JP2008174798A - Surface-treated aluminum material, resin-coated aluminum materials, and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aluminum or its alloy material, which is manufactured at a low cost without using a harmful chromium and has a corrosion resistance and an adhesion to a coating resin equivalent to or higher than those formed by phosphoric acid chromate treatment. <P>SOLUTION: The surface-treated aluminum material has a composite film comprising a silane coupling layer on a chemical conversion film containing a vanadium compound with a zirconium phosphate compound as a major component. It is preferable that the deposition amount of the chemical conversion film is 3-20 mg/m<SP>2</SP>as zirconium amount, also the mole ratio of zirconium to phosphorus in the chemical conversion film is 0.6-1.2, and the mole fraction of vanadium on the outermost surface of the chemical conversion film is 2-50%; also the silane coupling layer has amino group as a functional group, and the deposition amount is 1-20 mg/m<SP>2</SP>as Si amount. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a surface-treated aluminum material excellent in corrosion resistance and a resin-coated aluminum material excellent in adhesion between a resin coating layer coated on the surface. More specifically, the present invention relates to a surface-treated aluminum material that does not contain hexavalent and trivalent chromium in the chemical film component and is suitable for uses such as food containers, home appliances, and building materials. In the present specification, the aluminum material includes not only an industrial pure aluminum material but also various aluminum alloy materials.

  In recent years, aluminum materials have been widely adopted as resin coating materials for food containers, home appliances, and building materials. This is because aluminum is more recyclable than other metal materials and has excellent workability and aesthetics.

  Conventionally, phosphoric acid chromate treatment or chromate chromate treatment has been used as a base treatment for a resin-coated aluminum material. The chromate conversion coating formed by this chromate surface treatment solution has excellent corrosion resistance of the coating alone, and also has excellent characteristics of adhesion and corrosion resistance after various resin coatings are applied. However, in recent years, from the viewpoint of environmental protection, chromium-containing wastewater in chromate treatment leads to environmental pollution, and wastewater treatment also has a disadvantage that requires cost. Furthermore, in food-related applications, it is hexavalent. Due to the harmful effects of chromium on the human body, it has become necessary to eliminate the use of chromate treatment solutions.

  Various studies have been conducted on a treatment solution that does not contain hexavalent chromium, that is, a non-chromate treatment solution. For example, it contains a phosphate ion and a zirconium compound disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 7-48677), has a pH of 2 to 4, and further has an oxidizing agent of 500 ppm or less, and at least one of hydrofluoric acid or fluoride. A surface treatment with a treatment liquid containing 2000 ppm or less as fluorine, and a zirconium compound, a phosphoric acid compound, hydrofluoric acid, hydrogen peroxide, disclosed in Patent Document 2 (Japanese Patent Laid-Open No. 2003-155577), and A method of treating with an acidic aqueous solution containing vanadium ions has been proposed.

  When the treatment is performed using such a non-chromate treatment solution, a chemical conversion film containing zirconium oxide as a main component and further containing aluminum oxide and zirconium phosphate is formed on the aluminum alloy surface.

  However, these treatment methods have the advantage of not containing hexavalent chromium in the treatment liquid, but the film composition is affected by the treatment conditions, and the corrosion resistance and adhesion to the resin coating layer are inferior to the chromate treatment method. Therefore, it has a drawback that it can be used only for limited purposes.

Furthermore, as a surface treatment method for imparting corrosion resistance and adhesion using a water-soluble resin, water-soluble titanium and / or zirconium disclosed in Patent Document 3 (Japanese Patent Laid-Open No. 2003-313676) is disclosed. A composition for surface treatment containing a compound and a tannin substance has been proposed. Although the water-soluble tannin substance contributes to the improvement of the adhesion performance in the treatment method using the surface treatment composition described in the above publication, even when such an organic-inorganic composite film is used, the corrosion resistance is insufficient. Corrosion resistance of parts and scratches is inferior compared to the chromate treatment method. In general, organic polymer substances that contribute to the improvement of adhesion tend to undergo gelation by hydrolysis or dehydration condensation reaction in the treatment liquid, and therefore it is difficult to manage the treatment liquid. Furthermore, when the gelled organic polymer substance is transferred to the plate surface via a roll, it causes a defect in the surface quality, which is not preferable.
JP 7-48677 A Japanese Patent Laid-Open No. 2003-155577 JP 2003-313676 A

  The present invention has been made in view of the above-mentioned problems of the prior art, does not use harmful chromium, is low-cost, and has corrosion resistance and resin coating adhesion equal to or higher than those obtained by phosphoric acid chromate treatment. The object is to provide aluminum or an alloy material thereof.

  As a result of studying the above problems, the present inventor found that in the chemical conversion treatment, aluminum oxide is inevitably formed in the formation process of the chemical conversion film, and the amount of the aluminum oxide is a liquid composition constituting the chemical conversion treatment liquid. It was found that the amount of aluminum oxide present on the outermost surface of the chemical conversion film has an influence on the deterioration of corrosion resistance. And, the chemical resistance layer is improved by suppressing the growth of aluminum oxide by forming a chemical film layer containing a vanadium compound, and a composite in which a silane coupling agent having an amino group as a functional group is applied on this chemical film. It has been found that a surface-treated aluminum material having excellent adhesion to the resin coating layer can be obtained by forming a coating, whereby the chemical conversion coating layer containing vanadium and the silane coupling agent having an amino group are firmly bonded.

  Specifically, the invention according to claim 1 is characterized in that it has a composite film comprising a chemical conversion film containing a zirconium phosphate compound as a main component and containing a vanadium compound, and a silane coupling layer on the chemical conversion film. It is a surface-treated aluminum material.

The invention according to claim 2 is a conversion coating containing a zirconium phosphate compound as a main component and a vanadium compound. The amount of the conversion coating is 3 to 20 mg / m ² as the amount of zirconium, and the mole of zirconium with respect to phosphorus in the conversion coating. 2. The surface-treated aluminum material according to claim 1, wherein the ratio is 0.6 to 1.2, and the molar fraction of vanadium on the outermost surface of the chemical conversion film is 2 to 50%.

The invention according to claim 3 is characterized in that the silane coupling film has an amino group as a functional group and has an adhesion amount of 1 to ²⁰ mg / m ² as an amount of Si. It is a surface-treated aluminum material.

  The invention according to claim 4 is a zirconium phosphate compound obtained by treating an aluminum material with a non-chromium metal surface treatment agent containing a water-soluble fluorozirconium complex compound, a water-soluble phosphate compound, and a water-soluble vanadium compound. The surface-treated aluminum material is produced by applying a silane coupling agent on a chemical conversion film containing a vanadium compound as a main component.

  The invention according to claim 5 is characterized in that the water-soluble vanadium compound is at least one water-soluble vanadium compound selected from the group of inorganic and organic vanadium compounds having an oxidation number of vanadium of 3 to 5. The method for producing a surface-treated aluminum material according to claim 4.

  A sixth aspect of the present invention is a resin-coated aluminum material, wherein the surface of the aluminum material according to the first to third aspects is coated with a synthetic resin film.

  A seventh aspect of the invention is a method for producing a resin-coated aluminum material, wherein the surface of the composite film is coated with a synthetic resin film after the steps of the fourth to fifth aspects.

  In the present invention, the outermost surface refers to an analysis surface that does not exceed 3 nm after the start of measurement in the depth direction in the depth profile of Auger electron spectroscopy analysis.

  By defining the film composition of the chemical conversion film containing a zirconium phosphate compound as a main component and containing a vanadium compound, excellent corrosion resistance can be imparted. Subsequently, adhesiveness with a resin coating layer can be provided by prescribing the functional group and coating amount of the silane coupling agent to be applied as a post-treatment. That is, it is possible to obtain a very good surface-treated aluminum material that could not be obtained by the prior art.

A. Formation of chemical conversion film
Conventionally, when the above-described zirconium phosphate nonchromate treatment is applied to the surface of aluminum or an alloy thereof, the structure of the chemical conversion film is that aluminum fluoride, oxide, oxyhydroxide is formed at the interface between the aluminum substrate and the chemical conversion film. There has been proposed a model in which an aluminum oxide film made of a material exists, and a chemical conversion film made of zirconium phosphate, hydroxide, oxide, and hydrates thereof is formed thereon.

  As a result of detailed investigation of elemental analysis in the depth direction of a chemical conversion treatment film formed by a conventional method, a so-called depth profile, the inventors used an analytical instrument based on Auger electron spectroscopy and secondary ion mass spectrometry. The main component of the oxide film does not have a uniform structure in the depth direction or a layered structure consisting of several substances, but has a so-called gradient structure in which the element concentration continuously changes in the depth direction. It was confirmed.

  That is, in the chemical conversion film formed on the surface of aluminum or its alloy, the aluminum oxide film component increases with the increase in chemical conversion film components (zirconium and phosphorus) in the direction of the surface layer from the aluminum base material, and then aluminum It has a graded structure that decreases after the aluminum oxide film component reaches its maximum value as the base material component decreases, and at the outermost surface of the chemical coating film, the aluminum oxide film component simultaneously with the chemical conversion film component. Existence was confirmed.

  However, the aluminum oxide present in the chemical conversion film surface layer affects the corrosion resistance of the chemical conversion film, and the corrosion resistance deteriorates as the amount of aluminum oxide increases. Therefore, in order to obtain a good chemical conversion film, it is necessary to strictly control the chemical conversion treatment conditions or the concentration of the chemical conversion treatment liquid composition. In the conventional method of treating with zirconium or titanium or a mixture thereof and a treatment solution containing phosphate and fluoride, it has been difficult to obtain a chemical conversion film in which aluminum oxide is suppressed.

  Here, the inventors tend to be affected by such a gradient structure and film composition, and also the aluminum oxide formed on the outermost surface of the chemical conversion film, due to the liquid composition constituting the chemical conversion treatment liquid and the concentration thereof. I found out. In other words, when a chemical conversion treatment is performed by a spray method using a mixed aqueous solution composed of a water-soluble zirconium fluoro complex as a main component and an orthophosphoric acid compound and a fluorine compound, and further a water-soluble vanadium compound, it is formed on the surface of aluminum or an alloy thereof. The chemical reaction at the solid-liquid interface greatly affects the gradient structure and film composition, and the molar ratio of zirconium to phosphorus in the film can be arbitrarily adjusted.

Furthermore, by adding the water-soluble vanadium compound by the treatment liquid composition, it becomes possible to control the molar fraction of the aluminum oxide with respect to the chemical conversion film component on the outermost surface of the chemical conversion film. In the case of the chemical conversion treatment by the zirconium-based treatment, the aluminum oxide grows by forming an insoluble salt together with the anion in the treatment solution by the etching reaction in the formation process of the zirconium-based chemical film. When polyvalent metal ions such as vanadium are present in the treatment liquid, these metal ions are bonded to anions such as PO ₄ and F instead of cations such as zirconium ions, and anions (PO ₄ and F)) and an insoluble salt can be formed, so that the growth of aluminum oxide can be suppressed, and a chemical conversion film having excellent corrosion resistance can be obtained.

B. Post-treatment; Silane coupling agent
After the chemical conversion film is formed, a silane coupling agent is applied as a post-treatment. The silane coupling agent used in the present invention has an amino group as a functional group, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-Aminoethyl) aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, and one or more amino-based silane compounds consisting of derivatives thereof are selected. Since the silane coupling agent selected from these has good adhesion to both the chemical conversion film and the resin coating layer, the above-described amino-based silane coupling agent can be applied as a post-treatment to apply resin coating. A composite film excellent in adhesion to the layer can be formed. Here, the amino silane coupling agent described above is firmly bonded to the chemical conversion film layer containing vanadium according to the present invention. This is because the vanadium ion incorporated in the surface layer of the chemical conversion film has a vacant orbit in the 3d orbit of its electronic structure, and the coordination is between the vacant orbit and the amino group constituting the silane coupling agent. This is because a bond is formed. Therefore, in the composite film according to the present invention, a stronger bond can be obtained as compared with the conventional zirconium-based chemical conversion film not containing vanadium.

C. Resin-coated aluminum material
The resin-coated aluminum material according to the present invention is manufactured by forming a coating film with a resin film on the surface of the surface-treated aluminum material on which the composite film is formed. Any resin film may be used as long as it exhibits thermal adhesiveness to an aluminum substrate, and a resin film having various characteristics can be selected according to various characteristics required for the resin-coated aluminum material. . As an example of such a resin film, a thermoplastic resin film such as polyethylene terephthalate, polyethylene naphthalate, nylon 6, nylon 11, polycarbonate, and polyarylate is preferably used. In order to form a thermoplastic resin film, the aluminum substrate is heated by high-frequency induction heating, direct flame heating, etc., and the thermoplastic resin film is pressed onto the aluminum substrate, or the resin is thermally bonded to the aluminum substrate surface by extrusion coating. Or the like is used. These methods are publicly known and can be appropriately selected according to the purpose and application. In addition, a composite film provided with a silane coupling layer on a chemical conversion film containing a vanadium compound containing a zirconium phosphate compound as a main component is formed on the surface of the aluminum substrate. Since the amino group contained in the film makes a strong adhesion with the thermoplastic resin film, it is not necessary to provide an adhesive primer on the surface of the thermoplastic film or the surface of the aluminum chemical conversion treatment as in the past.

D. Surface treatment aluminum material
The contents of the present invention will be described in detail below. The surface-treated aluminum material of the present invention can be obtained by chemical conversion treatment of aluminum or an alloy thereof and forming a chemical conversion film on the surface. The chemical conversion film is obtained by subjecting the substrate surface to chemical conversion treatment using a non-chromate chemical conversion treatment solution containing a water-soluble fluorozirconium complex compound, a water-soluble phosphate compound, and a water-soluble vanadium compound. Here, as the water-soluble fluorozirconium complex compound, zirconium hydrofluoric acid, zirconium ammonium fluoride, potassium zirconium fluoride or the like is applied. As the water-soluble phosphoric acid compound, an orthophosphoric acid compound, a phosphonic acid compound, a phosphinic acid compound, or a condensed phosphoric acid compound is preferably used. The water-soluble vanadium compound is preferably a trivalent to pentavalent vanadium ion, such as metavanadic acid, orthovanadic acid and sodium salts, potassium salts, ammonium salts thereof, or vanadium sulfate, vanadyl sulfate, vanadium nitrate, vanadium acetate, etc. It is selected from inorganic vanadium compounds and organic vanadium complex compounds such as vanadium acetylacetonate and vanadyl acetylacetonate. Since the trivalent to pentavalent vanadium ion has a vacant orbit in the 3d orbital of its electronic structure, a stronger bond can be obtained between the vacant orbit and the amino group constituting the silane coupling agent. .

The chemical conversion film formed by the non-chromate chemical conversion treatment liquid containing the water-soluble fluorozirconium complex compound, the water-soluble phosphate compound, and the water-soluble vanadium compound is a composite chemical film containing zirconium, phosphorus, and vanadium as described above. The fluorozirconium complex compound and the phosphoric acid compound are a composite layer formed between the vanadium compound deposited on the surface of the base material in the form of an oxide or fluoride and simultaneously deposited. Further, since vanadium forms an insoluble salt with anions (PO ₄ , F, etc.) preferentially over aluminum ions, it is possible to suppress the growth of aluminum oxide. Furthermore, vanadium has a function of repairing a defective portion generated in the chemical conversion film by an oxidation-reduction reaction generated with an aluminum alloy as a base material, thereby contributing to an improvement in corrosion resistance.

In the present invention, the adhesion amount of the chemical conversion film may be 3 to ²⁰ mg / m ² as the amount of zirconium, more preferably in the range of 8 to 16 mg / m ² . If it is less than 3 mg / m ² , since the film thickness of the chemical film layer is thin, the corrosion resistance is not sufficient, and at the same time, problems arise in terms of chemical film performance such as boiling water blackening and boiling water elution. On the other hand, if it exceeds 20 mg / m ² , the chemical conversion film tends to break, and the corrosion resistance is poor.

  Further, the molar ratio of zirconium to phosphorus in the film is preferably 0.6 to 1.2, and if it is less than 0.6, it is inferior in terms of chemical film performance such as boiling water blackening or boiling water elution, and 1.2 or more, This is not preferable because the adhesion with the silane coupling agent applied as a post-treatment is lowered. The amount of zirconium and phosphorus is measured using a fluorescent X-ray analyzer. The mole fraction of the vanadium film component refers to the mole fraction determined from the vanadium strength in Auger electron spectroscopy.

Furthermore, on the outermost surface of the chemical conversion film, the chemical conversion treatment agent is adjusted so that the mole fraction of vanadium resulting from the water-soluble vanadium compound is 2 to 50% with respect to the chemical conversion film. Vanadium present in the treatment agent forms an insoluble salt with anions (such as PO ₄ and F) preferentially over aluminum ions, and therefore suppresses the growth of aluminum oxide, which adversely affects film performance. It becomes possible. If the molar fraction of vanadium is less than 2%, the formation of aluminum oxide cannot be sufficiently suppressed, and the repairing action for the defective portion of the chemical conversion film cannot be obtained, so that satisfactory corrosion resistance cannot be obtained. On the other hand, when the molar fraction of vanadium is 50% or more, the vanadium component inhibits the formation of the zirconium film, which is not preferable. Usually, in order to obtain the mole fraction of vanadium described above, it is preferable to adjust the treatment liquid so that the vanadium metal concentration in the chemical conversion treatment liquid is 25 to 500 ppm.

  In addition, as the chemical conversion treatment method using the chemical conversion treatment liquid, a spray method, a dipping method, and the like can be mentioned. However, in the present invention, the treatment method is not particularly limited. Also, the drying conditions after the chemical conversion treatment are not particularly limited, but considering the application of the silane coupling agent as a post treatment, the chemical conversion treatment plate is dried at a minimum to remove moisture. It is preferable. In general, a drying temperature of 60 to 150 ° C. and a drying time of 2 to 10 seconds are preferable.

The surface-treated aluminum material of the present invention is coated with a silane coupling agent as a post-treatment after the chemical conversion treatment. The kind of silane coupling agent to be used is selected from one or more of the amino silane coupling agents described above. The silane coupling agent can be appropriately diluted with water or a solvent and used. Moreover, as a coating method of a silane coupling agent, generally, a roll coating method, a bar coating method, etc. are mentioned, but the coating method is not particularly limited. The coating amount of the silane coupling agent is such that the adhesion amount of the silane coupling layer after drying is in terms of Si, that is, 1 to 20 mg / m ² as the amount of Si present in the silane coupling layer after drying. To do. By setting it as such application amount, the film | membrane with favorable uniformity is formed. Furthermore, by setting it as such application quantity, even if the unevenness | corrugation exists in the aluminum base-material surface by a rolling mark etc., favorable adhesiveness is exhibited stably. When the Si amount of the silane coupling layer is less than 1 mg / m ² , a silane coupling film that covers the entire surface of the aluminum base material after the acidic cleaning cannot be formed. On the other hand, when the Si amount of the silane coupling layer exceeds 20 mg / m ² , it can be completely covered with the silane coupling film. It will cause a decline. Moreover, as drying conditions after application | coating, 80-250 degreeC, 2 to 10 second, More preferably, 120-180 degreeC and 4 to 8 second are applied. By performing this drying, it becomes possible to accelerate the dehydration condensation reaction of the silane coupling agent, and it is possible to form a composite film having better adhesion.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to the example as described below.

In this example, JIS-A3004 alloy was examined as an aluminum material, and casting / processing and tempering were performed as follows.
A3004 alloy was cast by a DC casting method, homogenized, hot rolled, annealed, and then cold rolled to a thickness of 0.30 mm.

  This alloy plate was degreased at 60 ° C. for 5 seconds with a 2% by mass aqueous solution of Surf Cleaner EC370 manufactured by Nippon Paint Co., Ltd. and washed with water, and then at 60 ° C. with a 3% by mass aqueous solution of Surf Cleaner 420N-2 manufactured by Nippon Paint Co., Ltd. Etching treatment was performed for 10 seconds, washed with water, then smut treatment was performed at 50 ° C. for 3 seconds with a 2% by weight sulfuric acid aqueous solution. After washing with water, chemical conversion treatment was performed at 50 ° C. for 4 seconds. The chemical conversion treatment is carried out using a chemical conversion treatment liquid adjusted to be ammonium hexafluorozirconate; 0.15% by mass, phosphoric acid; 0.15% by mass, sodium vanadate; 0 to 1000 ppm. The alloy plate was chemically treated. As a chemical conversion treatment method, a spray method was adopted, and treatment at 50 ° C. for 4 seconds was performed.

  After the chemical conversion treatment, washing with water and drying were performed, and a bar coating method was adopted as a coating method in which a silane coupling agent was applied as a post-treatment. The details of these processing contents are shown in Table 1.

  After the composite film was formed by the above treatment, a Teijin DuPont PET film having a film thickness of 15 μm was thermocompression bonded at 250 ° C. in order to carry out an adhesion test on the resin film, thereby preparing a laminate coated plate.

In addition, the evaluation method of the chemical conversion treatment board and the resin coating board was as follows.
1) Amount of zirconium and phosphorus The amount of zirconium and phosphorus in the chemical conversion film of the chemical conversion treatment plate was measured by fluorescent X-ray analysis. The molar ratio of zirconium to phosphorus was calculated from the amount of film obtained.

2) Aluminum oxide film component and carbon mole fraction The film composition of the chemical conversion treatment plate was measured by Auger electron spectroscopy. The measurement elements were analyzed for aluminum, aluminum oxide, vanadium, oxygen, phosphorus and zirconium, which are main constituent elements such as a film.
The mole fraction of the aluminum oxide film component and the vanadium film component refers to the mole fraction obtained from the Auger electron intensity and vanadium intensity caused by oxidized aluminum in Auger electron spectroscopy. Note that aluminum atoms in the aluminum oxide film are present in a +3 valence state and have energy levels different from those of metallic aluminum, so that they can be identified and detected.

3) Corrosion resistance Scratches that reach the aluminum base material are put on the resin coating using a cutter, immersed in a mixed solution of 0.5 wt% sodium chloride and 1% citric acid at 70 ° C for 72 hours, and then the corrosion of the scratches or the resin coating The peel width was measured, and the width was evaluated.
Peel width less than 0.3mm ◎
Peel width 0.3mm or more and less than 0.5mm ○
Peel width 0.5mm or more ×

4) Peel adhesion (feathering);
A resin-coated plate was molded into a can lid and subjected to a retort treatment at 125 ° C. for 30 minutes. Thereafter, the film remaining width in the opening after the tab was pulled was measured.
Remaining width less than 0.4mm ◎
Residual width 0.4 mm or more and less than 0.7 mm ○
Remaining width 0.7mm or more ×

  Table 2 shows the composition analysis and adhesion performance evaluation results of the chemical conversion films according to Examples 1 to 9 and Comparative Examples 1 to 7.

  In Examples 1 to 9, the desired composite conversion coating according to the present invention was obtained in terms of the zirconium coating amount, the Zr / P molar ratio, the vanadium mole fraction, and the Si amount, and the resin coating performance was also good. Results were obtained.

  On the other hand, when vanadium is not contained in the chemical conversion treatment liquid shown in Comparative Examples 1 and 2, or when the amount of vanadium added in Comparative Examples 3 to 4 is small, vanadium shown in Comparative Examples 5 to 6 is used. When the amount added was large, the mole fraction of vanadium in the chemical conversion film deviated from the desired range, resulting in poor corrosion resistance. As shown in Comparative Example 2, Comparative Example 4, and Comparative Example 6, when a silane coupling agent species other than amino silane was applied, the adhesion was poor. As shown in Comparative Example 7, when divalent vanadium was used, the corrosion resistance and adhesion were inferior even when amino-based silane was applied.

Claims (7)

  A surface-treated aluminum material comprising a chemical conversion film comprising a zirconium phosphate compound as a main component and containing a vanadium compound, and a composite film comprising a silane coupling layer on the chemical conversion film. In a chemical conversion film containing a zirconium phosphate compound as a main component and containing a vanadium compound, the amount of chemical conversion film deposited is 3 to 20 mg / m ² as the amount of zirconium, and the molar ratio of zirconium to phosphorus in the chemical conversion film is 0.6 to 1. 2. The surface-treated aluminum material according to claim 1, wherein the mole fraction of vanadium on the outermost surface of the chemical conversion film is 2 to 50%. The surface-treated aluminum material according to claim 1 or 2, wherein the silane coupling film has an amino group as a functional group and has an adhesion amount of 1 to ²⁰ mg / m ² as a Si amount.   The aluminum material is treated with a non-chromium metal surface treatment agent containing a water-soluble fluorozirconium complex compound, a water-soluble phosphate compound, and a water-soluble vanadium compound, so that the zirconium phosphate compound is a main component and the vanadium compound is contained. A method for producing a surface-treated aluminum material, wherein a composite film is provided on a chemical conversion film by applying a silane coupling agent.   The surface treatment according to claim 4, wherein the water-soluble vanadium compound is at least one water-soluble vanadium compound selected from the group of inorganic and organic vanadium compounds having vanadium oxidation number of 3 to 5. Manufacturing method of aluminum material.   A resin-coated aluminum material, wherein the surface of the aluminum material according to claim 1 is coated with a synthetic resin film.   A method for producing a resin-coated aluminum material, wherein a synthetic resin film is coated on the surface of the composite film after the step according to claim 4.