JPH07331276A - Surface treatment of aluminum-containing metal material and composition therefor - Google Patents

Abstract

PURPOSE:To form a chemical coating film excellent in corrosion resistance, coating material adhesion and lubricity on the surface of an Al-containing metal material. CONSTITUTION:A treatment solution composed of an aqueous solution containing 0.01 to 1g/l phosphate ion, 0.01 to 0.5g/l (on metal base) water-soluble Zr or Ti compound, 0.01 to 2g/l (on Fe base) fluoride and 0.01 to 2g/l water-soluble polyamide containing tert-amine groups and/or polyalkylene groups and having pH1.8 to 4.0 is prepared from a composition containing an aqueous mixture containing the Zr compound and/or the Ti compound, the fluoride and the polyamide other than phosphate ion respectively in an amount 0.01 to 50 pts.wt. (on metal base), 0.01 to 200 pts.wt. (one Fe base) and 0.01 to 200 pts.wt. based on 1 pt.wt. phosphate ion. A layer of the treatment solution is formed on the surface of an Al-containing metal material and subjected to water-washing treatment and drying treatment, thus forming the coating film layer excellent in the above-mentioned properties.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment composition for an aluminum-containing metallic material, a surface treatment liquid and a surface treatment method. More specifically, the present invention is useful for imparting excellent boiling water black discoloration resistance, paint adhesion and lubricity to the surface of an aluminum-containing metallic material, for example, for forming a surface state suitable for aluminum can manufacturing. The present invention relates to a surface treatment composition, a surface treatment liquid, and a surface treatment method.

[0002]

2. Description of the Related Art Generally, aluminum drawn cans have D
After I processing (Drawing & Ironing),
The surface is washed with an acid cleaner to remove smut formed from aluminum fine powder, lubricating oil (coolant), metal soap, etc., and then the surface is treated for corrosion resistance and adhesion of the coating film. A phosphate conversion coating is applied for the purpose of improvement. There are roughly two types of chemical conversion coatings, a chromate treatment for forming a chromium phosphate coating and a non-chromate treatment for forming a composite coating of zirconium oxide, zirconium phosphate and the like.

Recently, a cleaning process using a non-chromate type chemical agent accounts for about 80% of the cleaning lines in Japan due to environmental protection problems. Usually, an aluminum can whose surface is coated with a chemical conversion film is thoroughly rinsed with a washer after chemical conversion and then dried in a draining oven. The can that has left the oven is then transferred to the printing and painting processes. In this printing and painting process, since the cans are placed on a dedicated conveyor, the cans normally arranged in about 5 to 30 rows are arranged in one row through a single filer.
At this time, the cans may come into contact with the guides, or the cans may come into contact with each other, thereby hindering the transportation thereof. It is considered that the reason for this is that the static friction coefficient of the aluminum can that has been subjected to cleaning / chemical conversion treatment is considerably high. Further, in recent years, the cause of this problem has become more frequent due to the increase in the transfer speed accompanying the increase in the number of cans made, and the decrease in production efficiency due to this has become a more serious problem. Therefore, it has been strongly desired to reduce the coefficient of static friction on the outer surface of the aluminum can without adversely affecting the corrosion resistance.

As a means for imparting lubricity to an aluminum can to improve the carrying efficiency of the can, for example, Japanese Patent Laid-Open No. 64-85 is available.
The method disclosed in No. 292 is mentioned. The method disclosed herein is such that the water-soluble organic phosphates or saturated fatty acids on the surface of the can are water-soluble during the final rinsing step (deionized water rinsing) of the above-mentioned can washer line and draining and drying. This is a method of spraying a derivative or the like to form an organic film having lubricity.

However, when using a cleaning device in which the deionized water used in the final rinsing step is recycled by using the activated carbon adsorption treatment, the film components are adsorbed on the activated carbon, so that the activated carbon Not only the deterioration is accelerated, but also the consumption of the drug is increased, which is economically disadvantageous. In addition, when the object to be treated has a shape that easily causes liquid accumulation, the residual liquid in that portion is thickened during drying, which causes uneven unevenness or peeling of the coating film. .

Further, in JP-A-5-239434, metal ions (Fe, Zr, Sn, Al, Ce) and / or water-soluble organic phosphoric acid esters or saturated fatty acids are used in the film forming process of the can washer line. A method for forming an organic-inorganic composite film having excellent lubricity by spraying an acidic aqueous solution containing a water-soluble derivative of the above and controlling the pH to 2 to 5 or immersing an aluminum-containing metallic material in the aqueous solution. Is disclosed. However, this method has not been able to obtain an aluminum-containing metal material having satisfactory blackening resistance. Therefore, at present, a composition for surface treatment of an aluminum-containing metal material that simultaneously satisfies excellent corrosion resistance, paint adhesion and lubricity,
The surface treatment liquid and the surface treatment method have not been obtained yet.

[0007]

SUMMARY OF THE INVENTION The present invention is to solve these problems of the prior art described above.
Specifically, it is intended to provide a novel surface treatment composition, a surface treatment liquid and a surface treatment method for forming a chemical conversion film having excellent corrosion resistance, paint adhesion and lubricity on the surface of an aluminum-containing metal material. Is.

[0008]

Means for Solving the Problems As a result of intensive investigations by the present inventors regarding means for solving the problems of the above-mentioned prior art, a specific amount of phosphate ion, a water-soluble zirconium compound and a titanium compound are selected. Using an aqueous treatment liquid containing at least one kind, a fluoride and a water-soluble polyamide, it is possible to newly form a film excellent in corrosion resistance, paint adhesion and lubricity on the surface of an aluminum-containing metal material. They have found the present invention and completed the present invention.

The composition for treating a surface of an aluminum-containing metallic material of the present invention comprises the following components: (1) Phosphate ion and 0.01 to 50 parts by weight of (2) metal atom based on 1 part by weight thereof. Part, at least one selected from water-soluble zirconium compounds and titanium compounds, and (3) 0.01 to 0.01 in terms of fluorine atoms.
200 parts by weight of fluoride, and (4) 0.01-2
100 parts by weight of a water-soluble polyamide having at least one of a tertiary amine group and a polyalkylene glycol group.

Further, the surface treatment liquid for an aluminum-containing metal material of the present invention comprises the following components: 0.01 to 1.0 g / liter of phosphate ions and 0.01 to 10,000 in terms of metal atoms.
0.5 g / liter of at least one selected from water-soluble zirconium compounds and titanium compounds, 0.01 to 2.0 g / liter of fluoride atom in terms of fluorine atom, and 0.01 to 2. 0 g / l of at least one of tertiary amine groups and polyalkylene glycol groups
A water-soluble polyamide having a seed,
It consists of an aqueous solution having a pH of 4.0.

Further, in the surface treatment method for an aluminum-containing metal material of the present invention, the surface treatment liquid is brought into contact with the surface of the aluminum-containing metal material to form a surface treatment liquid layer on the surface, and the surface treatment liquid layer is formed on the surface. It is characterized in that a chemical conversion film is formed on the surface by washing with water and drying by heating.

[0012]

The aluminum-containing metal material used in the present invention includes an aluminum material and an aluminum alloy material, and the aluminum alloy includes, for example, an aluminum-manganese alloy, an aluminum-magnesium alloy, and an aluminum-copper alloy. There are no restrictions on the shape and dimensions of aluminum-containing metal materials, including plate materials, pipe materials,
It may be either a wire rod or the like.

The surface-treating composition of the present invention comprises a phosphate ion and 1 part by weight thereof, which is 0.0 in terms of metal atom.
1 to 50 parts by weight of the water-soluble zirconium compound and / or titanium compound and 0.01 to 50 in terms of fluorine atoms.
It consists of an aqueous mixture, preferably an aqueous solution, containing 200 parts by weight of fluoride and 0.01 to 200 parts by weight of a water-soluble polyamide having tertiary amine and / or polyalkylene glycol groups. The total solid content concentration of the surface treatment composition is not limited,
Generally, it is preferably 10% by weight or less, and 0.01
It is more preferably ˜1 wt%.

The surface treatment liquid of the present invention is obtained from the above-mentioned composition for surface treatment, and contains at least one selected from a phosphate ion, a water-soluble zirconium compound and a titanium compound.
An acidic treatment liquid containing a fluoride and a water-soluble polyamide as essential components.

The surface treatment liquid of the present invention is 0.01 to 1.0.
g / l phosphate ion, 0.01-0.5 g /
0.01 to 2.0 g / liter of water-soluble zirconium compound and / or titanium compound (converted to metal atom)
Liters of fluoride (converted to fluorine atoms) and 0.01
An aqueous solution containing ˜2.0 g / liter of a tertiary amine group- and / or polyalkylene glycol group-containing water-soluble polyamide and having a pH of 1.8-4.0.

As the phosphate ion source, phosphoric acid (H
₃ PO ₄ ), sodium phosphate (Na ₃ PO ₄ ), ammonium phosphate ((NH ₄ ) ₃ PO ₄ ) and the like can be used. The concentration is preferably 0.01 to 1.0 g / liter, and particularly preferably 0.02 to 0.40 g / liter. Concentration of phosphate ion is 0.01g
When it is less than 1 liter / liter, the reactivity with respect to the surface of the aluminum-containing metal material is insufficient, and the film is not sufficiently formed. On the other hand, if it exceeds 1.0 g / liter, the film-forming property is saturated, the cost of the treatment liquid is high, and it is economically disadvantageous.

Examples of the water-soluble zirconium compound and titanium compound include oxides such as zirconium oxide and titanium oxide, hydroxides such as zirconium hydroxide and titanium hydroxide, zirconium fluoride and titanium fluoride. Nitrate salts such as fluoride, zirconium nitrate, titanium nitrate can be used, but other water-soluble compounds may be used. The concentration of these zirconium or titanium compounds is
Converted to metal atoms (zirconium, titanium), 0.0
The range of 1 to 0.5 g / liter is preferable, and particularly 0.0
The range of 2 to 0.08 g / liter is preferable. If the concentration is less than 0.01 g / liter, the film-forming property of the obtained surface treatment liquid is insufficient, and if it exceeds 0.5 g / l, the film-forming property is saturated, resulting in high cost and economical. Will be at a disadvantage.

As the fluoride, hydrofluoric acid (H
F), acids such as fluorozirconic acid (H ₂ ZrF ₆ ), fluorotitanic acid (H ₂ TiF ₆ ), and salts thereof (for example, ammonium salt, sodium salt, etc.) can be used, and the kind thereof is not particularly limited. Absent. The concentration of fluoride in the surface treatment liquid is 0.03 to 1.0 in terms of fluorine atoms.
The range of g / liter is preferable, and especially 0.03 to 0.6
A range of g / liter is preferred. Its concentration is 0.03g
If it is less than 1 liter / liter, the reactivity is poor and the film is not sufficiently formed. Further, if it exceeds 1 g / liter, the etching amount of the aluminum-containing metal surface increases, and the appearance deteriorates, which is not preferable. However, since the optimum concentration of fluoride is determined depending on the concentration of aluminum eluted from the metal material, it varies depending on this concentration of aluminum. This is because it is necessary for the aluminum from which the fluoride is eluted to be stably present as aluminum fluoride in the treatment liquid. For example, the required amount of fluorine is about 0.
It is 2 g / liter.

Among the water-soluble polyamides used in the present invention, those having an amino group include, for example, diamines and adipine having a tertiary amine group in the main chain such as aminoethylpiperazine and bisaminopropiperazine. Polyamides with dicarboxylic acids such as acids and sebacic acid, copolymerized polyamides with them and lactams, or lactams having a tertiary amino group in the side chain such as α-dimethylamino-ε-caprolactam Examples thereof include copolyamide. As the polyamide having a polyalkylene glycol group in the main chain, a polyamide composed of a diamine or dicarboxylic acid obtained from polyethylene glycol having a molecular weight of about 200 to 4000 and a diamine such as adipic acid or sebacic acid, or hexamethylenediamine, or those And a lactam copolymer polyamide.

In the surface treatment liquid of the present invention, at least one selected from these water-soluble polyamides is used.
The concentration is preferably 0.01 to 2.0 g / liter, particularly preferably 0.05 to 0.5 g / liter. When the concentration of polyamide is less than 0.01 g / liter, the amount of film formed is poor and the film has poor lubricity. On the other hand, if it exceeds 0.5 g / liter, the film-forming property is saturated, the cost of the treatment liquid is high, and it is economically disadvantageous.

The surface treatment liquid of the present invention has a pH of 1.8 to 4.0.
Adjusted to. If it is less than 1.8, etching will increase and it will be difficult to form a film, and if it exceeds 4.0, it will be difficult to form a film excellent in corrosion resistance. Therefore, the pH must be controlled in the range of 1.8-4.0. More preferable pH range is 2.0
Is about 3.0. The pH of the surface treatment solution is adjusted by using an acid such as phosphoric acid, nitric acid, hydrochloric acid, and hydrofluoric acid, or an alkali such as sodium hydroxide, sodium carbonate, and ammonium hydroxide.

When the stability of the treatment liquid is significantly reduced by metal ions such as copper and manganese which are alloy components eluted from the material, organic acids such as gluconic acid and oxalic acid are used to chelate these components. You may add.

Next, the surface treatment method of the present invention will be described. The treatment temperature and treatment time of the surface treatment liquid used in the method of the present invention are not particularly limited, but the treatment is preferably performed under the following conditions. That is, when the surface treatment liquid is applied to the surface of the aluminum-containing metal material by the spray method, it is preferable that the surface treatment liquid is contacted at a temperature of 25 to 50 ° C. for 15 to 40 seconds and then washed with water. When the metal material is dipped in the surface treatment solution, it is preferably dipped at a temperature of 25 to 50 ° C. for 15 to 60 seconds and then washed with water. The preferred embodiments of the method of the present invention are shown below.

<Process 1> Surface cleaning of metal material (for example, DI can): Degreasing Treatment temperature: 40 to 80 ° C. Treatment method: Spray Treatment time: 25 to 60 seconds Surface treatment with treatment liquid of the present invention Treatment temperature: 25 ~ 50 ° C Treatment method: Spray Treatment time: 15-40 seconds Washing with water Deionized washing with water Drying

<Process 2> Surface cleaning of metallic material: Degreasing (any of acid type, alkali type and solvent type) Treatment temperature: 40 to 80 ° C. Treatment method: Spray Treatment time: 25 to 60 seconds Water washing Chemical conversion coating treatment (Using a phosphate treatment agent) Treatment temperature: 30 to 50 ° C. Treatment method: Spray Treatment time: 8 to 30 seconds Surface treatment with the treatment liquid of the present invention Treatment temperature: 25 to 50 ° C. Treatment method: Spray treatment time: 3 to 30 seconds Washing with water Deionized water washing Drying

<Process 3> Surface cleaning of metal material: degreasing (any of acid type, alkali type and solvent type) Treatment temperature: 40 to 80 ° C. Treatment method: Spray Treatment time: 25 to 60 seconds Water washing Chemical conversion coating treatment (Using a phosphate treatment agent) Treatment temperature: 30 to 50 ° C. Treatment method: Spray Treatment time: 8 to 30 seconds Surface treatment with treatment liquid of the present invention Treatment temperature: 25 to 50 ° C. Treatment method: Spray treatment time: 3 ~ 30 seconds Rinse, Rinse Rinse, Dry

As mentioned above, the preferable range of the treatment temperature with the surface treatment liquid of the present invention is 25 to 50 ° C. If it is less than 25 ° C, the reactivity may be insufficient and a good film may not be formed. Further, if it exceeds 50 ° C., the zirconium compound becomes unstable, and some precipitates are generated, which may result in lack of stability of the treatment liquid. Similarly, regarding the treatment time, the treatment time in the case of the surface treatment process 1 is 15 to 5
0 seconds is appropriate. If it is less than 15 seconds, it may not react sufficiently and a film having excellent corrosion resistance may not be formed. Further, even if it is treated for more than 50 seconds, the improvement in performance may not be recognized. Particularly preferable processing time is 20 to 3
It is in the range of 0 seconds.

On the other hand, in the case of the surface treatment processes 2 and 3, a treatment time of 3 to 30 seconds is appropriate. If it is less than 3 seconds, it may not react sufficiently and a film having excellent corrosion resistance may not be formed. Further, when it exceeds 30 seconds, the improvement in performance may not be recognized. Particularly preferably, it is in the range of 5 to 15 seconds.

As the chemical conversion coating (phosphating agent) that can be used in the two-step treatment such as the processes 2 and 3, a known non-chromium conversion coating of aluminum can be used. Specifically, for example, Japanese Patent Publication No. 52-131937 and Japanese Patent Publication No. 58-3
The chemical conversion coatings described in, for example, 0344 and Japanese Patent Publication No. 57-39314. When these chemical conversion treatment liquids do not contain a component that inhibits the effect of the present invention (for example, SO ₄ ions), the treatment of the present invention liquid can be carried out immediately without chemical washing with water. When the chemical conversion liquid contains a component that inhibits the effect of the present invention, it is preferable to wash the liquid after the chemical conversion and then treat the liquid of the present invention.

[0030]

EXAMPLES The present invention will be further described below with reference to examples. (1) Test metal material: Aluminum DI can Aluminum D produced by DI processing of an aluminum plate
The I can was cleaned with a heated aqueous solution of an acidic degreasing agent (trademark: Palclean 500, manufactured by Nippon Parkerizing Co., Ltd.) and then subjected to surface treatment.

2. Evaluation method (1) Corrosion resistance The corrosion resistance of the aluminum DI can was evaluated by immersing the treated can in boiling water for 30 minutes and then blackening it. That is, it is preferable that blackening does not occur. (2) Lubricity The following tests were carried out using the slipperiness tester shown in FIGS. 1 (A), (B) and (C). Horizontal slant plate 1 of slipperiness tester
Three surface-treated aluminum DI cans were placed on the top, and 2 cans 2a therein were fixed so that the bottom side faced the front. The remaining one can 2b was set on it so that the opening side faced the front. In this state, tilt plate 1 to motor 3
Was tilted at a constant speed (3 ° / SEC), and the static friction coefficient was calculated by obtaining the tilt angle from the time required for the can to drop.

(3) Adhesion of paint In order to evaluate the adhesion of paint, an epoxyurea-based paint for cans is applied to the surface of treated cans to a coating film thickness of 5 to 7 μm, and 215
Baking was performed at 4 ° C. for 4 minutes, a cross cut was put on the evaluation surface with a cutter knife, and a cellotape peeling test was performed. (Primary Adhesion) After that, a test liquid having the composition shown below was boiled, the test can was immersed in the test liquid for 60 minutes, and then a cellotape peeling test was performed again (secondary adhesion). The adhesion was evaluated by the presence or absence of peeling of the coating film.・Test liquid (model juice) Sodium chloride (5 g / l) Citric acid (5 g / l) Solvent: Use deionized water

Example 1 The surface of a washed aluminum DI can was coated with aluminum DI.
A surface treatment liquid for a can (trade name: Alodine 404, manufactured by Nippon Parkerizing Co., Ltd.) was heated to 35 ° C. and sprayed for 20 seconds, and then surface treatment liquid (1) having the following composition
It is heated to 5 ° C, sprayed for 10 seconds, washed with tap water, sprayed with deionized water having a resistance value of 3,000,000 Ωcm or more for 10 seconds, and then dried in a hot air drying oven at 200 ° C for 2 minutes. did. Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment liquid (1) 75% phosphoric acid _{(H 3 PO 4) 138ppm (} PO 4: 100ppm) 20% fluozirconic acid _{(H 2 ZrF 6) 1137ppm (} Zr: 100ppm) 20% hydrofluoric acid (HF) 235 ppm (F: 170ppm) Water-soluble polyamide with a tertiary amine group 250ppm Water balance pH: 2.5 (adjusted with nitric acid and ammonia water)

Example 2 A surface treatment liquid for aluminum DI cans (Trademark: Alodine 404, manufactured by Nippon Parkerizing Co., Ltd.) was heated to 35 ° C. and sprayed for 25 seconds on the cleaned aluminum DI cans, and then the following composition was used. Surface treatment liquid (2) was heated to 30 ° C., immersed in it for 15 seconds, washed with water in the same manner as in Example 1, sprayed with deionized water for 10 seconds, and then treated with 2.
It was dried in a hot air drying oven at 00 ° C for 2 minutes. Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment solution (2) 75% phosphoric acid _{(H 3 PO 4) 206ppm (} PO 4: 150ppm) 20% fluozirconic acid _{(H 2 ZrF 6) 455ppm (} Zr: 40ppm) 20% hydrofluoric acid (HF) 210 ppm (F: 90ppm) Water-soluble polyamide with tertiary amine group 150ppm Water balance pH: 3.0 (adjusted with nitric acid and ammonia water)

Example 3 A surface treatment liquid for aluminum DI cans (trademark: Alodine 404, manufactured by Nihon Parkerizing Co., Ltd.) was heated to 35 ° C. and sprayed on the washed aluminum DI cans for 20 seconds. The surface treatment liquid (3) of composition is 45 ° C.
The mixture was warmed and sprayed for 5 seconds, then washed with water, deionized with water and dried in the same manner as in Example 1.
The corrosion resistance and adhesion of the cans were evaluated. Surface treatment liquid (3) 75% phosphoric acid _{(H 3 PO 4) 413ppm (} PO 4: 300ppm) 20% fluotitanic acid _{(H 2 TiF 6) 683ppm (} Ti: 40ppm) 20% hydrofluoric acid (HF) 262Ppm (F: 100ppm) 200ppm water containing polyalkylene glycol group Water-soluble polyamide balance pH: 2.5 (adjusted with nitric acid and ammonia water)

Example 4 A surface treatment liquid for aluminum DI cans (trade name: Alodine 404, manufactured by Nippon Parkerizing Co., Ltd.) was heated to 35 ° C. and sprayed for 20 seconds on a cleaned aluminum DI can, and then the following composition was used. The surface treatment solution (4) of Example 1 was heated to 50 ° C., and immersed therein for 30 seconds, and then, in Example 1.
It was washed with water, washed with deionized water and dried in the same manner as in. Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment liquid (4) 75% phosphoric acid _{(H 3 PO 4) 138ppm (} PO 4: 100ppm) 20% fluozirconic acid _{(H 2 ZrF 6) 1137ppm (} Zr: 100ppm) 20% hydrofluoric acid (HF) 235 ppm (F: 170ppm) 100ppm water-soluble polyamide water with polyalkylene glycol group The balance pH: 2.8 (adjusted with nitric acid and ammonia water)

Example 5 A surface treatment liquid for aluminum DI cans (trademark: Alodine 404, manufactured by Nippon Parkerizing Co., Ltd.) was heated to 35 ° C. and sprayed for 20 seconds on the cleaned aluminum DI cans, and then the following composition was used. The surface treatment liquid (5) was heated to 35 ° C. and sprayed for 8 seconds, then washed with water, washed with deionized water and dried as in Example 1. Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment liquid (5) 75% Phosphoric acid (H ₃ PO ₄ ) 138ppm (PO ₄ : 100ppm) 20% Fluorozirconic acid (H ₂ ZrF ₆ ) 1137ppm (Zr: 100ppm) 20% Hydrofluoric acid (HF) 235ppm (F: 170ppm) Water-soluble polyamide water having both a tertiary amino group and a polyalkylene glycol group of 100ppm Residual pH: 2.5 (adjusted with nitric acid and ammonia water)

Example 6 A surface treatment liquid for aluminum DI cans (trademark: Palcoat 3753 manufactured by Nippon Parkerizing Co., Ltd.) was heated to 50 ° C., sprayed for 30 seconds, and washed with water on the cleaned aluminum DI cans. A surface treatment liquid (6) having the following composition was heated to 35 ° C. and sprayed for 15 seconds. Next, as in Example 1, washing with water, washing with deionized water, and drying were performed. Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment solution (6) 75% phosphoric acid _{(H 3 PO 4) 412ppm (} PO 4: 300ppm) 20% fluotitanic acid _{(H 2 TiF 6) 683ppm (} Ti: 40ppm) 20% fluozirconic acid (H ₂ ZrF ₆ ) 455ppm (Zr: 40ppm) 20% hydrofluoric acid (HF) 157ppm (F: 80ppm) Water-soluble polyamide water with both tertiary amino group and polyalkylene glycol group 100ppm Residual pH: 3.0 (with nitric acid (Adjust with ammonia water)

Example 7 A surface treatment liquid (7) having the following composition was heated to 25 ° C. and sprayed for 30 seconds on a cleaned aluminum DI can,
Next, as in Example 1, washing with water, washing with deionized water, and drying were performed.
Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment liquid (7) 75% phosphoric acid _{(H 3 PO 4) 69ppm (} PO 4: 50ppm) 20% fluozirconic acid _{(H 2 ZrF 6) 455ppm (} Zr: 40ppm) 20% hydrofluoric acid (HF) 25 ppm (F: 55ppm) Water-soluble polyamide water having both tertiary amino group and polyalkylene glycol group 50ppm Residual pH: 3.0 (adjusted with nitric acid and ammonia water)

Example 8 A cleaned aluminum DI can was heated with a surface treatment solution (8) having the following composition at 40 ° C. and immersed in it for 35 seconds, and then washed with water as in Example 1. It was washed with deionized water and dried. Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment liquid (8) 75% phosphoric acid _{(H 3 PO 4) 110ppm (} PO 4: 80ppm) 20% fluozirconic acid _{(H 2 ZrF 6) 854ppm (} Ti: 50ppm) 20% hydrofluoric acid (HF) 10 ppm (F: 65ppm) 100ppm water-soluble polyamide water with polyalkylene glycol group balance pH: 3.0 (adjusted with nitric acid and ammonia water)

Comparative Example 1 A surface treatment liquid (trade name: Alodine 404, manufactured by Nippon Parkerizing Co., Ltd.) for aluminum DI cans was heated to 35 ° C. and sprayed on the washed aluminum DI cans for 25 seconds. It was washed with water, washed with deionized water and dried in the same manner as in Example 1. Then, the corrosion resistance and adhesiveness of this DI can were evaluated.

Comparative Example 2 Commercially available aluminum D was added to a washed aluminum DI can.
A surface treatment liquid for I can (trademark: Alodin 404, manufactured by Nippon Parkerizing Co., Ltd.) was heated to 35 ° C. and sprayed for 20 seconds, and then a surface treatment liquid (9) having the following composition was heated to 35 ° C. and heated to 10 ° C. After spraying for 2 seconds, washing with water, washing with deionized water and drying were carried out in the same manner as in Example 1.
The corrosion resistance and adhesion of the cans were evaluated. Surface treatment liquid (9) 75% Phosphoric acid (H ₃ PO ₄ ) 138ppm (PO ₄ : 100ppm) 20% Fluorozirconic acid (H ₂ ZrF ₆ ) 500ppm (Zr: 44ppm) 20% Hydrofluoric acid (HF) 210ppm (F: 95ppm) Water balance pH: 3.0 (adjusted with nitric acid and ammonia water)

Comparative Example 3 A surface treatment liquid (trade name: Alodine 404, manufactured by Nippon Parkerizing Co., Ltd.) for aluminum DI cans was heated to 35 ° C. and sprayed on the washed aluminum DI cans for 25 seconds. The surface treatment liquid (10) having a composition of 35
The mixture was heated to 0 ° C., sprayed for 20 seconds, washed in the same manner as in Example 1, washed with deionized water, and dried. Then this DI
The corrosion resistance and adhesion of the cans were evaluated. Surface treatment solution (10) 75% phosphoric acid (H ₃ PO ₄ ) 138ppm (PO ₄ : 100ppm) 20% hydrofluoric acid (HF) 210ppm (F: 40ppm) Tertiary amino group and polyalkylene glycol group 100ppm Water-soluble polyamide water with both balance pH: 3.0 (adjusted with nitric acid and ammonia water)

Comparative Example 4 A surface treatment liquid (trade name: Alodine 404, manufactured by Nippon Parkerizing Co., Ltd.) for aluminum DI cans was heated to 35 ° C. and sprayed on the washed aluminum DI cans for 25 seconds, and then the following composition was used. Surface treatment liquid (11) at 35 ℃
The mixture was heated and sprayed for 15 seconds, washed in the same manner as in Example 1, washed with deionized water, and dried. Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment liquid (11) 20% fluorozirconic acid (H ₂ ZrF ₆ ) 500ppm (Zr: 44ppm) 20% hydrofluoric acid (HF) 26ppm (F: 60ppm) Tertiary amino group and polyalkylene glycol group 100ppm Water-soluble polyamide water with both balance pH: 4.5 (adjusted with nitric acid and ammonia water)

Comparative Example 5 A surface treatment liquid (12) having the following composition was heated to 35 ° C. and spray-treated for 20 seconds on a washed aluminum DI can, followed by washing with water, washing with deionized water and drying as in Example 1. .
Then, the corrosion resistance and adhesiveness of this DI can were evaluated. Surface treatment liquid (12) 75% Phosphoric acid (H ₃ PO ₄ ) 138ppm (PO ₄ : 100ppm) 20% Fluorozirconic acid (H ₂ ZrF ₆ ) 500ppm (Zr: 44ppm) 20% Hydrofluoric acid (HF) 236ppm (F: 100ppm) Water-soluble polyamide water having both tertiary amino group and polyalkylene glycol group 100ppm Residual pH: 4.5 (adjusted with nitric acid and ammonia water)

Table 1 shows the test results of Examples 1-8 and Comparative Examples 1-5.

[Table 1]

As is clear from the results shown in Table 1, the surface-treated aluminum-containing metal materials obtained in Examples 1 to 8 using the surface-treating liquid or the surface-treating method of the present invention have corrosion resistance, paint adhesion and lubricity. , Both were excellent. On the other hand, the performance of the products of Comparative Examples 1 to 5 using surface treatment liquids other than the present invention was particularly inferior in lubricity.

[0048]

As described above, the surface treatment liquid and the surface treatment method using the surface treatment composition according to the present invention have excellent corrosion resistance and lubricity on the surface of the aluminum-containing metal material before coating. A film can be formed. Further, by applying the surface treatment liquid of the present invention to an aluminum DI can, aluminum DI before coating and printing can be obtained.
It has the excellent effect of imparting excellent corrosion resistance and lubricity to the surface of the can and achieving speedup of the production line.

[Brief description of drawings]

FIG. 1 (A) is an explanatory plan view showing an arrangement state of test cans in a slipperiness tester. FIG. 1 (B) is a front explanatory view of the slip tester of FIG. 1 (A). FIG. 1 (C) is a side view of the slip tester of FIG. 1 (A).

[Explanation of symbols]

 1 ... Inclined plate (horizontal position) 1a ... Inclined inclined plate 2a ... Can on front side of bottom 2b ... Can on front side of opening 3 ... Motor

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C10M 103: 06 B 107: 44) C10N 10:08 30:06 30:12 30:20 40:24 A

Claims (3)

[Claims] 1. The following components: (1) Phosphate ion, and (2) 0.01 to 50 parts by weight of a water-soluble zirconium compound and titanium compound in terms of metal atom with respect to 1 part by weight thereof. At least one selected, (3) 0.01 to 200 parts by weight of a fluoride in terms of fluorine atom, and (4) 0.01 to 200 parts by weight of a tertiary amine group and polyalkylene. A composition for surface treatment of an aluminum-containing metal material, which comprises an aqueous mixture containing a water-soluble polyamide having at least one selected from glycol groups. 2. The following components: 0.01 to 1.0 g / liter of phosphate ions and 0.01 to 0.5 g / liter of metal atoms,
At least one selected from water-soluble zirconium compounds and titanium compounds, 0.01 to 2.0 g / liter of a fluoride atom in terms of fluorine atom, and 0.01 to 2.0 g / liter of the third Water-soluble polyamide having at least one selected from a primary amine group and a polyalkylene glycol group.
A surface treatment liquid for an aluminum-containing metal material, which comprises an aqueous solution having a pH of 4.0. 3. The surface treatment liquid according to claim 2 is brought into contact with the surface of an aluminum-containing metal material to form a surface treatment liquid layer on the surface, which is washed with water and dried by heating, A surface treatment method for an aluminum-containing metal material, which comprises forming a chemical conversion film on the surface.