid]

Phosphoric acid and salts thereof contained in the chemical conversion treatment bath according to the present embodiment are not particularly limited, and examples thereof include H ₃ PO ₄ , (NH ₄ ) H ₂ PO ₄ , NaH ₂ PO ₄ and KH ₂ PO ₄ Alkaline earth metal phosphate salts such as alkali metal phosphate, calcium phosphate and magnesium phosphate, and the like.

The condensed phosphoric acid and salts thereof contained in the chemical conversion treatment bath according to the present embodiment are not particularly limited, and examples of the condensed phosphoric acid include pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, and ultraphosphoric acid, Examples of salts 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 two or more of them may be used in combination.

Phosphoric acid, and the like is preferably contained in an amount of 10 ppm or more in terms of phosphoric acid in the chemical conversion treatment bath according to the present embodiment, more preferably 10 to 500 ppm, and further preferably 10 to 100 ppm. When the concentration in the chemical conversion treatment bath such as phosphoric acid according to the present embodiment is less than 10 ppm in terms of phosphoric acid, it causes an evaporation black color change. On the other hand, when the concentration of phosphoric acid or the like in the chemical conversion treatment bath exceeds 500 ppm in terms of phosphoric acid, it causes dark water blackness and deteriorates the film adhesion.

[Such as phosphorous acid]

The phosphorous acid, hypophosphoric acid and salts thereof contained in the chemical conversion treatment bath according to the present embodiment are not particularly limited, and examples thereof include alkali metal salts such as sodium and potassium, calcium and magnesium Alkaline earth metal salts, and ammonium salts. These may be used alone, or two or more of them may be used in combination.

The phosphorous acid and the like are preferably contained in the chemical conversion treatment bath according to the present embodiment in terms of phosphorous acid in an amount of 10 ppm or more, more preferably in the range of 10 to 5000 ppm, and still more preferably in the range of 50 to 500 ppm. When the 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. On the other hand, when the concentration of phosphorous acid or the like in the chemical conversion treatment bath is 5000 ppm or more in terms of phosphorous acid, the film adhesion is deteriorated.

In addition, an antimicrobial agent, a surfactant, an antirust agent, and the like may be added to the chemical conversion treatment bath of the present embodiment, if necessary. Examples of the antibacterial agent include alcohols such as ethanol and isopropanol, guanidine group-containing compounds such as polyhexamethylenebiguanidine hydrochloride, 2- (4-thiazolyl) -benzimidazole, methyl-2-benzimidazole carbamate Phenol antimicrobial agents such as p-chloro-m-xylenol and p-chloro-m-cresol, 2,4,5,6-tetrachloroisophthalonitrile, 1,2- 2,4-dicyanobutane, pyridine antimicrobial agents such as sodium (2-pyridylthio-1-oxide) sodium and bis (2-pyridylthio-1-oxide) Methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, quaternary ammonium salts such as benzalkonium chloride and benzethonium chloride, Benzoic acid, ethyl p-oxybenzoate, sorbic acid, potassium sorbate, sodium dihydroacetate, and sodium propionate.

Examples of the surfactant include nonionic surfactants, cationic surfactants and anionic surfactants. Examples of the rust inhibitor include tannic acid, imidazoles, triazines, guanines, hydrazines , Buguanide, and the like.

In addition, a phenol-based water-soluble organic compound including a silane coupling agent, colloidal silica, amines, and a phenol resin may be added to the chemical conversion treatment bath for the purpose of improving the adhesion.

The pH of the chemical treatment bath according to the present embodiment at 25 캜 is preferably 2 to 4, more preferably 2.5 to 3.5. When the pH of the chemical conversion treatment bath is less than 2, the excess of the etching is not only difficult to form a chemical conversion film, but also the resistance to ink darkening and the adhesion to the coating film deteriorate. On the other hand, when the pH of the chemical conversion treatment bath is more than 4, the chemical conversion treatment bath becomes opaque, sludge is formed, formation of the chemical conversion coating becomes difficult, and the dark black denaturation is lowered.

An object to be treated with the chemical conversion treatment bath according to the present embodiment is an aluminum-based material. The aluminum-based metal is not particularly limited but may be aluminum, an aluminum- A magnesium alloy, an aluminum-magnesium-silicon alloy, an aluminum-zinc alloy, an aluminum-zinc-magnesium alloy and the like. In addition, the shape of the aluminum substrate to be treated is not particularly limited, and an arbitrary shape such as a plate, rod, or can can be subjected to chemical conversion treatment. More specifically, the aluminum-based metallization treatment bath according to the present embodiment can preferably treat an aluminum beverage can made of a 3000-series alloy, preferably.

According to the chemical conversion treatment bath of this embodiment, a uniform chemical conversion coating can be formed on the surface of the aluminum base. Therefore, corrosion resistance can be maintained even if the chemical conversion film is made thin, so that the adhesion of the chemical conversion film can be improved. For example, since aluminum beverage cans are subjected to strict drawing processing after formation of a chemical conversion film, adhesion of the chemical conversion film is required in addition to corrosion resistance, and the chemical conversion treatment bath according to this embodiment is also preferably used for such aluminum beverage cans and the like .

<Supply>

The replenishment agent used in the replenishment method for the aluminum-based metallization treatment bath according to the present embodiment is characterized in that it contains at least one of a zirconium salt and a titanium salt and an effective fluoride, and is selected from the group consisting of phosphoric acid, phosphorous acid and hydrogen peroxide It is preferable to further include at least one species.

A zirconium salt, and a titanium salt, an effective fluoride, phosphoric acid, phosphorous acid, and a silver complex salt to form a chemical conversion coating film, so that it is consumed accompanying formation of a chemical conversion coating film. Further, fluorine ions are liberated from the effective fluoride, which is consumed by forming aluminum ions and fluoroaluminum eluted in the chemical treatment bath. Furthermore, since phosphorous acid functions as a reducing agent for preventing the oxidation of the surface of the aluminum substrate etched by fluorine, it is lost its function as a reducing agent by itself.

Therefore, it is necessary to incorporate these components in the replenishment agent and supply it to the chemical conversion treatment bath for continuous use of the chemical conversion treatment bath.

The zirconium salt contained in the replenishment agent according to the present embodiment is not particularly limited, but includes a zirconium salt contained in the chemical conversion treatment bath according to the present embodiment. Likewise, examples of the titanium salt, the effective fluoride, the phosphoric acid, and the phosphorous acid include the effective fluoride, phosphoric acid, and phosphorous acid contained in the chemical treatment bath according to the present embodiment.

In addition, the pH adjusting agent may be contained in the replenishing agent according to the present embodiment in order to adjust the pH in the chemical conversion treatment bath. The pH adjuster is not particularly limited and includes common acids and alkalis such as nitric acid and ammonia.

In addition, the replenisher according to the present embodiment may include an antimicrobial agent, a surfactant, an antirust agent, and the like as necessary, as in the case of the chemical conversion treatment bath.

<Supply method>

Next, the supply method for the aluminum-based metallization treatment bath, which is performed using the supply agent according to the present embodiment, will be described.

The supply method according to the present embodiment is characterized in that the ratio of the aluminum ion concentration (mg / L) eluted into the chemical treatment bath by the aluminum-based metal being etched by fluorine and the fluorine ion concentration (mg / L) in the chemical treatment bath, F / Al &lt; / RTI &gt; of 1.8 to 4.5.

The aluminum ion concentration in the chemical treatment bath is increased by etching the aluminum-based metal in the chemical treatment bath with fluorine. When the aluminum ion concentration is increased, aluminum sludge is caused. However, because aluminum ions are combined with fluorine ions to become fluoroaluminum and solubilized, aluminum sludge can be prevented by the presence of a sufficient amount of fluoride ions in the aluminum ion.

Further, if the concentration of fluorine ions in the chemical conversion treatment bath is increased, etching by fluorine ions is excessive, and formation of a chemical conversion film is hindered. However, since aluminum ion and fluorine ion are combined to form fluoroaluminum, etching by fluorine ions is suppressed. Therefore, the presence of a sufficient amount of aluminum ion with respect to the fluorine ion suppresses excessive etching due to the fluorine ion.

Therefore, it is important to keep the ratio of the aluminum ion concentration and the fluorine ion concentration in the chemical conversion treatment bath within the above range. When F / Al is 1.8 or more, the aluminum ion is sufficiently solubilized in the chemical treatment bath to improve the uniformity of the chemical conversion film formed on the surface of the aluminum substrate. When F / Al is 4.5 or less, excessive etching by fluorine ions is suppressed So that a chemical conversion film having sufficient corrosion resistance can be formed on the surface of the aluminum substrate. F / Al is preferably 1.9 to 2.1.

The supply method according to the present embodiment replenishes the supply agent so that the pH at 25 DEG C in the chemical treatment bath becomes 2 to 4. When the pH of the chemical conversion treatment bath at 25 캜 is less than 2, the etching amount to the aluminum base material is increased as described above, and the aluminum ion concentration is increased. Similarly, when the pH is more than 4, the allowable dissolved concentration of aluminum ions is lowered, so that the aluminum ion concentration is lowered. Therefore, by keeping the pH within the above range, the aluminum ion concentration in the chemical conversion treatment bath can be maintained within a predetermined range, and F / Al can be easily maintained within a preferable range. A method of measuring the pH is not particularly limited, and a commercially available pH electrode or the like is used.

Further, the addition of the auxiliary agent according to the present embodiment so that the pH is maintained within the above range results in a reduction in the content or pH of the component such as the effective fluoride contained in the flux so that F / Al is maintained within the range of 1.8 to 4.5. It is preferable to adjust it.

Further, the supply method according to the present embodiment replenishes the supply agent so that the electrical conductivity of the chemical conversion treatment bath at 25 캜 is 0.5 to 5 mS / cm.

As described above, zirconium salt, titanium salt, effective fluoride, phosphoric acid, phosphorous acid, etc., which are film forming components in the chemical conversion treatment agent, are consumed due to continuous use of the chemical treatment bath, and the ion concentration in the chemical treatment bath is lowered. The electrical conductivity of the chemical conversion treatment bath is lowered. Therefore, by keeping the electric conductivity within the above range, the concentration of the film-forming component in the chemical treatment bath can be maintained within a predetermined range. A method of measuring the electrical conductivity is not particularly limited, and a commercially available EC electrode or the like is used.

In the case where the additive agent according to the present embodiment is added so that the electric conductivity is maintained within the above range, the content of the component such as the effective fluoride contained in the flux agent is adjusted so that the F / Al ratio is maintained within the range of 1.8 to 4.5 .

The method for supplying the supply agent according to the present embodiment is not particularly limited, but it is preferable that the supply of the supply agent according to the present embodiment is carried out at an infinitesimal amount so that the composition of each component in the chemical treatment bath is not greatly changed. For example, it is preferable that the pH and the electric conductivity are automatically controlled so as to be maintained within a predetermined value according to the detection values of the pH electrode and the EC electrode.

According to the supply method of the present embodiment described above, even when the chemical conversion treatment bath is continuously used to change the components in the chemical conversion treatment bath, the F / Al ratio of the chemical conversion treatment bath is maintained at 1.8 to 4.5, A chemical conversion film can be formed. Therefore, the chemical treatment bath to which the supply method of the present embodiment is applied can preferably treat the aluminum beverage cans and the like, which are required to have adhesion to the chemical conversion film and adhesion.

<Chemical conversion treatment method>

Next, a chemical conversion treatment method of an aluminum-based metal using the chemical conversion treatment bath according to the present embodiment will be described.

Prior to the conversion treatment, the aluminum substrate is pre-treated. For example, aluminum cans such as beverage cans are manufactured by a drawing process called drawing-and-ironing process (hereinafter referred to as "DI process"), and aluminum powder or lubricant Is attached to the surface. In addition, an oxide film is usually formed on the surface of the aluminum substrate and is immobilized. Therefore, it is preferable to remove these smuts and lubricating oil by an alkali treatment or an acid treatment, and at the same time to appropriately etch the surface of the aluminum base material. By performing such alkali treatment or acid treatment as a pretreatment, a strong chemical conversion film can be formed on the surface of the aluminum base material.

A method of treating the aluminum-based metal with a chemical treatment is not particularly limited, but the aluminum product or the like to be treated is immersed in a chemical treatment bath or the chemical treatment composition in a chemical treatment bath is sprayed or coated. The time required for the conversion treatment varies depending on the chemical conversion treatment composition, the treatment temperature and the treatment method depending on the chemical conversion treatment bath, but is usually 5 to 60 seconds.

In the chemical conversion treatment method according to the present embodiment, the temperature of the chemical conversion treatment bath is preferably room temperature to 60 ° C, more preferably 30 to 50 ° C. When the temperature of the chemical conversion treatment bath is less than room temperature (for example, 25 占 폚), the formation rate of the chemical conversion film is slow and the concentration of each component in the treatment bath must be raised in order to increase the formation rate. On the other hand, when the temperature of the chemical conversion treatment bath exceeds 60 캜, the treatment bath becomes cloudy and sludge tends to be generated. Further, since it requires a great deal of energy for maintaining the temperature of the chemical conversion treatment bath, it is economically disadvantageous.

[ Example ]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples and comparative examples, &quot;% &quot; means &quot;% by mass &quot; unless otherwise specified.

&Lt; Example 1 >

Each component was prepared so that the concentrations of zirconium ion, aluminum ion and fluorine ion were each an aqueous solution of the concentration shown in Table 1, and the chemical conversion treatment bath of Example 1 was used. (NH ₄ ) ₂ ZrF ₆ was used as the zirconium ion source and HF was used as the fluorine ion source. As the material to be treated, a lidless aluminum can body obtained by DI processing of an aluminum alloy (A3004) plate was subjected to a chemical conversion treatment under the conditions shown in Table 1 for the pH of the chemical conversion treatment bath, the treatment temperature and the treatment time. The pH in Table 1 means the pH at 25 ° C.

&Lt; Examples 3, 5, 7 and 9 >

The respective components were prepared so that the concentration of each component of phosphoric acid, phosphorous acid and hydrogen peroxide (H ₂ O ₂ ) in addition to zirconium ion, aluminum ion and fluorine ion had the concentrations shown in Table 1, and the compositions of Examples 3, 5, Treatment bath. The chemical treatment was carried out under the same conditions as in Example 1, except that the treatment conditions were as shown in Table 1.

&Lt; Example 2 >

The chemical treatment bath of Example 2 was supplied with 0.1% of a replenisher A containing 20 g / L of zirconium ions, 20 g / L of fluorine ions and 20 g / L of nitric acid to the chemical treatment bath of Example 1. The same components as in Example 1 were used as the respective component sources. The amount of each component in the chemical conversion treatment bath by the above diffusion was as shown in Table 1. A chemical conversion treatment was carried out under the same conditions as in Example 1, except that the treatment conditions were as shown in Table 1.

<Example 4>

The replenishment 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 was replenished to the chemical treatment bath of Example 3, Respectively. The same components as in Example 1 were used as the respective component sources. The amount of each component in the chemical conversion treatment bath by the above diffusion was as shown in Table 1. A chemical conversion treatment was carried out under the same conditions as in Example 1, except that the treatment conditions were as shown in Table 1.

&Lt; Example 6 >

A replenisher C containing 10 g / L 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 was replenished to the chemical conversion treatment bath of Example 5, 6 &lt; / RTI &gt; The same components as in Example 1 were used as the respective component sources. The amount of each component in the chemical conversion treatment bath by the above diffusion was as shown in Table 1. A chemical conversion treatment was carried out under the same conditions as in Example 1, except that the treatment conditions were as shown in Table 1.

&Lt; Example 8 >

A 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 was supplied to the chemical treatment bath of Example 7, 8 &lt; / RTI &gt; The same components as in Example 1 were used as the respective component sources. The amount of each component in the chemical conversion treatment bath by the above diffusion was as shown in Table 1. A chemical conversion treatment was carried out under the same conditions as in Example 1, except that the treatment conditions were as shown in Table 1.

&Lt; Example 10 >

The replenishment agent E containing 10 g / L of zirconium ions, 10 g / L of fluorine ions, 10 g / L of phosphoric acid, 10 g / L of phosphorous acid, 10 g / L of hydrogen peroxide and 20 g / L of nitric acid was added to the chemical conversion treatment bath of Example 9 in an amount of 0.1% And a conversion treatment tank of Example 10 was used. The same components as in Example 1 were used as the respective component sources. The amount of each component in the chemical conversion treatment bath by the above diffusion was as shown in Table 1. A chemical conversion treatment was carried out under the same conditions as in Example 1, except that the treatment conditions were as shown in Table 1.

The aluminum can bodies to be treated in the chemical treatment baths of Examples and Comparative Examples were pre-treated in the following manner. First, a lubricant and a lubricant were removed by spraying at 75 DEG C for 60 seconds using a commercially available acidic detergent (Nippon Paint & Surf Chemicals Co., Ltd., Surf Cleaner NHC260). Next, the water was spray-rinsed with tap water for 15 seconds.

Then, the chemical treatment composition according to the chemical treatment baths of Examples and Comparative Examples was sprayed on the aluminum can body to be treated under the conditions shown in Table 1, respectively. Then, it was spray-rinsed 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 of Examples and Comparative Examples used in the following evaluation tests.

[Boiling water corrosion resistance test]

The bottoms of the cans cut out from the treatment vessels of Examples 1 to 10 and Comparative Examples 1 and 2 were immersed in boiled tap water at 100 DEG C for 30 minutes and the degree of blackening of the outer surface of the can bottom was evaluated by naked eyes according to the following evaluation criteria. The evaluation results are shown in Table 1. Evaluation A was judged to be acceptable, and evaluations B and C were judged to be rejected.

A: No blackness

B: A little shade

C: strongly blackened

The treatment vessels of Examples 1 to 10 and Comparative Examples 1 and 2 were dried and cut to obtain test specimens. The epoxy-acrylic paint was applied by a bar coater to a dry film thickness of 5 m, The coating film formed by heating and curing for minutes was subjected to the following coating film adhesion test.

[Primary adhesion test]

The coating film obtained above was subjected to a 0T bending test as a primary adhesion test. Then, the coating film floating on the bent portion was removed with an adhesive tape, and the peeling widths on both sides of the bent portion were measured. The peeling width was determined to be within 0.1 mm, and when the peeling width exceeded 0.1 mm, it was evaluated as rejection. The results are shown in Table 1.

As a primary adhesion test, a cross-cut test of 1 mm was carried out by referring to the former JIS K5400. In the cross-cut test method, 100 chambers were formed on a coating film with a cutter knife in a width of 1 mm, and an adhesive tape was stuck thereon, then pulled off, and the number of chambers remaining was counted. The number of the remaining chambers of the coating was 100, and the others were evaluated as being unacceptable. The results are shown in Table 1.

[Secondary adhesion test]

The coating film obtained by immersing the coating film obtained above in boiling water for 30 minutes was subjected to a crosscut test of 1 mm in the same manner as described above for the secondary adhesion test. The number of the remaining chambers of the coating was 100, and the others were evaluated as being unacceptable. The results are shown in Table 1.

From the comparison of Examples 1 to 10 and Comparative Example 1, it can be understood that the aluminum substrate treated by the chemical treatment baths of Examples 1 to 10 is superior to the aluminum substrate treated by the chemical treatment bath of Comparative Example 1 in boiling water corrosion resistance and adhesion The results of the test were found to be excellent. From these results, it was confirmed that the chemical conversion coating having high corrosion resistance and high adhesion to the aluminum base can be formed by setting the F / Al in the chemical conversion treatment bath to 4.5 or less.

From the comparison of Examples 1 to 10 and Comparative Example 2, it can be understood that the aluminum substrate treated by the chemical treatment baths of Examples 1 to 10 is superior to the aluminum substrate treated by the chemical treatment bath of Comparative Example 2 in boiling water corrosion resistance and adhesion The results of the test were found to be excellent. From these results, it was confirmed that a chemical conversion coating having high corrosion resistance and high adhesion to an aluminum base can be formed by setting F / Al in the chemical conversion treatment bath to 1.8 or more.

Thus, it has been confirmed that the above-described method can maintain the chemical conversion treatment bath capable of forming a chemical corrosion film having a high corrosion resistance by maintaining the F / Al ratio in the chemical conversion treatment bath at 1.8 to 4.5.

Claims (6)

As a method for supplying a supply agent to an aluminum-based metalization treatment bath,
Wherein the replenishment agent comprises at least one of a zirconium salt and a titanium salt and an effective fluoride,
Wherein the supplying agent is replenished so that the ratio of the fluorine ion concentration (mg / L) to the aluminum ion concentration (mg / L) in the aluminum-based metalization treatment bath and the F / Al ratio is 1.8 to 4.5, The supply method for bath. The method according to claim 1,
Wherein the replenishment agent further comprises at least one member selected from the group consisting of phosphoric acid, phosphorous acid, and hydrogen peroxide. 3. The method according to claim 1 or 2,
Wherein the aluminum-based metallization treatment bath comprises at least one of a zirconium salt and a titanium salt, an effective fluoride, at least one member selected from the group consisting of phosphoric acid, condensed phosphoric acid, and salts thereof and at least one member selected from the group consisting of a phosphorous acid, At least one member selected from the group consisting of copper, aluminum, and combinations thereof. 4. The method according to any one of claims 1 to 3,
The replenishment agent is replenished so that the pH of the chemical conversion treatment bath becomes within a predetermined range, thereby replenishing the replenishment agent so that the F / Al ratio is 1.8 to 4.5. 5. The method according to any one of claims 1 to 4,
Wherein the supply agent is supplied so that the electrical conductivity of the chemical conversion treatment bath becomes within a predetermined range, thereby replenishing the supply agent so that the F / Al ratio is 1.8 to 4.5. 6. The method according to any one of claims 1 to 5,
Wherein the aluminum-based metallization treatment bath is an aluminum beverage can treatment target.