CN1123649C - Aqueous composition and solution and process for metallic surface-treating an aluminum-containing metal material - Google Patents
Aqueous composition and solution and process for metallic surface-treating an aluminum-containing metal material Download PDFInfo
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- CN1123649C CN1123649C CN95103560A CN95103560A CN1123649C CN 1123649 C CN1123649 C CN 1123649C CN 95103560 A CN95103560 A CN 95103560A CN 95103560 A CN95103560 A CN 95103560A CN 1123649 C CN1123649 C CN 1123649C
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Abstract
A highly corrosion-resistant, strongly paint-adherent conversion coating is formed on the surface of aluminiferous metal substrates by contacting such surfaces for 0.5 to 60 seconds with a sludging-free water-based surface treatment bath that has a pH of 1.5 to 4.0 and contains a zirconium compound, phosphoric acid compound, oxidizing agent, and a compound that is a source of hydrogen fluoride (in a quantity that produces a concentration of from 0.0001 to 0.2 g/L HF in the treatment bath). This contact is preferably followed by a water rinse and drying.
Description
The present invention relates to an aqueous composition and solution and a process for the metal surface treatment of an aluminium-containing metal material. More particularly, the present invention relates to an aqueous composition and solution and a method for treating the metal surface of an aluminum-containing metal material, such as an aluminum or aluminum alloy material, to impart excellent corrosion resistance and paint adhesion to the metal surface prior to coating the metal surface with a paint.
In particular, the aqueous compositions and solutions and processes of the present invention can be advantageously used for aluminum-containing metal cans produced by drawing and ironing processes. Namely: by using the aqueous compositions and solutions and methods of the present invention prior to the application of the painting and printing steps, a chemical conversion layer that imparts excellent corrosion resistance and paint adhesion to the can is formed on the surface of the draw-ironed can in a relatively short period of time as compared to the prior art.
The aqueous solution for metal surface treatment of the present invention is a transparent liquid and exhibits high resistance to sludge formation even when aluminum produced from an aluminum-containing metal material is dissolved therein. Therefore, the method of the present invention for metal surface treatment of an aluminum-containing metal material can be favorably carried out while preventing sludge from being deposited on a metal surface treatment apparatus.
The conventional surface treatment liquids for aluminum-containing metal materials are simply classified into chromate-based treatment liquids and non-chromate-based treatment liquids. Typical chromate-type treatment solutions are classified into chromic acid-chromate chemical conversion treatment solutions and phosphoric acid-chromate chemical conversion treatment solutions.
Chromic acid-chromate chemical conversionThe chemical liquid is put into practical use in about 1950 and is still widely used for producing the leftover materials of the heat exchanger. The chromic acid-chromate chemical conversion treatment liquid comprises chromic acid (CrO) as a main component3) And Hydrogen Fluoride (HF), and optionally a chemical conversion-promoting agent, which form a chemical conversion layer containing an amount of hexavalent chromium on the surface of the metallic material.
Phosphoric acid-chromate chemical conversion solutions are given by us patent 2,438,877, patented in 1945. These chemical conversion solutions include chromic acid (CrO) as a main component3) Phosphoric acid (H)3PO4) And Hydrogen Fluoride (HF), the chemical conversion layer formed from this chemical conversion solution includes hydrated chromium phosphate (CrPO) as a main component4·4H2O). Because the chemical conversion coating is free of hexavalent chromium, phosphoric acid-chromate chemical conversion solutions are still widely used to produce the base coat of the paint layer on the body and lid portions of the beverage can.
As described above, since chromate type surface treatment liquids contain harmful hexavalent chromium, there is a strong demand for the use of hexavalent chromium-free surface treatment liquids to prevent environmental pollution.
Typical hexavalent chromium-free non-chromate type surface treatment liquids are disclosed in japanese unexamined patent application 52-131937. The surface treatment solution is comprised of an aqueous acidic coating solution containing zirconium, titanium or mixtures thereof, phosphate and fluoride, and has a pH of about 1.0 to about 4.0. When the non-chromate type surface treatment liquid is applied to the surface of a metal material, a chemical conversion layer comprising zirconium oxide or titanium oxide as a main component is formed on the metal surface.
Non-chromate type surface treatment solutions are widely used for surface treatment of drawn-ironed aluminum cans due to the advantage of not containing harmful hexavalent chromium. For industrial applications, non-chromate surface treatments must take 15 seconds or more in order to impart the necessary properties, such as sufficiently high corrosion resistance, to aluminum cans. However, in view of the fact that the production of aluminum cans (which are produced by the drawing and ironing method, hereinafter referred to as DI aluminum cans) has recently increased significantly, the production speed of DI aluminum cans is strongly required to be greatly increased, and the surface treatment apparatus is required to be compact in order to reduce the necessary space of the apparatus. Further, it is also strongly desired to shorten the time necessary for the surface treatment of the aluminum-containing metal material.
Currently, the above non-chromate treatment liquids such as phosphoricacid-chromate type treatment liquids and zirconium type treatment liquids are mainly used for surface treatment of general DI aluminum cans, and the outer surfaces of the aluminum cans are sterilized at high temperatures before coating in the process of producing the DI aluminum cans.
If the outer surface has poor corrosion resistance, the aluminum surface is easily oxidized and discolored to black. This phenomenon is called blacking-tarnishing. Therefore, prior to painting, a chemical conversion layer itself formed on the surface of the aluminum can is required to have high corrosion resistance.
Japanese unexamined patent publication No. 1-246370 discloses a method for surface-treating a metal material, which can be accomplished in a short time.
In the method, the surface of an aluminum-containing metal material is cleaned with an alkaline degreasing agent, and then the cleaned surface is treated with an acidic aqueous solution containing 0.01 to 0.5 g/l of zirconium ions, 0.01 to 0.5 g/l of phosphate ions, 0.001 to 0.05 g/l of available fluoride ions, and optionally 0.01 to 1 g/l of vanadium ions and having a pH of 1.5 to 4.0. However, this method has not been completely successful in obtaining satisfactory blackening-tarnishing resistance.
Japanese examined patent publication No. 57-39314 discloses another non-chromate surface treatment method. In the method, the surface of an aluminum-containing metal material is treated with an acidic aqueous solution containing one or both of a titanium salt and a zirconium salt, hydrogen peroxide, and one or both of phosphoric acid and condensed phosphoric acid. This process then has the disadvantage that the acidic aqueous solutions are not stable on storage and have an unsatisfactory activity for the formation of surface coatings. Moreover, the japanese patent does not explicitly disclose the necessary treatment temperature, time and operation of the acidic aqueous solution. Moreover, the method disclosed in the Japanese patent has not successfully established a blackening-tarnishing resistance strength high enough for industrial use.
Japanese examined patent publication No. 56-33468 discloses another non-chromate type surface treatment liquid. The surface treatment liquid is an acidic aqueous solution containing zirconium, titanium or a mixture thereof, phosphate and fluoride and having a pH of 1.5 to 4.0.
The liquid has the advantage that it contains effective fluoride and is free of solid matter and harmful hexavalent chromium that may precipitate from the liquid. However, this liquid has the following disadvantages.
When the surface treatment liquid is sprayed onto the surface of the aluminum can in a short time of 15 to 30 seconds, the resulting coating is uneven and exhibits unstable corrosion resistance due to the generation of uneven flow rate of the sprayed liquid on the local surface of the can and uneven contact conditions between the liquid and the surface of the can.
When a chemical conversion layer is formed at an increased thickness on the outer surface of the bottom of the can to stabilize its corrosion resistance, the chemical conversion layer is also formed in excess on the bulging portion or neck portion of the can, which must be handled after painting. This excessively thick chemical conversion layer allows easy separation of the coating formed thereon.
In particular, when the surface treatment liquid is aged and dissolved from an aluminum can and the content of aluminum accumulated in the liquid becomes high, the difference in the thickness of the chemical conversion layer between the can portions becomes particularly significant.
In order to eliminate the above-mentioned disadvantages, when the usual surface treatment liquids are used industrially for aluminum cans, the effective fluoride content is required to be lower than the content at which they are kept constant to obtain the best aimed results. This requirement is also a disadvantage of conventional surface treatment fluids. Although the conventional surface treatment liquid is characterized by containing no solid matter likely to be deposited therein, when the conventional surface treatment liquid is put to practical use and contaminated with aluminum ions dissolved therein from an aluminum can, undesirable deposition often occurs to soil the equipment and clog the treatment liquid nozzle.
An object of the present invention is to provide an aqueous composition and a solution for metal surface treatment of an aluminum-containing metal material and a method for imparting excellent corrosion resistance and paint adhesion to the surface of the aluminum-containing metal material in a short time.
It is another object of the present invention to provide an aqueous composition and solution and a method for treating metal surfaces of aluminum-containing metal materials to coat the metal surfaces with a chemically converted layer having a high degree of uniformity and excellent corrosion resistance and paint adhesion to the metal surfaces, which method has a high degree of stability while preventing the generation of sludge.
The aqueous composition for treating a metal surface of an aluminum-containing metal material according to the present invention comprises phosphate ions, at least one zirconium compound, at least one fluorine compound and an oxidizing agent in the following weight ratios:
0.5-80, expressed as phosphate ions: 0.5-50, expressed as zirconium ions: 3-100, represented by fluorine atoms: 1-50, expressed as oxidant.
The aqueous solution for metal surface treatment of an aluminum-containing metal material of the present invention comprises the above-defined aqueous composition for metal surface treatment.
The aqueous metal surface treatment solution of the present invention preferably comprises 0.005 to 0.8 g/l of phosphate ions, 0.005 to 0.5 g/l of at least one zirconium compound expressed as zirconium atoms, 0.03 to 1 g/l of at least one fluorine compound expressed as fluorine atoms and 0.01 to 5 g/l of an oxidizing agent, and has a pH of 1.5 to 4.0.
The method of the present invention for metal surface treatment of an aluminum-containing metal material with the aqueous metal surface treatment solution as defined above comprises the steps of:
(1) contacting the aqueous metal surface treatment solution with a metal surface of an aluminum-containing metal material at a temperature between 20 ℃ and 90 ℃ for a time sufficient to form a chemical conversion layer on the surface of the aluminum-containing metal material;
(2) cleaning the surface of the chemical conversion layer by water; and
(3) drying the surface of the chemical conversion layer cleaned with water.
Aqueous metal surface treatment compositions and solutions for aluminum-containing metallic materials include as essential ingredients phosphate ions, at least one zirconium compound, at least one fluorine compound, and an oxidizing agent dissolved in water, and are generally acidic. In the present invention, it is important that the aqueous metal surface treatment composition and solution contain fluorine and an oxidizing agent. This important feature effectively stabilizes the aqueous metal surface treatment solution, significantly improving the corrosion resistance (blackening-tarnishing resistance) and paint adhesion of the resulting chemical conversion layer.
The aqueous composition for metal surface treatment of the present invention comprises phosphate ions, at least one zirconium compound, at least one fluorine compound and an oxidizing agent in the following weight ratios:
0.5-80, expressed as phosphate ions: 0.5-50, expressed as zirconium ions: 3-100, expressed as fluoride ion: 1-500, expressed as oxidant, preferably 1-80, expressed as phosphate ion: 1-15, expressed as zirconium ions: 3-100 represents fluorine atom: 1: 100, expressed as oxidant, more preferably from 3 to 20, expressed as phosphate ion: 4-8, expressed as zirconium atoms: 3-60, represented by fluorine atoms: 20-50, expressed as oxidant, and a pH of 1.0 to 4.0.
The aqueous composition of the present invention is used for preparing an aqueous solution for metal surface treatment of an aluminum-containing metal material by diluting the aqueous composition with water.
In preparing the aqueous solution for metal surface treatment which can be used in the method of the present invention, the concentrations of the respective components are adjusted to:
phosphate radical ion: 0.005-0.8 g/l, preferably 0.01-0.8 g/l,
zirconium compound: 0.005 to 0.5 g/l, preferably 0.01 to 0.15 g/l, in terms of zirconium atom,
fluorine compound (b): 0.03 to 1 g/l, in terms of fluorine atom,
oxidizing agent: 0.01 to 5 g/l, preferably 0.01 to 1 g/l.
Further, the pH of the aqueous solution for metal surface treatment is preferably adjusted to 1.5 to 4.0.
The phosphate ions contained in the aqueous composition and solution for metal surface treatment are derived from phosphoric acid (H)3PO4) And water-soluble salts of phosphoric acid such as water-soluble alkali metal phosphates and ammonium phosphates. When the concentration of phosphate ions in the aqueous solution for metal surface treatment is less than 0.005 g/l, the resulting solution does not exhibit satisfactory reactivity with the metal surface, and therefore it is difficult to form a chemical conversion layer in an amount sufficient to impart satisfactory corrosion resistance and paint adhesion to the metal surface. When the phosphate ion concentration is more than 0.8 g/l, the effect of the resulting aqueous solution for forming a chemical conversion layer is saturated, and the economic efficiency of the aqueous solution becomes poor.
In the aqueous metal surface treatment compositions and solutions, the zirconium compound may be provided by zirconium oxide, zirconium hydroxide, zirconium nitrate, and zirconium fluoride. If the concentration of the zirconium compound in the aqueous solution is less than 0.005 g/l in terms of zirconium atom, it is difficult to form a chemical conversion layer in a satisfactory amount on the metal surface. Further, when the concentration of the zirconium compound in the aqueous solution is more than 0.5 g/l in terms of zirconium atom, the chemical conversion layer forming function of the aqueous solution is saturated, and the aqueous solution exhibits low economic efficiency.
In the metal surface treatment compositions and solutions of the present invention, the fluorine compound may be selected from Hydrogen Fluoride (HF), fluorozirconic acid (H)2ZrF6) Fluotitanic acid (H)2TiF6) Silicofluoric acid, borofluoric acid and water soluble salts of the above acids.
When the concentration of the fluorine compound in the aqueous solution for metal surface treatment is less than 0.03 g/l in terms of fluorine atom, the resulting aqueous solution cannot exhibit satisfactory reactivity with respect to the metal surface, and the chemical conversion layer cannot be formed in a thickness sufficient to impart satisfactory corrosion resistance and paint adhesion to the metal surface. Moreover, if the concentration of the fluorine compound is higher than 1 g/l, the resulting aqueous solution exhibits too strong corrosiveness, so that the metal surface is excessively corroded, and thus the appearance of the treated surface is deteriorated.
Generally, the optimum concentration of the fluorine compound in the aqueous solution for metal surface treatment varies depending on the amount of aluminum dissolved from the aluminum-containing metal material into the aqueous solution, because the fluorine compound serves as a stabilizer by which the aluminum to be coated is stabilized in the form of aluminum fluoride in the aqueous solution. For example, when the dissolved aluminum concentration in the aqueous solution is 0.1 g/l, the necessary concentration of fluorine is about 0.2 g/l.
The oxidizing agent usable in the present invention includes at least one selected from, for example, hydrogen peroxide, nitrous acid, tungstic acid, molybdic acid, peroxyacids such as peroxyboric acid and peroxyphosphoric acid, salts of the above acids, and organic peroxy compounds such as t-butyl hydroperoxide, and t-hexyl hydroperoxide. The oxidizing agent is not limited to the above-mentioned compounds. However, hydrogen peroxide can be advantageously used in the present invention because the waste liquid from the aqueous hydrogen peroxide-containing metal surface treatment solution does not require a specific post-treatment for removing the decomposition products of hydrogen peroxide, whereas other oxidizing agents require a specific post-treatment.
When the concentration of the oxidizing agent in the aqueous solution for metal surface treatment is less than 0.01 g/l, the reaction-promoting action of the oxidizing agent cannot be completely achieved.
And when the concentration of theoxidizing agent is higher than 5 g/l, the reaction-promoting effect of the oxidizing agent is saturated, thus reducing the economic efficiency of the aqueous solution.
The aqueous metal surface treatment compositions of the present invention generally have a pH of from 1.0 to 4.0, while the aqueous metal surface treatment solutions of the present invention preferably have a pH of from 1.5 to 4.0. If the pH of the aqueous solution is less than 1.5, the etching action of the resulting aqueous solution on the metal surface may be excessively strong, and it is difficult to form a satisfactory chemical conversion layer. Whereas if the pH is more than 4.0, it may be difficult to form a chemical conversion layer having satisfactory corrosion resistance with the resulting aqueous metal surface treatment solution. More preferably, the pH of the aqueous solution for metal surface treatment is adjusted to 2.0 to 3.5, and particularly preferably 2.3 to 3.0. The adjustment of the pH of the aqueous solution for the treatment of metal surfaces is effected by adding an acid, such as phosphoric acid, nitric acid, hydrochloric acid and/or hydrofluoric acid, or a base, such as sodium hydroxide, sodium carbonate and/or ammonium hydroxide.
When the aqueous metal surface treatment solution of the present invention is used for an alloy material made of aluminum and copper or manganese, sometimes the stability of the aqueous metal surface treatment solution is significantly lowered by metal ions of alloy components such as copper or manganese ions dissolved into the aqueous solution from the alloy. In this case, an organic acid for chelating a metal such as gluconic acid or oxalic acid may be added to the aqueous metal surface treatment solution to chelate the alloy component metal.
In an embodiment of the present invention, the fluorine compound is selected from hydrogen fluoride-generating compounds, i.e., hydrogen fluoride source compounds, and is used in an amount sufficient to generate hydrogen fluoride in a concentration of 0.0001 to 0.2 g/l in an aqueous solution, and the pH of the aqueous metal surface treatment solution is 1.5 to 4.0.
The hydrogen fluoride-producing compound may be selected from hydrogen fluoride and ammonium fluoride.
In this embodiment, the aqueous metal surface treatment composition comprises, in addition to the hydrogen fluoride-generating compound, phosphate ions, at least one zirconium compound and an oxidizing agent in a weight ratio of 0.5 to 40: 0.5 to 50 (in terms of zirconium atoms) to 0.1 to 500.
The hydrogen fluoride generated from the hydrogen fluoride-generating compound in the aqueous solution for metal surface treatment is effective to make the reaction rate of the resulting aqueous solution on the metal surface uniform over the entire metal surface, thus forming a chemical conversion layer uniformly on the metal surface. Moreover, the hydrogen fluoride effectively increases the reaction rate for forming the chemical conversion layer and the quality uniformity of the final chemical conversion layer.
Moreover, hydrogen fluoride controlled to a concentration of 0.001 to 0.2 g/l advantageously prevents excessive deposition of zirconium compounds due to an increase in aluminum concentration as the aqueous solution ages and degrades. That is, the formation of sludge can be prevented by controlling the hydrogen fluoride concentration in the aqueous solution for metal surface treatment.
In the present invention, the increase in the interfacial pH between the metal surface and the aqueous metal surface treatment solution effects the formation of a chemical conversion layer. In this connection, it is well known that the chemical structure of hydrogen fluoride and a fluorine aluminum complex generated in an aqueous solution for metal surface treatment changes with a change in pH value in the aqueous solution. In other words, in an acidic aqueous solution containing aluminum and fluorine, there is free fluoride ion (F)-) Hydrogen fluoride, aluminum fluoride, and fluorine compounds of different types in the following content ratiosThe pH in the aqueous solution changes.
The increase in the pH of the interface between the metal surface and the aqueous metal surface treatment solution is caused by a decrease in the concentration of hydrogen fluoride in the interface. Therefore, in order to maintain the high performance of the metal surface treatment aqueous solution for forming the chemical conversion layer and the appearance of the metal surface treatment aqueous solution under a transparent condition, it is necessary to appropriately control the concentration of hydrogen fluoride.
The hydrogen fluoride concentration can be measured by the following method.
Diluting a commercially available fluoride ion standard solution with commercially available pH and ionic strength adjusting solution to obtain fluoride ion (F)-) Three standard solutions at concentrations of 1 mg/liter, 10 mg/liter and 100 mg/liter. The standard fluoride ion solution is maintained at a constant temperature, for example, 40 ℃. The standard fluoride ion solution was used to calculate fluoride ion concentration data measured by a fluoride ion meter.
For example at 40A fluorine ion concentration of a sample of an aqueous solution for metal surface treatment is measured by a fluorine ion meter at DEG C, and the measured fluorine ion concentration is converted into a molar concentration (F)-). Further, the pH value of the aqueous solution is measured, and the hydrogen concentration [ H]is calculated from the measured pH data+〕。
The hydrogen fluoride [ HF]concentration (g/l) was measured by the following equation.
pH＝log10[H+]
logKHF＝3.17
As described above, the hydrogen fluoride concentration in the aqueous solution for metal surface treatment is controlled to be 0.0001 to 0.2 g/l in the embodiment of the present invention. If the hydrogen fluoride concentration is less than 0.0001 g/l, zirconium-containing sludge can be easily produced from the aqueous solution. Whereas if the hydrogen fluoride concentration is more than 0.2 g/l, the resulting aqueous solution exhibits an excessive corrosive action on the metal surface, and it may be difficult to form a desired chemical conversion layer.
In the process of the present invention, an aqueous metal surface treatment solution is prepared from an aqueous metal surface treatment composition, if necessary, by diluting the composition with water and adjusting the pH of the aqueous solution to 1.5 to 4.0.
The aluminum-containing metal material to be surface-treated is subjected to pretreatment including a cleaning (degreasing) step with a cleaning liquid, which may be an acidic aqueous solution, an alkaline aqueous solution or an organic solvent, and a rinsing step with water.
The method of the present invention is carried out on the pretreated metal material, followed by a post-treatment comprising washing with water, washing with deionized water and drying steps.
Surface treatment of metals
(1) Cleaning surfaces (degreasing) with aqueous acid or alkaline solutions or organic solvents
(2) Cleaning with water
(3) Surface treatment (method of the invention)
Treatment temperature: 20-90 deg.C
The treatment method comprises the following steps: by dipping or spraying
Treatment time: 0.5-60 seconds
(4) Cleaning with tap water
(5) Cleaning with deionized water
(6) Drying
In the method of the present invention, the aqueous metal surface treatment solution is contacted with the metal surface of the aluminum-containing metal material at a temperature of from 20 ℃ to 90 ℃, preferably from 25 ℃ to 50 ℃, more preferably from 30 ℃ to 50 ℃ for a time sufficient to form a chemical conversion layer on the metal surface of the aluminum-containing metal material.
The contact time is not limited to a particular period as long as a satisfactory chemical conversion layer containing zirconium is formed on the metal surface during the contact time. The preferred contact time is from 0.5 to 60 seconds, more preferably from 2 to 30 seconds.
The treatment temperature was from 20 ℃ (room temperature) to 90 ℃. However, in view of the stability and ease of treatment of the aqueous solution for metal surface treatment and the feasibility of the method, the treatment temperature is preferably controlled to 25 ℃ to 50 ℃, more preferably 30 ℃ to 50 ℃. When the treatment temperature is too low, the reaction for forming the chemical conversion layer may proceed at a very low reaction rate, and thus it is difficult to form a satisfactory chemical conversion layer within an industrially usable time. When the treatment temperature is too high, the zirconium compound dissolved in the aqueous solution for metal surface treatment may become chemically unstable, and a part of the zirconium compound may be deposited from the aqueous solution.
The metal surface treatment aqueous solution may be brought into contact with the surface of the aluminum-containing metal material by immersing the metal material in an aqueous solution or spraying an aqueous solution onto the surface of the metal material.
In the dipping method, the metal material is preferably left in the aqueous metal surface treatment solution for 0.5 to 60 seconds, preferably 2 to 30 seconds, more preferably 5 to 15 seconds.
The spraying of the aqueous solution for metal surface treatment may be performed in one operation or two or more intermittent operations. The intermittent spraying operation is preferably carried out at intervals of 1 to 5 seconds, more preferably 2 to 3 seconds, and the total contact time as the total of the number of times of spraying and the interval time is preferably 0.5 to 60 seconds, more preferably 2 to 30 seconds, and particularly more preferably 5 to 10 seconds.
In the method of the present invention, the resultant chemical conversion layer comprising zirconium formed on the surface of the aluminum-containing metal material preferably contains 7 to 18mg/m2Zirconium atom of (2). If the zirconium atom content is less than 7mg/m2The resulting chemical conversion layer may exhibit unsatisfactory corrosion resistance, whereas if the zirconium atom content is more than 18mg/m2The resulting chemical conversion layer may exhibit unsatisfactory paint adhesion. The aluminum-containing metal material which can be used in the present invention includes aluminum materials and aluminum alloy materials. The aluminum alloy includes an alloy of aluminum and at least one of manganese, magnesium, and silicon.
The aluminum-containing metal materials that can be used in the present invention are not limited to those having a specific shape and size, and they may be in the form of plates, sheets and strips, and other models.
Examples
The invention will be explained by the following examples.
In examples and comparative examples, the following metal materials were used.
Metal material
(a) Aluminium-manganese alloy (a3004) cans produced by the drawing and ironing process.
(b) An aluminium-manganese alloy (A3004) plate having a thickness of about 0.3 mm.
The DI cans and aluminum alloy panels were cleaned with a hot aqueous solution of an acidic degreaser available from Nihon Parkering co., Ltd under the trade name parkean 500 and then surface treated.
In each of examples 1 to 11 and comparative examples 1 to 4, the resulting product was subjected to the test explained below.
(a) Corrosion resistance test
The corrosion resistance of the DI cans was evaluated by immersing the cans in boiling water to test the blackening and tarnishing properties.
Discoloration-tarnish was determined by immersing the surface treated DI cans in boiling tap water for 30 minutes. The DI cans were evaluated for discoloration-tarnish by visual inspection and classified as follows.
Class discoloration-tarnish
3 no blackening and tarnishing
2 part blackened-tarnished
1 complete blackening-tarnishing
(b) Paint adhesion
Epoxy urea resin paint for aluminium cans was applied to the can faces in a thickness of 5-7 μm and baked at 215 ℃ for 4 minutes. The paint cans were cut into square test specimens (width 5mm, height 150 mm). The polyamide film was heat bonded to the painted surface of the test piece at 200 ℃ under pressure to provide a test piece. The test pieces were subjected to a 180-degree peel test in which the polyamide film was peeled off from the painted surface of the can to determine the peel strength of the polyamide film from the painted can surface. The higher the peel strength, the higher the paint adhesion of the surface-treated aluminum can. Generally, an aluminum can having a peel strength of 4.0kgf/5mm or more is very satisfactory in practical use.
Example 1
An aqueous metal surface treatment solution (1) having the following composition was prepared.
Surface treatment aqueous solution (1)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 69ppm (50ppm PO) of aqueous solution4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous solution 500ppm (44ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF)210ppm (95ppm F)30 wt.% hydrogen peroxide (H)2O2) 332ppm (100pm H) of aqueous solution2O2)
pH3.0 (adjusted with aqueous ammonia)
The above aqueous metal surface treatment solution was heated at 40 ℃ and sprayed onto the surface of a clean DI aluminum can using three spray operations, 2 seconds each with 3 seconds intervals for a total contact time of 12 seconds. The treated surface was washed with tap water and then with deionized water having a resistivity of 3,000,000 Ω cm or more for 10 seconds. Thereafter, the washed matter was dried in a hot air dryer at 180 ℃ for 2 minutes.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 2
An aqueous metal surface treatment solution (2) having the following composition was prepared.
Surface treatment aqueous solution (2)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 69ppm (50ppm PO) of aqueous solution4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous 1000ppm (88ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 210ppm (150ppm F)30 wt.% hydrogen peroxide (H)2O2) 166ppm (50ppm H) of aqueous solution2O2)
pH3.3 (adjusted with aqueous ammonia)
In the above metal surface treatment aqueous solution (2) kept at 50 ℃, the cleaned DI aluminum can was immersed for 15 seconds. The impregnated aluminum cans were removed from the aqueous solution and the treated surfaces were rinsed with tap water and then with deionized water for 10 seconds as described in example 1. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 3
An aqueous metal surface treatment solution (3) having the following composition was prepared.
Surface treatment aqueous solution (3)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) Aqueous solution 14ppm (10ppm PO)4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous 1000ppm (88ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 210ppm (150ppm F)30 wt.% hydrogen peroxide (H)2O2) 1660ppm (500ppm H) aqueous solution2O2)
pH2.5 (adjusted with aqueous sodium hydroxide solution)
The above aqueous metal surface treatment solution (3) was heated at 50 ℃ and sprayed on the surface of a clean DI aluminum can using a two-pass spraying operation for 2 seconds each with 1 second interval for a total contact time of 5 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 4
An aqueous metal surface treatment solution (4) having the following composition was prepared.
Surface treatment aqueous solution (4)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 138ppm aqueous solution (100ppm PO)4Ion)20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous 250ppm (22ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 100ppm (47ppm F)30 wt.% hydrogen peroxide (H)2O2) Aqueous solution 830ppm (250ppm H)2O2)
pH4.0 (adjusted with aqueousammonia)
The aqueous metal surface treatment solution was heated at 50 c and sprayed onto the cleaned DI aluminum can surfaces using six spray operations, 3 seconds each with 2 second intervals for a total contact time of 28 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 5
An aqueous metal surface treatment solution (5) having the following composition was prepared.
Surface treatment aqueous solution (5)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 138ppm aqueous solution (100ppm PO)4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous 500ppm (44ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 210ppm (95ppm F)30 wt.% hydrogen peroxide (H)2O2) Aqueous solution 322ppm (100ppm H)2O2)
pH2.0 (adjusted with aqueous ammonia)
The above aqueous metal surface treatment solution was heated at 35 c and sprayed onto the surface of a clean DI aluminum can using three spray operations, two seconds each with 2 seconds intervals for a total contact time of 10 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 6
An aqueous metal surface treatment solution (6) having the following composition was prepared.
Surface treating aqueous solution (6)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 69ppm (50ppm PO) of aqueous solution4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous 500ppm (44ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF)210ppm (95ppm F) sodium tungstate (Na)2WO4·2H2O) 1000ppm(800ppm WO4)
pH2.5 (adjusted with aqueous nitric acid)
The above aqueous metal surface treatment solution was heated at 35 c and sprayed onto the surface of a clean DI aluminum can using three spray operations, 3 seconds each with 5 seconds intervals for a total contact time of 19 seconds. The treated surface was washed with tap water and then rinsed with the same deionized water as in example 1. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 7
An aqueous metal surface treatment solution (7) having the following composition was prepared.
Surface treatment aqueous solution (7)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 69ppm (50ppm PO) of aqueous solution4Ion)20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous solution 500ppm (44ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 210ppm (95ppm F)30 wt.% sodium nitrite NaNO21000ppm (133ppm NO) aqueous solution2)
pH2.5 (adjusted with aqueous nitric acid)
The above aqueous metal surface treatment solution (7) was heated at 35 ℃ andsprayed onto the cleaned DI aluminum can surfaces using 4 spray operations, 2 seconds each, 2 seconds apart, for a total contact time of 14 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 8
An aqueous metal surface treatment solution (8) having the following composition was prepared.
Surface treatment aqueous solution (8)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 690ppm aqueous solution (500ppm PO)4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous 500ppm (44ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 210ppm (95ppm F)30 wt.% hydrogen peroxide (H)2O2) 166ppm (50ppm H) of aqueous solution2O2)
pH3.0 (adjusted with nitric acid solution)
The above aqueous metal surface treatment solution (8) was heated at 35 ℃ and sprayed on the surface of a clean DI aluminum can using three spray operations, 2 seconds each with 2 second intervals for a total contact time of 10 seconds. The treated surface was washed with tap water and then with deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 9
An aqueous metal surface treatment solution (9) having the following composition was prepared.
Surface treatment aqueous solution (9)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 25ppm (18ppm PO) of aqueous solution4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous solution 228ppm (20ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 150ppm (54ppm F)30 wt.% hydrogen peroxide (H)2O2) 667ppm (200ppm H) of aqueous solution2O2)
pH2.5 (adjusted with aqueous nitric acid)
The above aqueous metal surface treatment solution (9) was heated at 35 ℃ and sprayed on the surface of a clean DI aluminum can using three spraying operations, two seconds each, 2 seconds apart, for a total contact time of 10 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 10
An aqueous metal surface treatment solution (10) having the following composition was prepared.
Aqueous surface treatment solution (10)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) Aqueous solution 14ppm (10ppm PO)4Ion)20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous solution 114ppm (10ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 150ppm (41ppm F)30 wt.% hydrogen peroxide (H)2O2) Aqueous solution 3333ppm (1000ppm H)2O2)
pH2.8 (adjusted with aqueous ammonia)
The above aqueous metal surface treatment solution (10) was heated at 35 ℃ and sprayed on the cleaned DI aluminum can surfaces using three spray operations, 2 seconds each with 2 second intervals for a total contact time of 26 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Example 11
An aqueous metal surface treatment solution (11) having the following composition was prepared.
Aqueous surface treatment solution (11)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) Aqueous solution 413ppm (300ppm PO)4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous solution 1706ppm (150ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 150ppm (216ppm F)30 wt.% hydrogen peroxide (H)2O2) 16667ppm (5000ppm H) aqueous solution2O2)
pH2.5 (adjusted with aqueous ammonia)
The above aqueous metal surface treatment solution (11) was heated at 40 ℃ and sprayed on the surface of a clean DI aluminum can for 3 seconds using a one-shot spray operation for a total contact time of 3 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test. Comparative example 1
An aqueous metal surface treatment solution (12) having the following composition was prepared.
Aqueous surface treatment solution (12)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 69ppm (50pm PO) of aqueous solution4Ion) 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous 500ppm (44ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 210ppm (95ppm F) pH3.0 (adjusted with aqueous ammonia solution)
The above aqueous metal surface treatment solution (12) was heated at 35 ℃ and spray-cleaned DI aluminum can surfaces were sprayed using three spray operations, two seconds each, 2 seconds apart, for a total contact time of 10 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
Comparative example 2
An aqueous metal surface treatment solution (13) having the following composition was prepared.
Surface treatment aqueous solution (13)
The amount of component used was 75 wt.% phosphoric acid (H)3PO4) 69ppm (50ppm PO) of aqueous solution4Ion) 20 wt.% zirconium fluorideAcid (H)2ZrF6) Aqueous solution 57ppm (5ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 210ppm (40ppm F) pH3.0 (adjusted with aqueous ammonia solution)
The above aqueous metal surface treatment solution (13) was heated at 35 ℃ and sprayed on the surface of a clean DI aluminum can using three spray operations, two seconds each, 2 seconds apart, for a total contact time of 10 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test. Comparative example 3
An aqueous metal surface treatment solution (14) having the following composition was prepared.
Surface treatment aqueous solution (14)
Component amounts 20 wt.% fluorozirconic acid (H)2ZrF6) Aqueous 500ppm (44ppm Zr)20 wt.% aqueous Hydrogen Fluoride (HF) 210ppm (95ppm F) pH3.0 (adjusted with aqueous ammonia solution)
The aqueous metal surface treatment solution (14) was heated at 40 c and sprayed onto the cleaned DI aluminum can surfaces using three spray operations, two seconds each, spaced 2 seconds apart, for a total contact time of 10 seconds. The treated surface was washed with tap water and then with the same deionized water as in example 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test. Comparative example 4
An aqueous metal surfacing solution sold under the trade name Allofin404 by Nihon Parkerlizing was heated to 30 c and the cleaned DI aluminum can surfaces were sprayed using three spray operations, 2 seconds each with 2 second intervals for a total contact time of 10 seconds. The treated surface was washed with tap water and then with the same deionized water as in claim 1 for 10 seconds. Thereafter, the mixture was dried in the same manner as in example 1.
Table 1 shows the results of the corrosion resistance test and the paint adhesion test.
TABLE 1
Table 1 clearly shows that in examples 1 to 11, the resulting chemical conversion layers formed fromthe aqueous metal surface treatment solutions according to the method of the present invention exhibited excellent corrosion resistance and paint adhesion, whereas the comparative chemical conversion layers formed from comparative examples 1 to 4 were unsatisfactory in at least one of corrosion resistance, peel strength of the paint layer and zirconium content in the comparative chemical conversion layers.
Furthermore, it has been demonstrated that the use of the aqueous metal surface treatment solutions and methods of the present invention results in the formation of a chemical conversion coating having satisfactory zirconium content and excellent corrosion resistance and paint adhesion on the surface of aluminum-containing metal materials (e.g., DI aluminum cans) in a short contact time prior to the painting and printing steps. Further, the present invention enables a metal surface treatment method to be efficiently performed at high speed using a small-sized treatment apparatus.
In each of examples 12 to 18 and comparative examples 5 to 11, the surface-treated cans were subjected to a corrosion test, a transparency test and a sludge fixation test as described below.
Also in each of examples and comparative examples, the aluminum alloy sheet (a3004) was subjected to the same metal surface treatment, and the obtained surface-treated aluminum alloy sheet was subjected to a corrosion test, a paint adhesion test, a transparency test and a sludge fixation test as described below.
(a) Corrosion resistance test
The test pot was observed to darken-tarnish in boiling water to evaluate the corrosion resistance and uniformity of the chemical conversion layer.
The surface treated aluminum cans were immersed in boiling tap water for 30 minutes. The degree of blackening-tarnishing occurring in the convex portion of the can surface (in which the treatment liquid flows at a high speed) and the degree of blackening-tarnishing occurring in the concave portion (in which the treatment liquid flows at a low speed) were evaluated by visual observation.
The protruding portion corresponds to the ridge portion and the recessed edge portion of the can; and the recessed portion corresponds to the domed portion of the DI aluminum can.
The corrosion resistance was rated in the following three categories:
corrosion resistance like
3 do not turn black-tarnish
2 part blackened-tarnished
1 total blackening-tarnishing
The uniformity of the chemical conversion layer was evaluated as follows
Uniformity of class
2 in the convex and concave parts, no blackening and tarnishing are observed
1 blacking-tarnishing visible on at least one side of the convex and concave portions
(b) Paint adhesion
The surface of the surface-treated aluminum alloy sheet (A3004) was coated with an epoxy urea paint for aluminum cans to a thickness of 5 to 7 μm, and baked and dried at 215 ℃. The painted aluminum alloy sheet was folded using a folding tester to provide a test specimen for paint peeling test. The paint peel test was performed by applying tape to the painted surface of the folded sample and peeling the tape from it. The tested sides were visually observed and evaluated as follows.
Paint-like adhesion
2 paint layer is not peeled off
1 partial or total stripping of the paint
(c) Transparency test
The aqueous solutions for metal surface treatment used in each of examples and comparative examples were allowed to stand at a constant temperature of 40 ℃ for 15 days. The zirconium content of the aqueous solution before and after the test was measured. When a difference in the amount of zirconium was found between before and after the test, it was confirmed that a deposit was formed and the transparency of the aqueous solution was decreased.
(d) Sludge fixation test
The aqueous solutions for metal surface treatment used in each of examples and comparative examples were continuously spray-operated at 40 ℃ for 16 hours using a small spray device. The fixation of sludge in the nozzle was observed with the naked eye.
Example 12
An aqueous metal surface treatment solution (15) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (15):
content of the components
Phosphoric acid 30ppm as PO4Ion meter
30ppm of fluorozirconic acid (calculated as zirconium)
Hydrogen peroxide 100ppm as H2O2Meter
100ppm of aluminum nitrate in terms of Al
Hydrogen Fluoride (HF) 11ppm
pH: 3.0 (adjusted with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content. Aluminum nitrate was used in order to artificially age the aqueous solution with aluminum.
The aqueous metal surface treatment solution (15) was sprayed onto the clean surface of the DI aluminum can using a single spray operation at 40 ℃ for 20 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results.
Example 13
An aqueous metal surface treatment solution (16) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (16):
content of the components
Phosphoric acid 20ppm as PO4Ion meter
Fluorozirconic acid 10ppm, calculated as zirconium
Hydrogen peroxide 300ppm as H2O2Meter
Aluminum nitrate 5ppm in terms of Al
9ppm of Hydrogen Fluoride (HF)
pH: 2.7 (adjustment with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content.
The aqueous metal surface treatment solution (16) was sprayed onto the clean surface of the DI aluminum can using a single spray operation at 40 deg.C for 40 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results.
Example 14
An aqueous metal surface treatment solution (17) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (17):
content of the components
Phosphoric acid 40ppm as PO4Ion meter
40ppm fluorozirconic acid calculated as zirconium
Hydrogen peroxide 200ppm, as H2O2Meter
Aluminum nitrate 200ppm, as Al
Hydrogen Fluoride (HF) 15ppm
pH: 2.3 (adjustment with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content.
The aqueous metal surface treatment solution (17) was sprayed onto the clean surface of the DI aluminum can using a one-shot spray operation at 40 ℃ for 15 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results.
Example 15
An aqueous metal surface treatment solution (18) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (18):
content of the components
Phosphoric acid 150ppm as PO4Ion meter
Fluorozirconic acid 100ppm, calculated as zirconium
Hydrogen peroxide 400ppm as H2O2Meter
300ppm of aluminum nitrate in terms of Al
Hydrogen Fluoride (HF) 70ppm
pH: 2.5 (adjustment with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content.
The clean surface of the DI aluminum can was immersed in the aqueous metal surface treatment solution (18) at 30 ℃ for 10 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results.
Example 16
An aqueous metal surface treatment solution (19) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (19):
content of the components
Phosphoric acid 400ppm as PO4Ion meter
Fluorozirconic acid 200ppm, calculated as zirconium
Hydrogen peroxide 500ppm as H2O2Meter
500ppm of aluminum nitrate in terms of Al
Hydrogen Fluoride (HF) 100ppm
pH: 2.5 (adjustment with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content.
The aqueous metal surface treatment solution (19) was sprayed onto the clean surface of the DI aluminum can using a one-shot spray operation at 30 ℃ for 5 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results.
Example 17
An aqueous metal surface treatment solution (20) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (20):
content of the components
Phosphoric acid 50ppm as PO4Ion meter
30ppm of fluorozirconic acid (calculated as zirconium)
Hydrogen peroxide 200ppm, as H2O2Meter
Aluminum nitrate 200ppm, as Al
Hydrogen Fluoride (HF) 13ppm
pH: 2.3 (adjustment with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content.
The aqueous metal surface treatment solution (20) was sprayed onto the clean surface of a DI aluminum can using a one-shot spray operation at 40 ℃ for 15 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results.
Example 18
An aqueous metal surface treatment solution (21) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (21):
the amount of the components
Phosphoric acid 50ppm as PO4Ion meter
30ppm of fluorozirconic acid (calculated as zirconium)
Hydrogen peroxide 200ppm, as H2O2Meter
100ppm of aluminum nitrate in terms of Al
Hydrogen Fluoride (HF) 7ppm
pH: 3.5 (adjustment with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content.
An aqueous metal surface treatment solution (21) was sprayed onto the clean surface of a DI aluminum can using a one-shot spray operation at 40 ℃ for 15 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results. Comparative example 5
An aqueous metal surface treatment solution (22) having the following composition wasprepared.
Composition of aqueous metal surface treatment solution (21):
content of the components
Phosphoric acid 30ppm as PO4Ion meter
30ppm of fluorozirconic acid (calculated as zirconium)
Aluminum nitrate 200ppm, as Al
Hydrogen Fluoride (HF) 15ppm
pH: 3.0 (adjusted with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content. The aqueous solution (22) is free of oxidizing agent.
An aqueous metal surface treatment solution (22) was sprayed onto the clean surface of a DI aluminum can using a single spray operation at 40 ℃ for 10 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results. Comparative example 6
An aqueous metal surface treatment solution (23) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (23):
content of the components
Phosphoric acid 50ppm as PO4Ion meter
Hydrofluoric acid 22ppm, calculated as zirconium
Hydrogen peroxide 500ppm as H2O2Meter
100ppm of aluminum nitrate in terms of Al
Hydrogen Fluoride (HF) 10ppm
pH: 2.5 (adjustment with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content. The aqueous solution (23) does not contain a zirconium compound.
An aqueous metal surface treatment solution (22) was sprayed onto the clean surface of a DI aluminum can using a one-shot spray operation at 50 deg.C for 10 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results. Comparative example 7
An aqueous metal surface treatment solution (24) having the following composition was prepared.
Composition of the aqueous metal surface treatment solution (24):
content of the components
40ppm fluorozirconic acid calculated as zirconium
Hydrogen peroxide 500ppm as H2O2Meter
Aluminum nitrate 200ppm, as Al
Hydrogen Fluoride (HF) 50ppm
pH: 3.0 (adjusted with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content. The aqueous solution (24) is free of phosphate ions.
An aqueous metal surface treatment solution (24) was sprayed onto the clean surface of a DI aluminum can using a single spray operation at 35 deg.C for 20 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results. Comparative example 8
An aqueous metal surface treatment solution (25) having the following composition was prepared.
Composition of aqueous metal surface treatment solution (25):
content of the components
Phosphoric acid 50ppm as PO4Ion meter
50ppm of fluorozirconic acid calculated as zirconium
Hydrogen peroxide 300ppm as H2O2Meter
Aluminum nitrate 200ppm, as Al
0.05ppm of Hydrogen Fluoride (HF)
pH: 2.7 (adjustment with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content. The aqueous solution (25) contains fluorine atoms at a concentration of less than 0.03 g/l.
The aqueous metal surface treatment solution (25) was sprayed onto the clean surface of the DI aluminum can using a one-shot spray operation at 40 ℃ for 15 seconds. The surface-treated tank was rinsed with tap water, then sprayed with deionized water for 10 seconds, and dried in a hot air dryer.
Table 2 shows the test results. Comparative example 9
An aqueous metal surface treatment solution (26) having the following composition was prepared.
Metal surface treatment aqueous solution (26)
Content of the components
Phosphoric acid 40ppm as PO4Ion meter
Zirconia 40ppm, in Zr
Hydrogen peroxide 300ppm as H2O meter
Aluminum nitrate 200ppm, as Al
0.01ppm of Hydrogen Fluoride (HF)
pH: 2.8 (adjustment with aqueous ammonia)
Hydrofluoric acid is used to adjust the hydrogen fluoride content, and the aqueous solution (26) contains fluorine atoms at a concentration of less than 0.03 g/l.
An aqueous metal surface treatment solution (26) was sprayed onto the cleaned surface of a DI aluminum can in a single spray operation at 40 deg.C for 10 seconds. The surface-treated aluminum cans were washed with tap water, rinsed with deionized water for 10 seconds, and then dried in a hot air dryer.
The test results are shown in Table 2. Comparative example 10
An aqueous metal surface treatment solution (27) having the following composition was prepared.
Composition of aqueous solution (27) for metal surface treatment
Content of the components
Phosphoric acid 40ppm as PO4Ion meter
Fluozirconic acid 40ppm, calculated as Zr
300ppm of aluminum nitrate in terms of Al
Hydrogen Fluoride (HF) 15ppm
pH: 3.0 (adjusted with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content. The aqueous solution (27) is free of oxidizing agent.
An aqueous metal surface treatment solution (27) was sprayed onto the clean surface of a DI aluminum can using a single spray operation at 40 ℃ for 15 seconds. The surface-treated aluminum cans were washed with tap water, rinsed with deionized water for 10 seconds, and then dried in a hot air dryer.
The test results are shown in Table 2. Comparative example 11
An aqueous metal surface treatment solution (28) having the following composition was prepared.
Composition of aqueous solution (28) for metal surface treatment
Content of the components
Phosphoric acid 100ppm as PO4Ion meter
Fluorozirconic acid 100ppm in Zr
300ppm of aluminum nitrate in terms of Al
Hydrogen Fluoride (HF) 20ppm
pH: 3.0 (adjusted with aqueous ammonia)
Hydrofluoric acid was used to adjust the hydrogen fluoride content. The aqueous solution (28) is free of oxidizing agent.
An aqueous metal surface treatment solution (28) was sprayed onto the clean surface of a DI aluminum can using a single spray operation at 40 deg.C for 30 seconds. The surface treated aluminum cans were washed with tap water, then rinsed with deionized water for 10 seconds, and dried in a hot air dryer.
The test results are shown in Table 2.
TABLE 2
As is clear from Table 2, in the products of examples 12 to 18 of the present invention, the resulting chemical conversion layers were excellent in corrosion resistance, uniformity (blackening-tarnishing resistance) and paint adhesion, and the aqueous metal surface treatment solutions of these examples exhibited satisfactory stability and high resistance to sludge fixation during storage.
In comparative examples 5 to 11, none of the obtained aqueous metal surface treatment solutions and the chemical conversion layers was satisfactory in all the test results.
Claims (16)
1. An aqueous composition for treating a metal surface with an aluminum alloy material, comprising phosphate ions, at least one zirconium compound, at least one fluorine compound and an oxidizing agent, the weight ratio of each component being:
0.5 to 80 expressed as phosphate ions; expressed as zirconium atom, 0.5-50; represented by fluorine atom, 3 to 100: expressed as an oxidizing agent, 1 to 500,
the aqueous composition has a pH of 1.0 to 4.0.
2. The aqueous metal surface treatment composition according to claim 1, wherein the phosphate ion is provided by at least one selected from phosphoric acid and water-soluble metal and ammonium salts of phosphoric acid.
3. The aqueous metal surface treatment composition according to claim 1, wherein the zirconium compound is selected from the group consisting of oxides, hydroxides, nitrates and fluorides of zirconium.
4. The aqueous metal surface treatment composition according to claim 1, wherein the fluorine compound is selected from the group consisting of hydrofluoric acid, ammonium fluoride, fluorozirconic acid, fluorotitanic acid, silicofluoric acid and borofluoric acid, and water-soluble salts of the above acids.
5. The aqueous metal surface treatment composition according to claim 1, wherein the oxidizing agent comprises at least one selected from the group consisting of: hydrogen peroxide, nitrous acid, tungstic acid, molybdic acid, peroxy acids and water-soluble salts of the above acids, and organic peroxy compounds.
6. An aqueous solution of the aqueous composition of claim 1 for the surface treatment of aluminum alloys of metals comprising 0.005 to 0.8 g/l of phosphate ions, 0.005 to 0.5 g/l of at least one zirconium compound expressed as zirconium atoms, 0.03 to 1 g/l of at least one fluorine compound expressed as fluorine atoms and 0.01 to 5 g/l of an oxidizing agent, and having a pH of 1.5 to 4.0.
7. The aqueous solution according to claim 6, wherein the fluorine compound generates hydrogen fluoride in the aqueous solution.
8. The aqueous solution according to claim 7 wherein the hydrogen fluoride producing compound is selected from the group consisting of hydrogen fluoride and ammonium fluoride.
9. The aqueous solution according to claim 7, wherein the concentration of hydrogen fluoride in the aqueous solution is from 0.0001 to 0.2 g/l.
10. The aqueous metal surface treatment solution according to claim 6, comprising 0.01 to 0.8 g/l of phosphate ions, 0.01 to 0.15 g/l of at least one zirconium compound expressed as zirconium atoms, 0.03 to 1 g/l of at least one fluorine compound expressed as fluorine atoms and 0.01 to 1 g/l of an oxidizing agent, and having a pH of 2 to 4.0.
11. An aqueous solution according to claim 6, comprising 0.005 to 0.4 g/l of phosphate, 0.005 to 0.5 g/l of at least one zirconium compound expressed as zirconium atoms, at least one hydrogen fluoride-generating compound in an amount sufficient to generate hydrogen fluoride in the aqueous solution in a concentration of 0.0001 to 0.2 g/l of hydrogen fluoride, and 0.01 to 5 g/l of an oxidizing agent, and having a pH of 1.5 to 4.0.
12. A method of treating a metal surface of an aluminum-alloy material with the aqueous solution of claim 6, comprising the steps of:
(1) contacting the aqueous metal surface treatment solution with the metal surface of the aluminum alloy material at a temperature of 20 ℃ to 90 ℃ for a time sufficient to form a chemicalconversion layer on the surface of the aluminum alloy material;
(2) washing the chemical conversion layer with water; and
(3) drying the surface of the water-washed chemical conversion layer.
13. The metal surface treatment method according to claim 12, wherein the contact time is 0.5 to 60 seconds.
14. The metal surface treatment method according to claim 12, wherein the surface treatment temperature is 25 ℃ to 50 ℃.
15. The metal surface treatment method according to claim 12, wherein the contacting step (1) is performed by immersing the aluminum alloy material in the aqueous metal surface treatment solution.
16. The metal surface treatment method according to claim 12, wherein the contacting step (1) is performed by spraying the metal surface treatment aqueous solution onto the surface of the aluminum alloy material at least once.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP53779/94 | 1994-03-24 | ||
| JP53779/1994 | 1994-03-24 | ||
| JP5377994 | 1994-03-24 | ||
| JP32054594A JP3349851B2 (en) | 1994-12-22 | 1994-12-22 | Surface treatment composition for aluminum-containing metal material excellent in sludge suppression property and surface treatment method |
| JP320545/1994 | 1994-12-22 | ||
| JP320545/94 | 1994-12-22 |
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| CN1124303A CN1124303A (en) | 1996-06-12 |
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| JP3437023B2 (en) * | 1995-11-20 | 2003-08-18 | 日本ペイント株式会社 | Aluminum-based metal surface treatment bath and treatment method |
| JP4351926B2 (en) * | 2003-02-17 | 2009-10-28 | 日本ペイント株式会社 | Antirust treatment agent and antirust treatment method |
| SG129274A1 (en) * | 2003-02-19 | 2007-02-26 | Mitsubishi Gas Chemical Co | Cleaaning solution and cleaning process using the solution |
| JP5159148B2 (en) * | 2007-04-10 | 2013-03-06 | 日本パーカライジング株式会社 | Composite material and manufacturing method thereof |
| CN102586770B (en) * | 2012-03-23 | 2013-10-16 | 广东科富科技股份有限公司 | Method for preparing titanium-zirconium/polyhydroxy esterified product composite conversion coating of aluminum alloy surface |
| TWI493077B (en) * | 2012-04-27 | 2015-07-21 | China Steel Corp | A water-based metal surface treatment agent and a metal surface treatment method using the same |
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| ES2832656T3 (en) * | 2016-11-23 | 2021-06-10 | Chemetall Gmbh | Composition and procedure for chromium-free pretreatment of aluminum surfaces |
| CN109576695A (en) * | 2019-01-17 | 2019-04-05 | 温岭德利众机械制造有限公司 | A kind of method of aluminum component passivator and aluminium workpiece surface processing |
| CN114324740B (en) * | 2021-12-30 | 2024-01-30 | 中国航空工业集团公司金城南京机电液压工程研究中心 | Method for analyzing mixed acid solution of tri-acid deoxidization |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5424232A (en) * | 1977-07-26 | 1979-02-23 | Nippon Packaging Kk | Surface treating method of aluminum |
| JPS5424262A (en) * | 1977-07-26 | 1979-02-23 | Minoru Nakamura | Method of making metal granules |
| EP0337075A2 (en) * | 1988-02-15 | 1989-10-18 | Nippon Paint Co., Ltd. | Surface treatment composition and surface treatment bath for aluminium and aluminium alloys |
| EP0411606A2 (en) * | 1989-08-01 | 1991-02-06 | Nippon Paint Co., Ltd. | Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method |
| GB2259970A (en) * | 1991-09-27 | 1993-03-31 | Samir Abed Issa Albasri | Oral communication device |
| GB2259920A (en) * | 1991-09-10 | 1993-03-31 | Gibson Chem Ltd | Surface conversion coating solution based on molybdenum and phosphate compounds |
| EP0726968A1 (en) * | 1993-07-05 | 1996-08-21 | Henkel Corporation | Composition and process for treating tinplate and aluminum |
| EP0754250A1 (en) * | 1994-03-24 | 1997-01-22 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
-
1995
- 1995-03-22 MY MYPI9500717 patent/MY130189A/en unknown
- 1995-03-24 CN CN95103560A patent/CN1123649C/en not_active Expired - Fee Related
- 1995-03-24 KR KR1019950006343A patent/KR0179687B1/en not_active IP Right Cessation
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5424232A (en) * | 1977-07-26 | 1979-02-23 | Nippon Packaging Kk | Surface treating method of aluminum |
| JPS5424262A (en) * | 1977-07-26 | 1979-02-23 | Minoru Nakamura | Method of making metal granules |
| EP0337075A2 (en) * | 1988-02-15 | 1989-10-18 | Nippon Paint Co., Ltd. | Surface treatment composition and surface treatment bath for aluminium and aluminium alloys |
| EP0411606A2 (en) * | 1989-08-01 | 1991-02-06 | Nippon Paint Co., Ltd. | Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method |
| GB2259920A (en) * | 1991-09-10 | 1993-03-31 | Gibson Chem Ltd | Surface conversion coating solution based on molybdenum and phosphate compounds |
| GB2259970A (en) * | 1991-09-27 | 1993-03-31 | Samir Abed Issa Albasri | Oral communication device |
| EP0726968A1 (en) * | 1993-07-05 | 1996-08-21 | Henkel Corporation | Composition and process for treating tinplate and aluminum |
| EP0754250A1 (en) * | 1994-03-24 | 1997-01-22 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
Also Published As
| Publication number | Publication date |
|---|---|
| KR0179687B1 (en) | 1999-02-18 |
| MY130189A (en) | 2007-06-29 |
| CN1124303A (en) | 1996-06-12 |
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