JP6721406B2 - Aluminum alloy material, aluminum alloy material with adhesive resin layer, method for producing aluminum alloy material, and method for producing aluminum alloy material with adhesive resin layer - Google Patents

Description

The present invention relates to an aluminum alloy material, an aluminum alloy material with an adhesive resin layer, a method for producing an aluminum alloy material, and a method for producing an aluminum alloy material with an adhesive resin layer.

From the viewpoint of reducing the weight of members used in transportation machines such as automobiles, ships, and aircraft, attention has been focused on the development of technology for joining dissimilar materials such as carbon fiber, aluminum alloy, and steel materials having different strengths, materials, and masses. There is. In particular, an adhesive resin (resin adhesive) has been actively studied in recent years because it does not corrode materials due to electrolytic corrosion and can bond various materials without corroding. However, in a high-humidity environment, water enters the interface between the metal and the adhesive resin, corrosion and deterioration of the metal surface occur, and the metal and the adhesive resin easily peel off at the interface, resulting in a significant decrease in the adhesive strength. .. Therefore, pretreatment that protects the interface between the metal and the adhesive resin from corrosion and does not reduce the adhesive strength even in a wet environment is an important factor that determines the adhesive durability.

Here, as the pretreatment for adhesion, a surface treatment for improving the corrosion resistance of the metal surface and the paint adhesion is known from the viewpoint of corrosion protection.

For example, in Patent Document 1, an adhesive formed on a metal such as aluminum by treating a metal such as aluminum with an aqueous composition containing a tetraalkyl silicate such as tetraethyl orthosilicate and a hydrated oxide sol such as silica sol. And other techniques for improving the initial adhesion and long-term stability of adhesion of the coating film.

Further, in Patent Document 2, after treating a metal substrate with a first treatment solution consisting essentially of at least one kind of multifunctional silane having at least two tri-substituted silyl groups, at least one kind of organo Techniques for improving the corrosion resistance of metals by applying a second coating containing a second treatment solution containing a functional silane are described.

Further, Patent Document 3 describes a method of improving the corrosion resistance of a metal by treating a metal base material with a solution containing aminosilane and polysilyl-functional silane.

In addition, Patent Document 4 describes a method of improving corrosion resistance by rinsing the surface of a galvanized steel sheet with an aqueous solution containing a silicic acid compound and then treating the surface with a silane coupling agent.

Further, in Patent Document 5, a solution containing a silicate ester, an aluminum inorganic salt and polyethylene glycol and further containing a silane coupling agent is applied on a zinc-based plated steel sheet and dried to form a film. Describes a method for improving paint adhesion and white rust resistance.

Further, Patent Document 6 discloses a method for improving coating adhesion by treating the surface of a metal material such as aluminum or an aluminum alloy with an aqueous solution containing water glass such as sodium water glass and silane such as aminosilane. Have been described.

Further, in Patent Document 7, by treating a metal sheet with an alkaline solution containing an inorganic silicate, an organofunctional silane, and a crosslinking agent containing two or more trialkoxysilyl groups, corrosion resistance and paint adhesion are improved. The method is described.

Japanese Patent Publication No. 10-510307 Japanese Patent No. 4376972 Japanese Patent No. 4589364 US Pat. No. 5,108,793 Japanese Patent No. 3289769 Special table 2014-502287 gazette Japanese Patent Publication No. 9-510259

However, in the method described in Patent Document 1, the adhesive strength is remarkably reduced by the long-term wet deterioration test, and therefore the adhesive durability cannot be said to be sufficient.

Further, in the methods described in Patent Document 2 and Patent Document 3, the adhesion durability of the produced silane film is not sufficient, and there is a problem in practicality in the process such as high temperature drying or long-time treatment. ..

Further, the methods described in Patent Documents 4 to 7 are intended only for the purpose of preventing corrosion of the metal surface and improving the adhesiveness of the paint. Therefore, the formed film has a large thickness, but a thick film has a low mechanical strength of the film itself, becomes brittle against tension and stress, and high adhesive strength cannot be obtained.

In addition, the aluminum alloy material after the surface treatment is subjected to oil treatment after the surface treatment for improving workability, and then molded and adhered. Here, when a lubricating oil, a press oil, or a mechanical oil such as a processing oil is contained between the surface treatment film and the adhesive, the adhesiveness of the adhesive is significantly reduced, and high adhesive strength cannot be obtained. There is a demand for the development of an aluminum alloy material that does not deteriorate the adhesion durability even when mechanical oil such as press oil or processing oil adheres to the surface.

In view of the above problems, the present invention, even when exposed to a high temperature wet environment, the adhesive strength is less likely to decrease, aluminum alloy material excellent in adhesion durability, aluminum alloy material with an adhesive resin layer, aluminum alloy A main object of the present invention is to provide a method for manufacturing a material and a method for manufacturing an aluminum alloy material with an adhesive resin layer.

In order to solve the above-mentioned subject, the present inventor has conducted an earnest experiment and, as a result, the amount of Mg, the amount of Si and the amount of Cu are within a specific range on the surface of the aluminum substrate, and in the FT-IR spectrum. It has been found that excellent adhesion durability can be obtained by forming a film made of an oxide of aluminum containing silicon having specific absorption, and further forming a film containing a polymer of a specific silane compound. Invented.

That is, the present invention is an aluminum alloy base material, a first coating formed on at least a part of the surface of the aluminum alloy base material, the oxide comprising aluminum containing silicon, and at least a part of the first coating. An aluminum alloy material comprising a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a second coating containing the hydrolyzate or a polymer thereof, the first coating Has two absorption bands in the wave number range of 1000 to 1300 cm ⁻¹ in the difference spectrum before and after the film treatment obtained by injecting parallel polarized light with an incident angle of 75° by Fourier transform infrared spectroscopy. One absorption band is in the range of wave numbers of 1080 to 1140 cm ⁻¹ and wave numbers of 1180 to 1240 cm ⁻¹ , and the first coating contains 15 atomic% or more and less than 70 atomic% of Si and 0.1 atomic% or more of 30 Mg. Provided is an aluminum alloy material containing less than atomic% and Cu regulated to less than 0.6 atomic %.

Here, the amount of Si, the amount of Mg, and the amount of Cu in a 1st film|membrane are the values measured by the high frequency glow discharge optical emission spectroscopy (GD-OES:Glow Discharge-Optical Emission Spectroscopy).

In the aluminum alloy material of the present invention, it is preferable that the film does not substantially contain a particulate inorganic compound having a diameter of 1 nm or more.

In the aluminum alloy material of the present invention, the amount of Si in the first coating is preferably 20 atomic% or more and less than 65 atomic %, and more preferably 30 atomic% or more and less than 60 atomic %.

In the aluminum alloy material of the present invention, the second coating may further contain a silane coupling agent having a reactive functional group capable of chemically bonding with the organic resin component, its hydrolyzate, or its polymer.

In the aluminum alloy material of the present invention, it is preferable that coating amount of the second coating is a 0.01 to 30 mg / ^{m 2,} more preferably from 0.2 to 20 / ^{m 2,} 0.5 to 10 mg More preferably, it is /m ² .

In the aluminum alloy material of the present invention, the aluminum alloy base material is made of an Al-Mg alloy, an Al-Cu-Mg alloy, an Al-Mg-Si alloy or an Al-Zn-Mg alloy. Good.

The present invention also provides an aluminum alloy material with an adhesive resin layer, in which an adhesive resin layer is formed on the second coating of the aluminum alloy material described above.

In the aluminum alloy material of the present invention, the adhesive resin layer may contain at least one selected from an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, and an acrylic resin.

Further, the present invention provides a first film forming step of forming a first film made of an oxide of aluminum containing silicon on at least a part of the surface of an aluminum alloy base material, and a molecule on at least a part of the first film. A silane compound having two or more hydrolyzable trialkoxysilyl groups therein, a second film forming step of forming a second film containing a hydrolyzate thereof or a polymer thereof, wherein the first film forming step comprises A heat treatment step of forming an oxide film on the surface of the aluminum alloy substrate, and an etching treatment step and a silicate treatment step after the heat treatment step, the silicate treatment step being after the etching treatment step or the etching. At the same time as the treatment step, and as the silicate treatment step, the oxide film is treated with a first aqueous solution containing 0.005% by mass to 2% by mass of tetraalkyl silicate or an oligomer thereof, and in the second film forming step, A method for producing an aluminum alloy material, comprising treating the first coating with a second aqueous solution containing a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof. Also provide.

In the method for producing an aluminum alloy material of the present invention, it is preferable to control the etching amount in the etching treatment stage to less than 700 nm.

In the method for producing an aluminum alloy material of the present invention, in the first film forming step, the silicate treatment step is after the etching treatment step, and at least one of acid treatment and alkaline solution treatment is performed as the etching treatment step. May be.

In the method for manufacturing an aluminum alloy material of the present invention, the silicate treatment step may be the same as the etching treatment step in the first film forming step.

Furthermore, the present invention comprises an aluminum alloy material with an adhesive resin layer, which comprises an adhesive resin layer forming step of forming an adhesive resin layer on the second coating of the aluminum alloy material produced by the method for producing an aluminum alloy material described above. A method of manufacturing the same is also provided.

According to the present invention, it is possible to realize an aluminum alloy material in which the adhesive strength does not easily decrease even when exposed to a high temperature and humid environment, and which has excellent adhesive durability.

FIG. 1 is a cross-sectional view schematically showing the configuration of the aluminum alloy material according to the first embodiment of the present invention. FIG. 2 is a flowchart showing a method for manufacturing the aluminum alloy material shown in FIG. FIG. 3 is a sectional view schematically showing a configuration of an aluminum alloy material with an adhesive resin layer according to a modified example of the first embodiment of the present invention. FIG. 4 is a flowchart showing a method for manufacturing the aluminum alloy material with the adhesive resin layer shown in FIG. FIG. 5: is sectional drawing which shows typically the structural example of the joined body which concerns on the 2nd Embodiment of this invention. FIG. 6A is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention. FIG. 6B is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention. FIG. 7: is sectional drawing which shows typically the other structural example of the joined body which concerns on the 2nd Embodiment of this invention. FIG. 8A is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention. FIG. 8B is a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present invention. FIG. 9A is a side view schematically showing the method for measuring the cohesive failure rate. FIG. 9B is a plan view schematically showing the method for measuring the cohesive failure rate.

Hereinafter, modes for carrying out the present invention will be described in detail. The present invention is not limited to the embodiments described below.

(First embodiment)
First, the aluminum alloy material according to the first embodiment of the present invention will be described.
The aluminum alloy material according to the present embodiment includes an aluminum alloy base material, a first coating formed on at least a part of the surface of the aluminum alloy base material, and made of an oxide of aluminum containing silicon, and the first coating. An aluminum alloy material having a second coating formed on at least a part of the silane compound having two or more trialkoxysilyl groups in the molecule, a hydrolyzate thereof or a polymer thereof, the first coating Has two absorption bands in the wave number range of 1000 to 1300 cm ⁻¹ in the difference spectrum before and after the film treatment obtained by injecting parallel polarized light with an incident angle of 75° by Fourier transform infrared spectroscopy. One absorption band is in the range of wave numbers of 1080 to 1140 cm ⁻¹ and wave numbers of 1180 to 1240 cm ⁻¹ , and the first coating contains 15 atomic% or more and less than 70 atomic% of Si and 0.1 atomic% or more of 30 Mg. It is an aluminum alloy material containing less than atomic% and Cu regulated to less than 0.6 atomic %.

FIG. 1 is a cross-sectional view schematically showing the structure of the aluminum alloy material of this embodiment. As shown in FIG. 1, the aluminum alloy material 10 of the present embodiment is a first coating made of an aluminum oxide containing silicon on at least a part of the surface of an aluminum alloy base material 3 (hereinafter, also referred to as base material 3). 1 (hereinafter, also referred to as film 1) is formed, and at least a part of the first film 1 contains a silane compound having two or more trialkoxysilyl groups in the molecule, its hydrolyzate or its polymer. A second film 2 (hereinafter, also referred to as film 2) is formed.

[Base material 3]
The base material 3 is made of an aluminum alloy. The type of aluminum alloy forming the base material 3 is not particularly limited, and various non-heat-treatment type or heat-treatment type aluminum specified in JIS or similar to JIS are used depending on the use of the member to be processed. The alloy can be appropriately selected and used. Here, as the non-heat treatment type aluminum alloy, there are pure aluminum (1000 series), Al-Mn series alloy (3000 series), Al-Si series alloy (4000 series) and Al-Mg series alloy (5000 series). Further, as the heat treatment type aluminum alloy, there are Al—Cu—Mg based alloys (2000 series), Al—Mg—Si based alloys (6000 series) and Al—Zn—Mg based alloys (7000 series).

For example, when the aluminum alloy material 10 of the present embodiment is used as a member for automobiles, the 0.2% proof stress of the base material 3 is preferably 100 MPa or more from the viewpoint of strength. Aluminum alloys capable of forming a base material satisfying such characteristics include those containing a relatively large amount of magnesium, such as 2000 series, 5000 series, 6000 series and 7000 series, and these alloys are necessary. It may be tempered according to. In addition, among various aluminum alloys, it is preferable to use the 6000 series aluminum alloy because it has excellent age hardening ability, a relatively small amount of alloying elements, and excellent scrap recyclability and formability.

[First coating 1]
The first coating 1 (hereinafter, also referred to as coating 1) is a coating formed on at least a part of the surface of the base material 3 and made of an oxide of aluminum containing silicon. In the aluminum alloy material 10 of the present embodiment, the film 1 has a wave number of 1000 in the difference spectrum before and after the film treatment, which is obtained by injecting parallel polarized light with an incident angle of 75° by Fourier transform infrared spectroscopy (FT-IR). Has two absorption bands in the range of ˜1300 cm ^−1, the two absorption bands are in the range of wave numbers of 1080 to 1140 cm ⁻¹ and 1180 to 1240 cm ⁻¹ , and the film 1 contains 15 atomic% of Si. The above content is less than 70 atomic% and the content of Mg is 0.1 atomic% or more and less than 30 atomic %, and Cu is regulated to less than 0.6 atomic %. The film 1 is a film that is denser and has a higher corrosion resistance than an ordinary aluminum oxide film, and is provided to increase the bonding strength with an adhesive and to improve the adhesion durability. Hereinafter, the suitable range of the amount of each component contained in the film 1 will be described. In the aluminum alloy material shown in FIG. 1, the coating 1 is formed on the entire one surface of the base material 3, but the present embodiment is not limited to this. For example, the film 1 may be formed only on a part of the surface of the base material 3. Further, the coating film 1 may be formed on both surfaces of the base material 3.

<FT-IR spectrum>
The thin film derived from tetraalkyl silicate or its oligomer has two different absorption bands derived from asymmetric stretching vibration of Si—O—Si bond in the wave number range of 1000 to 1300 cm ⁻¹ , and these two absorption bands are , Respectively in the range of 1,080 to 1140 cm ⁻¹ and 1,180 to 1240 cm ⁻¹ . However, in these two absorption bands, the peaks are averaged as the film becomes thicker, resulting in a single broad peak. Here, if the film becomes thick, it becomes a brittle film having low mechanical strength, and it becomes impossible to obtain high adhesion durability. Therefore, it is important to have two different absorption bands in the relevant area in order to determine whether or not the film is a suitable film having excellent adhesion durability. In the aluminum alloy material 10 of the present embodiment, the film 1 is in the difference spectrum before and after coating treatment with FT-IR, range of wave numbers 1080～1140Cm ^-1 and a wavenumber 1180～1240Cm ^-1 derived from tetraalkyl silicate or its oligomer Since it has two absorption bands and the film is sufficiently thin, it has high adhesion durability. In the present specification, “having an absorption band in a certain wave number range” means having a maximum absorption wavelength in the wave number range. The shape of the absorption band may have an inflection point, and may have a peak or a shoulder.

The film having the above-mentioned two absorption bands in the difference spectrum before and after the film treatment by FT-IR is formed, for example, by subjecting an oxide film formed on an aluminum alloy substrate to a silicate treatment described later. You can Here, in the present specification, the silicate treatment means a treatment using a tetraalkyl silicate or an oligomer thereof. When an oxide film on an aluminum alloy substrate is silicate-treated with tetraalkyl silicate or an oligomer thereof and the film after the treatment is thin, two absorption bands appear in the difference spectrum before and after the film treatment by FT-IR. It has an absorption band in the range of the wave number 1080 to 1140 cm ⁻¹ and the wave number 1180 to 1240 cm ⁻¹ .
The difference spectrum before and after the film treatment means the absorption spectrum of the surface of the aluminum alloy material on which the first film is formed, on which the first film is formed, and the aluminum alloy base material on which the first film is not formed. Is the difference between the absorption spectrum of

In the present embodiment, when the film 1 contains a particulate inorganic compound having a diameter of 1 nm or more (hereinafter, also simply referred to as “particulate inorganic compound”), the film becomes thick and the adhesive strength and the adhesive durability may decrease. There is. Therefore, it is preferable that the film 1 does not substantially contain the particulate inorganic compound. In addition, "the coating film does not substantially include the particulate inorganic compound" is not limited to an embodiment that does not include the particulate inorganic compound at all, and it is allowed to contain the particulate inorganic compound at an impurity level. It Specifically, it is permissible that the particulate inorganic compound is contained up to 5% by mass or less with respect to the entire film 1. Examples of the particulate inorganic compound include sols of inorganic oxides such as silica and alumina. The diameter of the particulate inorganic compound represents the diameter of the solid content after the treatment liquid is dried, which is observed by a transmission electron microscope (TEM) or the diluted treatment liquid is measured by an in-liquid particle counter.

<Mg content: 0.1 atom% or more and less than 30 atom%>
The aluminum alloy constituting the base material of the aluminum alloy material usually contains magnesium (Mg) as an alloy component, and an oxide film which is a composite oxide of aluminum and magnesium is formed on the surface of the base material 3. When formed, magnesium will be present on the surface in a concentrated state. Therefore, when the adhesive resin is formed on the oxide film, the magnesium on the surface becomes a weak boundary layer at the adhesive interface, and the initial bonding strength is reduced.

Further, in a high temperature and humid environment where water, oxygen, etc. permeate, it causes hydration at the interface with the adhesive resin and corrosion of the base material, and reduces the bonding strength of the aluminum alloy material. Specifically, when the Mg content in the coating is 30 atomic% or more, the bonding strength of the aluminum alloy material tends to decrease. Therefore, in the aluminum alloy material 10 of the present embodiment, the Mg content in the film 1 is restricted to less than 30 atomic %. Thereby, the adhesion durability can be improved. From the viewpoint of improving the adhesion durability, the Mg content of the coating film 1 is preferably less than 25 atom %, more preferably less than 20 atom %, and even more preferably less than 10 atom %.

On the other hand, the lower limit of the Mg content of the film 1 is 0.1 atom% or more from the viewpoint of economy. The Mg content in the film 1 referred to here can be measured by high frequency glow discharge optical emission spectroscopy (GD-OES).

The method of adjusting the Mg content of the coating film 1 is not particularly limited, but examples thereof include acidic solutions of acids such as nitric acid, sulfuric acid and hydrofluoric acid or mixed acids, or potassium hydroxide, sodium hydroxide and silicic acid. A method of surface-treating with an alkaline solution containing salts and carbonates can be applied. This method adjusts the Mg content of the film 1 by dissolving magnesium in an acid or alkaline solution. By adjusting the treatment time, temperature, concentration and pH of the surface treatment solution, the film 1 The amount of Mg can be in the above range. Even if Mg is contained to the extent of the impurity element, Mg may be concentrated in the film 1 when heat treatment at a high temperature is performed, and adjustment by surface treatment with acid or alkali may occur. Are required as appropriate. It is also possible to adjust the surface treatment chemicals by including Mg ions therein.

<Si content: 15 atomic% or more and less than 70 atomic%>
Silicon has the effect of improving the corrosion resistance of the film 1 and stabilizing it in a wet environment, and further has the effect of improving the adhesion to the second film (film 2) described later. Therefore, by including silicon in the film 1, it becomes possible to enhance the adhesion durability.

However, when the Si content in the coating film 1 is less than 15 atomic %, the above-mentioned effect tends to be small, and when the Si content is 70 atomic% or more, spot weldability and uniformity of chemical conversion treatment may be poor. It tends to decrease. Therefore, in the aluminum alloy material 10 of the present embodiment, the Si content in the film 1 is set to 15 atom% or more and less than 70 atom %.

From the viewpoint of improving the adhesion durability, the Si content in the film 1 is preferably 20 atomic% or more, and more preferably 30 atomic% or more. Further, from the viewpoint of spot weldability and uniformity of chemical conversion treatment, the Si content in the film 1 is preferably less than 65 atom %, more preferably less than 60 atom %.

The Si content in the coating film 1 is adjusted, for example, by performing a surface treatment with an acid or an alkali, similar to the method described as the method for adjusting the Mg amount. Further, it is adjusted depending on the conditions of the treatment with the silicate aqueous solution, which will be described later.

<Cu content: less than 0.6 atom%>
When the base material 3 is excessively etched by a degreasing process or a pickling process when forming the film 1, Cu contained in the base material 3 is concentrated on the surface and the Cu content of the film 1 is increased. .. The presence of Cu on the surface of the coating 1 reduces the adhesion with the coating 2.

Therefore, in the aluminum alloy material of the present embodiment, the Cu content in the film 1 is restricted to less than 0.6 atom %. In addition, the amount of Cu in the film 1 is preferably less than 0.5 atom% from the viewpoint of improving the adhesion to the film 2.

In order to control the Cu content in the film 1, it is necessary to adjust the etching amount by the pretreatment, but the etching method is not limited, and for example, the same treatment method as described in the numerical limitation of Mg. Can be applied. That is, for example, etching can be performed by treatment with an acid or alkali solution.

Here, the element concentrations such as the amount of Mg, the amount of Si, and the amount of Cu in the film 1 can be measured by, for example, a high-frequency glow discharge optical emission spectroscopy (GD-OES: Glow Discharge-Optical Emission Spectroscopy). In the present embodiment, each element except oxygen (O), nitrogen (N) and carbon (C), specifically aluminum (Al), magnesium ( Mg), copper (Cu), metal elements such as iron (Fe) and titanium (Ti), and elements such as silicon (Si) were measured, and the content of Mg, Si, Cu, etc. was calculated as a percentage from the results. The value is the amount of each element.

<Film thickness>
The film thickness of the film 1 is preferably 1 to 30 nm. When the film thickness of the coating film 1 is less than 1 nm, the rust preventive oil used for producing the base material 3 and the ester in the press oil used for producing a joined body or an automobile member from the aluminum alloy material 10 Adsorption of components is suppressed. Therefore, the degreasing property, the chemical conversion treatment property, and the adhesion durability of the aluminum alloy material 10 can be secured without providing the film 1. However, in order to control the film thickness of the film 1 to be less than 1 nm, excessive acid cleaning or the like is required, so that productivity is deteriorated and practicability is likely to be lowered. In addition, alkali degreasing and excessive etching by acid cause the Cu contained in the base material 3 to be concentrated on the surface, which causes a decrease in adhesion durability.

On the other hand, when the film thickness of the film 1 exceeds 30 nm, the amount of the film becomes excessive and the surface is likely to have irregularities. When the surface of the coating film 1 has irregularities, for example, in automobile applications, chemical conversion spots are likely to occur during the chemical conversion treatment performed before the coating step, resulting in deterioration of chemical conversion properties. The film thickness of the film 1 is more preferably 2 nm or more and less than 20 nm from the viewpoint of chemical conversion and productivity.

The coating amount after drying is preferably adjusted to 0.2 mg/m ² or more and 20 mg/m ² or less. Further, the amount of the film after drying is adjusted to more preferably 1 mg/m ² or more and 15 mg/m ² or less, and further preferably 2 mg/m ² or more and 10 mg/m ² or less. If the coating amount of the aqueous silicate solution is too small, the amount of the tetraalkyl silicate or its oligomer may be too small, and good adhesion durability may not be obtained. Further, if the coating amount of the silicate aqueous solution becomes too large, the formed film becomes too thick and peeling occurs in the film, which may impair the adhesion durability.

[Second coating 2]
The second coating 2 (hereinafter, also referred to as coating 2) contains a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, its hydrolyzate or its polymer as a main component. A silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule not only forms a dense siloxane bond by self-polymerization but also forms a chemically stable bond with high reactivity with a metal oxide. Therefore, the wet durability of the film 1 can be further enhanced. Further, the film containing the silane compound, a hydrolyzate thereof or a polymer thereof has high mutual solubility with an organic compound such as a mechanical oil or an adhesive, and even if the mechanical oil adheres to the film, its influence can be mitigated. Therefore, it also plays a role of preventing the deterioration of the adhesion durability due to oiling. The type of the silane compound is not particularly limited, but from the viewpoint of economy, a silane compound (bissilane compound) having two hydrolyzable trialkoxysilyl groups in the molecule is preferable, and for example, bistrialkoxysilylethane or bistrialkoxy. Silylbenzene, bistrialkoxysilylhexane, bistrialkoxysilylpropylamine, bistrialkoxysilylpropyl tetrasulfide and the like can be used. Above all, bistriethoxysilylethane (BTSE) is preferable from the viewpoint of versatility and economy. Here, as the silane compound, the hydrolyzate thereof, or the polymer thereof, only one kind may be used alone, or two or more kinds may be used in combination.

The amount of the silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, its hydrolyzate or its polymer in the film 2 is preferably 0.01% by mass or more, and 0.2% by mass. % Or more, and more preferably 0.5% by mass or more. The upper limit is also not particularly limited, but may be 100% by mass, for example.

In addition to the silane compound, its hydrolyzate or its polymer, the film 2 further contains a silane coupling agent having a reactive functional group capable of chemically bonding with an organic resin component, its hydrolyzate or its polymer. You can leave. Examples of the silane coupling agent include silane coupling agents having a reactive functional group such as an amino group, an epoxy group, a methacryl group, a vinyl group or a mercapto group. By using the silane coupling agent, its hydrolyzate or its polymer together with the silane compound, its hydrolyzate or its polymer, a chemical bond is formed between the film 2 and the resin, and the adhesion durability is improved. It can be further increased. The functional groups of the silane coupling agent are not limited to those described above, and silane coupling agents having various functional groups can be appropriately selected and used according to the adhesive resin used. Preferable specific examples of the silane coupling agent include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-aminoethyl)-aminopropyltrimethoxysilane, and 3-(N- Aminoethyl)-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxy Examples thereof include propyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. Here, as the silane coupling agent, one type may be used alone, or two or more types may be used in combination.

However, if the coating amount of the coating film 2 is too thin, it is likely to be affected by the element on the surface of the base material 3. On the other hand, if the coating amount of the coating film 2 is too large, the coating film 2 itself undergoes cohesive failure, resulting in adhesive durability May decrease. Therefore, from the viewpoint of improving the adhesion durability, it is preferable that the coating amount of the coating 2 after drying is 0.01 mg/m ² or more and less than 30 mg/m ² . The amount of the coating film 2 after drying is more preferably 0.2 mg/m ² or more and less than 20 mg/m ^2, and even more preferably 0.5 mg/m ² or more and less than 10 mg/m ² .

[Production method]
Next, a method for manufacturing the aluminum alloy material of this embodiment will be described. FIG. 2 is a flowchart showing the method for manufacturing the aluminum alloy material 10 of this embodiment shown in FIG. As shown in FIG. 2, when manufacturing the aluminum alloy material 10 of the present embodiment, a base material manufacturing step S1, a first film forming step S2, and a second film forming step S3 are performed. Hereinafter, each step will be described.

<Step S1: Substrate manufacturing process>
The shape of the base material is not particularly limited, and depending on the shape of the member produced using the aluminum alloy material, etc., in addition to a plate shape, a cast material, a forged material, an extruded material (for example, a hollow rod shape), etc. It may have any shape that can be taken as. In the base material manufacturing step S1, for example, when a plate-shaped base material (substrate) is manufactured, the substrate is manufactured in the following procedure, for example. First, an aluminum alloy having a predetermined composition is melted by continuous casting and cast to produce an ingot (melt casting step). Next, the produced ingot is subjected to homogenizing heat treatment (homogenizing heat treatment step). Then, the homogenized heat-treated ingot is hot-rolled to produce a hot-rolled sheet (hot-rolling step). Then, this hot-rolled sheet is subjected to rough annealing or intermediate annealing at 300 to 580° C., and subjected to cold rolling at a final cold rolling rate of 5% or more at least once to obtain a cold-rolled sheet (substrate) having a predetermined sheet thickness. (Cold rolling step).

In the cold rolling step, it is preferable that the temperature of the rough annealing or the intermediate annealing is 300° C. or higher, and thereby the effect of improving the formability is more exerted. Further, the temperature of the rough annealing or the intermediate annealing is preferably set to 580° C. or lower, which facilitates suppressing the deterioration of the formability due to the occurrence of burning. On the other hand, the final cold rolling rate is preferably 5% or more, whereby the effect of improving the formability is more exerted. The conditions for the homogenizing heat treatment and hot rolling are not particularly limited, and the conditions for obtaining a hot rolled sheet can be used. Moreover, the intermediate annealing may not be performed.

<Step S2: First film forming step>
In the first film forming step (step S2), the film 1 is formed on at least a part (that is, a part or all) of the surface of the base material 3 manufactured in the base material manufacturing step of step S1. In the present embodiment, specifically, the first film forming step (step S2) includes, for example, a heat treatment step of heat treating the base material 3 to form an oxide film on the surface of the base material 3, and the heat treatment step. The subsequent etching and silicate treatment steps are provided. Here, as the silicate treatment step, treatment is performed with an aqueous solution containing tetraalkyl silicate or an oligomer thereof. Thereby, the film 1 is formed so that the amount of Mg, the amount of Si, and the amount of Cu in the film are in a specific range and have a specific absorption in the FT-IR spectrum.

In the heat treatment in the heat treatment stage, the base material 3 is heated to, for example, 400 to 580° C. to form an oxide film on the surface of the base material 3. The heat treatment also has the effect of adjusting the strength of the aluminum alloy material 10. The heat treatment performed here is a solution treatment when the base material 3 is formed of a heat treatment type aluminum alloy, and an annealing is performed when the base material 3 is formed of a non-heat treatment type aluminum alloy. It is a heat treatment in (final annealing).

From the viewpoint of improving strength, this heat treatment is preferably rapid heating at a heating rate of 100° C./minute or more. Further, by setting the heating temperature to 400° C. or higher and performing rapid heating, the strength of the aluminum alloy material 10 and the strength of the aluminum alloy material 10 after heating (baking) after coating can be further increased. On the other hand, by setting the heating temperature to 580° C. or less and performing rapid heating, it is possible to suppress deterioration of formability due to occurrence of burning. Further, from the viewpoint of improving the strength, the holding time in the heat treatment is preferably 3 to 30 seconds. Thus, when the base material 3 is heated at a heating temperature of 400 to 580° C., an oxide film having a film thickness of 1 to 30 nm is formed on the surface of the base material 3, for example. Before the heat treatment, alkali degreasing or the like may be performed if necessary.

In the etching step after the heat treatment, a part or all of the surface of the oxide film formed on the base material 3 is treated with an acid solution (pickling) and an alkali solution (alkali washing, alkali degreasing). At least one of The chemical solution (acid detergent) used for pickling is not particularly limited, but for example, a solution containing at least one selected from the group selected from sulfuric acid, nitric acid, and hydrofluoric acid can be used. Further, the acid detergent may contain a surfactant in order to enhance the degreasing property. The conditions of pickling can be appropriately set in consideration of the alloy composition of the base material 3, the thickness of the oxide film, and the like, and are not particularly limited, but for example, the pH is 2 or less, the treatment temperature is 10 to 80°C, The processing time of 1 to 120 seconds can be applied.

Further, the chemical solution used in the alkali cleaning (alkali degreasing) is not particularly limited, but for example, a solution containing at least one selected from the group selected from sodium hydroxide and potassium hydroxide can be used. .. The condition of the treatment with the alkaline solution can be appropriately set in consideration of the alloy composition of the base material 3, the thickness of the oxide film, and the like, and is not particularly limited, but for example, the pH is 10 or more, the treatment temperature is 10 to 80. The conditions of the temperature and the processing time of 1 to 120 seconds can be applied.

In the case of carrying out the alkali cleaning, it is preferable to carry out the pickling after the alkali cleaning. The reason for this is as follows. That is, it is difficult to remove Mg on the surface of the base material by alkali cleaning, and it is necessary to increase the etching amount due to the presence of Mg on the surface of the base material. However, this is because it is necessary to remove Mg by pickling, because an increase in the amount of etching causes a concentration of Cu.

Further, it is preferable to perform rinsing after cleaning with each chemical. The rinsing method is not particularly limited, and examples thereof include spraying and dipping. Examples of the cleaning liquid used for rinsing include industrial water, pure water, ion-exchanged water and the like.

Excessive etching of an aluminum alloy containing copper causes concentration of copper on the surface and causes deterioration of the adhesive resin in a high temperature wet environment which is a deterioration environment. Therefore, the treatment conditions are adjusted so that the etching amount of the oxide film is preferably less than 700 nm, more preferably less than 500 nm.

Here, the etching amount in the etching treatment stage in the specification of the present application is the amount of dissolution of the oxide film or the base material including the oxide film, and the amount of weight loss before and after the etching treatment is measured to obtain the thickness (film thickness). ) Can be estimated as For the sake of convenience, the conversion of the weight reduction amount into the film thickness shall be performed by calculating the aluminum thickness using the aluminum density: 2.7 g/cm ³ . In addition to the oxide film, when a part of the base material under the oxide film is also etched, the total etching amount of the oxide film and the base material is the above-mentioned etching amount.

In addition, in the silicate treatment step, the substrate having an oxide film is treated with an aqueous solution containing tetraalkyl silicate or an oligomer thereof (hereinafter, also referred to as a silicate aqueous solution or a first aqueous solution). Here, the treatment with the silicate aqueous solution includes application of the silicate aqueous solution, dipping in the silicate aqueous solution, and the like. When the treatment with the silicate aqueous solution is performed, the aluminum oxide film becomes dense and has excellent corrosion resistance, the strength of the film itself is improved, and the corrosion resistance is also improved. The silicate treatment step is performed as the final step of substantially forming a film in the film forming step, and pickling is not performed after the treatment with the silicate aqueous solution. However, when washing and/or drying is performed after the treatment with the aqueous silicate solution, the washing and/or drying is also included in the silicate treatment step, and the order thereof does not matter.

The concentration of the tetraalkyl silicate or its oligomer in the aqueous silicate solution applied to the oxide film is preferably 0.005 mass% or more and 2 mass% or less. When the concentration of the tetraalkyl silicate or its oligomer in the silicate aqueous solution is 0.005 mass% or more, the film becomes dense and a film excellent in strength and corrosion resistance can be formed. From the same viewpoint, the concentration of the tetraalkyl silicate or oligomer in the aqueous silicate solution is more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more. On the other hand, if the concentration of the tetraalkyl silicate or its oligomer in the silicate aqueous solution is excessively high, the film may become too thick and the adhesion durability may be significantly reduced. Therefore, from the viewpoint of preventing this, the concentration of silicate in the aqueous silicate solution is preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.8% by mass or less.

When preparing the silicate aqueous solution, it is preferable to first add a predetermined amount of tetraalkyl silicate to ethanol and then dilute it with water to a predetermined concentration. By doing so, it becomes easy to prepare a uniform aqueous solution. The amount of ethanol is preferably 5 to 20 vol% with respect to water.

Further, since tetraalkyl silicate is excessively polymerized under basic conditions, it is necessary to adjust the pH of the silicate aqueous solution to a neutral to acidic range from the viewpoint of stability. Therefore, the pH of the aqueous silicate solution is 7 or less, preferably 6.5 or less, and more preferably 6 or less. On the other hand, the lower limit of the pH of the aqueous silicate solution is not particularly limited, but is, for example, 1 or more. The pH adjuster is not particularly limited, and hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, or carboxylic acid such as acetic acid can be used. However, in consideration of volatility and corrosiveness of the base material, acetic acid is desirable.

The tetraalkyl silicate or its oligomer contained in the aqueous silicate solution is preferably a tetraalkyl silicate or its oligomer that does not produce by-products that may cause corrosion of the film or deterioration of the adhesive resin after the reaction. From this viewpoint, for example, tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropyl orthosilicate or the like, or an oligomer thereof is preferable, and among them, from the viewpoint of economy and safety, tetraethyl orthosilicate or an oligomer thereof is preferable. Here, as the tetraalkyl silicate or the oligomer thereof, only one kind may be used alone, or two or more kinds may be used in combination.

Further, it is preferable that the silicate aqueous solution does not substantially contain a particulate inorganic compound having a diameter of 1 nm or more (particulate inorganic compound). Here, examples of the particulate inorganic compound include sol of inorganic oxide such as silica and alumina. A particulate inorganic compound such as silica is generally used for densification of a tetraalkyl silicate film and for uniforming the film thickness, but the resulting film becomes thick. On the other hand, since a thin film is formed in the present invention, it is not desirable to use silica sol or the like which exerts such an effect. The phrase "the silicate aqueous solution does not substantially contain the particulate inorganic compound" is not limited to an embodiment in which the particulate inorganic compound is not contained at all, and it is acceptable that the particulate inorganic compound is contained at the impurity level. To be done. Specifically, it is permissible for the silicate aqueous solution to contain a particulate inorganic compound up to 0.05% by mass or less.

In addition to the tetraalkyl silicate or its oligomer, the aqueous silicate solution may further contain one or more stabilizers, auxiliary agents, etc., if desired. For example, as the stabilizer, a carboxylic acid having 1 to 4 carbon atoms such as formic acid and acetic acid, an organic compound such as alcohol having 1 to 4 carbon atoms such as methanol and ethanol, and the like may be contained.

Examples of the application method of the silicate aqueous solution include dipping treatment, spraying, roll coating, bar coating and the like.

Further, after treating the oxide film with the silicate aqueous solution, washing (rinsing) may be carried out if necessary.

After the treatment with the silicate aqueous solution, the silicate aqueous solution is dried. The drying temperature is preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher. Further, if the drying temperature is too high, the characteristics of the aluminum alloy are affected, so that the drying temperature is preferably 220° C. or lower, more preferably 200° C. or lower, and further preferably 190° C. or lower. The drying time depends on the drying temperature, but is preferably 2 seconds or more, more preferably 5 seconds or more, and further preferably 10 seconds or more. The drying time is preferably 20 minutes or less, more preferably 5 minutes or less, and further preferably 2 minutes or less.

The coating amount of the silicate solution is to form a film having a FT-IR spectrum as described above, from the viewpoint of obtaining a satisfactory improvement in adhesion durability, coating amount after drying 0.1 mg / ^{m 2} or more 20 mg / ^{m 2} It is preferable to make adjustments as follows. Further, the amount of the film after drying is adjusted to more preferably 1 mg/m ² or more and 15 mg/m ² or less, and further preferably 2 mg/m ² or more and 10 mg/m ² or less. If the coating amount of the aqueous silicate solution is too small, the amount of the tetraalkyl silicate or its oligomer may be too small, and good adhesion durability may not be obtained. Further, if the coating amount of the silicate aqueous solution becomes too large, the formed film becomes too thick and peeling occurs in the film, which may impair the adhesion durability.

Although the silicate treatment step is performed after the etching step in the film forming step of step S1 described above, these steps may be performed once. Specifically, for example, the oxide film may be treated with a neutral or acidic aqueous solution containing tetraalkyl silicate or an oligomer thereof.

<Step S3: Second film forming step>
In step S3, as the second film forming step, the film 2 containing a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in its molecule, its hydrolyzate or its polymer is formed. The film 2 is an aqueous solution mainly containing a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, its hydrolyzate or its polymer (hereinafter, also referred to as a silane compound aqueous solution or a second aqueous solution). 1 is formed by processing 1. The silane compound aqueous solution may further contain a silane coupling agent, its hydrolyzate, or its polymer. The silane compound aqueous solution may further contain one or more stabilizers, auxiliary agents, etc., if desired. For example, as the stabilizer, a carboxylic acid having 1 to 4 carbon atoms such as formic acid and acetic acid, an organic compound such as alcohol having 1 to 4 carbon atoms such as methanol and ethanol, and the like may be contained.

The coating amount of the second aqueous solution, from the viewpoint of the adhesion durability, coating amount of the film 2 after drying, per side, it is preferable to be 0.01 mg / ^{m 2} or more 30 mg / ^m of less than ^2. The coating amount of the coating 2 is, for example, diluting a silane compound with a solvent (water, an organic solvent, or a mixture thereof) to reduce the solid content concentration and viscosity, or adjusting the wet coating amount with a coater count. It can be easily controlled by doing. The concentration of the silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the second aqueous solution, its hydrolyzate or its polymer is not particularly limited, but is, for example, 0.005 mass% to It is 5% by mass, preferably 0.01% by mass to 2% by mass, and more preferably 0.05% by mass to 1% by mass.

Moreover, the application method of the second aqueous solution is not particularly limited, and an existing method can be applied. Specifically, apply a coating method by dipping, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a reverse gravure coater, a dip coater, a method using various coating machines such as electrostatic coating, or a spray coating method. You can

After the second aqueous solution is applied, it is dried by heating. By heating and drying, the formation of a covalent bond between the trialkoxysilyl group contained in the silane compound in the film 2 and the metal element in the film 1 is promoted, and further water as a solvent is removed to form the film 2 Densify and stabilize. The heating temperature is preferably 60° C. or higher, more preferably 75° C. or higher, even more preferably 90° C. or higher. Further, if the heating temperature is too high, the functional groups of the silane compound are decomposed and the properties of the aluminum alloy are affected. Therefore, the heating temperature is preferably 250° C. or lower, more preferably 200° C. or lower, and further preferably 150° C. It is as follows. The drying time, which depends on the heating temperature, is preferably 2 seconds or more, more preferably 5 seconds or more, and further preferably 10 seconds or more. The drying time is preferably 20 minutes or less, more preferably 5 minutes or less, and further preferably 2 minutes or less.

<Other processes>
In the manufacturing process of the aluminum alloy material 10 of the present embodiment, other steps may be included between or before and after each step as long as the above-mentioned steps are not adversely affected. For example, a preliminary aging treatment step of performing a preliminary aging treatment may be provided after the second film forming step S3. This preliminary aging treatment is preferably performed by heating at a low temperature of 40 to 120° C. for 8 to 36 hours within 72 hours. By performing the pre-aging treatment under these conditions, the formability and the strength after baking can be improved. In addition, for example, a foreign matter removing step of removing foreign matter on the surface of the aluminum alloy material 10 or a defective article removing step of removing defective articles generated in each step may be performed.

Then, the manufactured aluminum alloy material 10 may be coated with a mechanical oil such as a press oil on the surface thereof before the production of the joined body or the processing into the automobile member. As the press oil, one containing an ester component is mainly used. The method and conditions for applying the press oil to the aluminum alloy material 10 are not particularly limited, and the method and conditions for applying a normal press oil can be widely applied. For example, a press containing ethyl oleate as an ester component. The aluminum alloy material 10 may be immersed in oil. The ester component is not limited to ethyl oleate, and various compounds such as butyl stearate and sorbitan monostearate can be used.

Here, since the aluminum alloy material 10 of the present embodiment is provided with the film 2 having a high solubility of mechanical oil on the outermost surface, the adhesive resin is satisfactorily bonded thereon even after the mechanical oil is applied. be able to.

As described above in detail, in the present embodiment, the oxide film formed on the surface of the aluminum alloy substrate 3 is subjected to silicate treatment to form the film 1 made of aluminum oxide containing silicon, and then the silane compound aqueous solution. The aluminum alloy material 10 is manufactured by treating the coating 1 with the above to form the coating 2. Thereby, a covalent bond between the silane compound and the metal oxide is formed at the interface between the coating 1 and the coating 2, and excellent adhesion durability can be obtained. Further, if the amount of Mg in the film 1 is adjusted to a specific range, the formation of an oxide film containing Mg, which is mechanically brittle and has low corrosion resistance, can be suppressed, and deterioration of the adhesive resin interface can be suppressed. Furthermore, if the film 1 contains a specific amount of Si and the amount of Cu in the film 1 is controlled to be less than the specified amount, the adhesiveness between the film 1 and the film 2 is improved. As a result, the aluminum alloy material 10 of the present embodiment suppresses interfacial peeling even when exposed to a high temperature wet environment, and can suppress a decrease in adhesive strength over a long period of time.

(Modification of the first embodiment)
Next, an aluminum alloy material with an adhesive resin layer according to a modified example of the first embodiment of the present invention will be described. FIG. 3 is a cross-sectional view schematically showing the configuration of the aluminum alloy material with an adhesive resin layer of this modification. In FIG. 3, the same components as those of the aluminum alloy material 10 shown in FIG. 1 are designated by the same reference numerals, and detailed description thereof will be omitted. As shown in FIG. 3, the aluminum alloy material 11 with an adhesive resin layer of the present modified example is an adhesive resin layer made of an adhesive resin so as to cover the coating 1 and the coating 2 of the aluminum alloy material of the first embodiment described above. 4 are formed.

[Adhesive resin layer 4]
The adhesive resin layer 4 is made of an adhesive resin or the like, and the aluminum alloy material 11 with an adhesive resin layer of the present modification is joined to other members via the adhesive resin layer 4. The other members include another aluminum alloy material having a film formed thereon like the aluminum alloy material 11 having an adhesive resin layer, an aluminum alloy material having no oxide film formed thereon, a resin molded body, and the like. ..

The adhesive resin that constitutes the adhesive resin layer 4 is not particularly limited, and is conventionally used when joining aluminum alloy materials such as epoxy resin, urethane resin, nitrile resin, nylon resin, and acrylic resin. Adhesive resins that have been used can be used. Of these, epoxy resins are preferable from the viewpoint of adhesive strength. Further, the adhesive resin may be used alone or in combination of two or more.

The thickness of the adhesive resin layer 4 is also not particularly limited, but is preferably 10 to 500 μm, more preferably 50 to 400 μm. When the thickness of the adhesive resin layer 4 is less than 10 μm, when the aluminum alloy material 11 with an adhesive resin layer and an aluminum alloy material not provided with another adhesive resin layer are joined via the adhesive resin layer 4. , High adhesion durability may not be obtained. On the other hand, when the thickness of the adhesive resin layer 4 exceeds 500 μm, the adhesive strength may be reduced.

[Production method]
Next, a method of manufacturing the aluminum alloy material 11 with the adhesive resin layer of the present modification will be described. FIG. 4 is a flow chart showing the method for manufacturing the aluminum alloy material 11 with the adhesive resin layer of the present modification. As shown in FIG. 4, when manufacturing the aluminum alloy material 11 with an adhesive resin layer of the present modification, an adhesive resin layer forming step S4 is performed in addition to steps S1 to S3 described above.

<Step S4: Adhesive Resin Layer Forming Step>
In the adhesive resin layer forming step S4, the adhesive resin layer 4 is formed so as to cover the film 1 and the film 2. The method for forming the adhesive resin layer 4 is not particularly limited. For example, when the adhesive resin is a solid, heat is applied for pressure bonding, or this is dissolved in a solvent to form a solution, Further, when the adhesive resin is in a liquid state, a method of spraying or coating the surface of the film 2 as it is can be mentioned.

Further, also in the aluminum alloy material 11 with an adhesive resin layer of the present modification, similar to the above-described first embodiment, the first film forming step S2, the second film forming step S3 and/or the adhesive resin layer forming step S4. After that, a preliminary aging treatment step for performing the preliminary aging treatment may be provided.

In the aluminum alloy material with the adhesive resin layer of this modification, since the adhesive resin layer is provided in advance, the work such as applying the adhesive resin to the surface of the aluminum alloy material is omitted when manufacturing the joined body or the automobile member. can do. The configurations and effects of the aluminum alloy material with the adhesive resin layer of this modification other than the above are the same as those of the first embodiment described above.

(Second embodiment)
Next, a joined body according to the second embodiment of the present invention will be described. The joined body according to the present embodiment uses the above-described aluminum alloy material according to the first embodiment or a modified aluminum alloy material with an adhesive resin layer. 5 to 8B are cross-sectional views schematically showing a configuration example of the joined body of this embodiment. 5 to 8B, the same components as those of the aluminum alloy material 10 and the aluminum alloy material 11 with an adhesive resin layer shown in FIGS. 1 and 3 are denoted by the same reference numerals, and detailed description thereof will be omitted.

[Structure of bonded body]
In the joined body of the present embodiment, for example, like the joined body 20 shown in FIG. 5, the two aluminum alloy materials 10 shown in FIG. 1 are arranged so that the surfaces on which the coating 1 and the coating 2 are formed face each other. It is possible to adopt a configuration in which they are arranged at the same position and are bonded to each other via the adhesive resin 5. That is, in the bonded body 20, one surface of the adhesive resin 5 is bonded to the coating 2 side of the one aluminum alloy material 10 and the other surface is bonded to the coating 2 side of the other aluminum alloy material 10.

Here, as the adhesive resin 5 in the joined body of the present embodiment, the same adhesive resin as the above-described adhesive resin forming the adhesive resin layer 4 can be used. Specifically, the adhesive resin 5 may be an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, an acrylic resin, or the like. The thickness of the adhesive resin 5 is not particularly limited, but is preferably 10 to 500 μm, and more preferably 50 to 400 μm from the viewpoint of improving the adhesive strength.

As described above, in the bonded body 20, since both surfaces of the adhesive resin 5 are the coating 1 and the coating 2 of the aluminum alloy material 10 of the first embodiment, when they are used for automobile members, they are exposed to a high temperature and humid environment. Even if this is done, the adhesive strength at the interface between the adhesive resin 5 and the film 1 or film 2 is unlikely to decrease, and the adhesive durability is improved. In addition, in the joined body 20 of the present embodiment, regardless of the type of the adhesive resin 5, the adhesive durability at the interface is improved in all the adhesive resins conventionally used for joining aluminum alloy materials.

Further, like the bonded body 21a shown in FIG. 6A or the bonded body 21b shown in FIG. 6B, the surface of the aluminum alloy material 10 shown in FIG. It is also possible to adopt a configuration in which another aluminum alloy material 6 or resin molded body 7 on which the first coating and the second coating are not formed is joined.

Here, as the other aluminum alloy material 6 on which the first coating and the second coating are not formed, the same material as the above-mentioned base material 3 can be used, and specifically, it is defined in JIS. Alternatively, those made of various non-heat treatment type or heat treatment type aluminum alloys similar to JIS can be used.

Examples of the resin molded body 7 include glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), boron fiber reinforced plastic (BFRP), aramid fiber reinforced plastic (AFRP, KFRP), polyethylene fiber reinforced plastic ( Fiber reinforced plastic moldings formed of various fiber reinforced plastics such as DFRP) and Zylon reinforced plastic (ZFRP) can be used. By using these fiber-reinforced plastic molded products, it becomes possible to reduce the weight of the bonded product while maintaining a constant strength.

In addition to the fiber reinforced plastics described above, the resin molded body 7 includes polypropylene (PP), acrylic-butadiene-styrene copolymer (ABS) resin, polyurethane (PU), polyethylene (PE), polyvinyl chloride (PVC). Fiber reinforced with nylon, nylon 6, nylon 6,6, polystyrene (PS), polyethylene terephthalate (PET), polyamide (PA), polyphenylene sulfide (PPS), polybutylene terephthalate (PBT), polyphthalamide (PPA), etc. It is also possible to use no engineering plastics.

In the joined bodies 21a and 21b shown in FIGS. 6A and 6B, one surface of the adhesive resin 5 is joined to the coating 1 and the coating 2 sides of the aluminum alloy material 10, and therefore, as with the above-described joined body 20, a vehicle member. When it is used for, it is not affected by the type of the adhesive resin even if it is exposed to a high temperature and humid environment, and the adhesive durability at the interface is improved. Further, since the joined body 21b shown in FIG. 6B joins the aluminum alloy material 10 and the resin molded body 7, it is lighter than the joined body of aluminum alloy materials, and by using this joined body 21b. Further weight reduction of the automobile can be realized. The structures and effects of the bonded bodies 21a and 21b shown in FIGS. 6A and 6B other than the above are the same as those of the bonded body 20 shown in FIG.

Further, like the joined body 22 shown in FIG. 7, the aluminum alloy material 11 with the adhesive resin layer 4 shown in FIG. 3 and the aluminum alloy material 10 without the adhesive resin layer 4 shown in FIG. It is also possible to adopt a configuration in which and are joined. Specifically, the coating 1 and the coating 2 sides of the aluminum alloy material 10 are joined to the adhesive resin layer 4 side of the aluminum alloy material 11 with the adhesive resin layer. As a result, the film 1 and film 2 sides of the aluminum alloy material 10 and the film 1 and film 2 sides of the aluminum resin material 11 with an adhesive resin layer are respectively bonded via the adhesive resin layer 4 of the aluminum alloy material 11 with an adhesive resin layer. It is arranged so as to face each other.

In the bonded body 22, since both surfaces of the adhesive resin layer 4 are bonded to the coating 1 and coating 2 sides of the aluminum alloy material 10 and the coating 1 and coating 2 side of the aluminum alloy material 11 with the adhesive resin layer, respectively, the above-described bonding is performed. Similar to the body 20, when the joined body 22 is used for a vehicle member, even if it is exposed to a high temperature and humid environment, it is not affected by the type of the adhesive resin, and the adhesive durability at the interface is improved. The configuration and effects of the bonded body 22 shown in FIG. 7 other than the above are the same as those of the bonded body 20 shown in FIG.

Further, as in the bonded body 23a shown in FIG. 8A or the bonded body 23b shown in FIG. 8B, the first resin layer is provided on the side of the adhesive resin layer 4 of the aluminum alloy material 11 with the adhesive resin layer having the adhesive resin layer 4 shown in FIG. It is also possible to adopt a configuration in which another aluminum alloy material 6 on which the coating and the second coating are not formed or a resin molded body 7 such as a fiber reinforced plastic molded body is joined. In these bonded bodies 23a and 23b, one surface of the adhesive resin layer 4 is bonded to the coating 1 and coating 2 sides of the adhesive resin layer-attached aluminum alloy material 11, so that the bonded body 23 is bonded in the same manner as the bonded body 20 described above. When it is used as a member for automobiles, it is not affected by the type of adhesive resin even when exposed to a high temperature and humid environment, and the adhesive durability at the interface is improved.

Further, since the joined body 23b shown in FIG. 8B joins the adhesive resin layer-attached aluminum alloy material 11 and the resin molded body 7, it is lighter than the joined body of aluminum alloy materials, and a reduction in weight is required. It is suitable for existing automobiles and vehicle members. The configurations and effects of the bonded bodies 23a and 23b shown in FIGS. 8A and 8B other than the above are the same as those of the bonded body 20 shown in FIG.

[Production method]
As a method of manufacturing the above-described joined bodies 20 to 23, particularly a joining method, a conventionally known joining method can be used. The method for forming the adhesive resin 5 on the aluminum alloy material is not particularly limited, but, for example, an adhesive sheet prepared in advance with the adhesive resin 5 may be used, or the adhesive resin 5 may be formed on the surface of the film 2. It may also be formed by spraying or applying on. As with the aluminum alloy material 10 and the aluminum alloy material 11 with an adhesive layer, the joined bodies 20 to 23 may be coated with a press oil on the surface thereof before being processed into an automobile member.

Although not shown, when an aluminum alloy material having the coating 1 and the coating 2 on both surfaces is used for the joined body of the present embodiment, these aluminum alloy materials are provided via the adhesive resin 5 or the adhesive resin layer 4. It is possible to further join another aluminum alloy material or resin molded body on which the coating 1 and the coating 2 are not formed.

(Third Embodiment)
Next, an automobile member according to the third embodiment of the present invention will be described. The automobile member of the present embodiment uses the joined body of the second embodiment described above, and is, for example, an automobile panel or the like.

The method for manufacturing the automobile member of the present embodiment is not particularly limited, but a conventionally known manufacturing method can be applied. For example, the joined bodies 20 to 23b shown in FIGS. 5 to 8B are subjected to cutting, pressing, or the like to manufacture an automobile member having a predetermined shape.

Since the automobile member of the present embodiment is manufactured from the bonded body of the second embodiment described above, even if it is exposed to a high temperature wet environment, the adhesive resin or the adhesive resin layer and the oxide film (first film) The elution of the aluminum alloy substrate can be suppressed with almost no influence of hydration. As a result, in the automobile member of the present embodiment, it is possible to suppress interfacial peeling when exposed to a high temperature and humid environment and suppress a decrease in adhesive strength.

Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention. In this example, an aluminum alloy material was prepared under the following methods and conditions, and the adhesion durability and the like were evaluated.

<Example 1>
A 6000 series aluminum alloy of JIS6016 (Mg: 0.54% by mass, Si: 1.11% by mass, Cu: 0.14% by mass) was used to produce an aluminum alloy cold-rolled plate having a plate thickness of 1 mm. Then, this cold-rolled sheet was cut into a length of 100 mm and a width of 25 mm to obtain a base material, which was heat-treated to a body temperature of 550° C. and cooled.
Subsequently, the base material was alkali degreased with an aqueous solution of pH 13 containing potassium hydroxide at 50° C. for 40 seconds, and further pickled with a solution of pH 1 containing sulfuric acid and hydrofluoric acid at a temperature of 50° C. and a treatment time of 40 seconds. Then, it was washed with water and dried. Then, an aqueous solution (TEOS aqueous solution) containing 0.013% by mass of tetraethyl orthosilicate (TEOS) was uniformly applied to the surface with a bar coater, and dried by heating at 100° C. for 1 minute to form a first film. Furthermore, an aqueous solution (BTSE aqueous solution) containing 0.10% by mass of bistriethoxysilylethane (BTSE) was uniformly applied to the surface with a bar coater, and dried by heating at 100° C. for 1 minute to form a second film, The aluminum alloy material of Example 1 was produced.

Next, the press oil was diluted with toluene to adjust the concentration, and then applied on the surface of the aluminum alloy material of Example 1 on the side of the second coating so that the coating amount after drying was 1 g/m ² .

<Example 2>
An aluminum alloy material of Example 2 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.325% by mass. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 2 on the second coating side so that the applied amount after drying was 1 g/m ² .

<Example 3>
An aluminum alloy material of Example 3 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.065 mass% and the concentration of the BTSE aqueous solution was 1 mass %. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 3 on the side of the second coating so that the applied amount after drying was 1 g/m ² .

<Example 4>
An aluminum alloy material of Example 4 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.065 mass% and the concentration of the BTSE aqueous solution was 0.01 mass %. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 4 on the side of the second coating so that the coating amount after drying was 1 g/m ² .

<Example 5>
An aluminum alloy material of Example 5 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.065 mass% and the concentration of the BTSE aqueous solution was 0.025 mass %. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 5 on the second coating side so that the coating amount after drying was 1 g/m ² .

<Example 6>
An aluminum alloy material of Example 6 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.13% by mass and the concentration of the BTSE aqueous solution was 0.1% by mass. Further, press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 6 on the side of the second coating so that the applied amount after drying was 1 g/m ² .

<Example 7>
An aluminum alloy material of Example 7 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.065 mass% and the concentration of the BTSE aqueous solution was 0.41 mass %. Further, the press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 7 on the second coating side so that the coating amount after drying was 1 g/m ² .

<Example 8>
An aluminum alloy material of Example 8 was obtained in the same manner as in Example 2, except that the base material was washed with water after applying the TEOS aqueous solution, heated and dried at 100° C. for 1 minute, and then applied with the BTSE aqueous solution. Further, press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 8 on the side of the second coating so that the applied amount after drying was 1 g/m ² .

<Example 9>
An aluminum alloy material of Example 9 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.013% by mass and the concentration of the BTSE aqueous solution was 0.025% by mass. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 9 on the side of the second coating so that the applied amount after drying was 1 g/m ² .

<Example 10>
An aluminum alloy material of Example 10 was obtained in the same manner as in Example 9 except that 0.1% by mass of 3-aminopropyltriethoxysilane (APS) was added to the BTSE aqueous solution. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 10 on the second coating side so that the coating amount after drying was 1 g/m ² .

<Example 11>
An aluminum alloy material of Example 11 was obtained in the same manner as in Example 9 except that 0.1% by mass of 3-glycidoxypropyltriethoxysilane (GPS) was added to the BTSE aqueous solution. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 11 on the side of the second coating so that the coating amount after drying was 1 g/m ² .

<Example 12>
An aluminum alloy material of Example 12 was obtained in the same manner as in Example 4 except that an aqueous solution containing 0.1% by mass of bistriethoxysilylbenzene (BTSB) was used instead of the BTSE aqueous solution. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 12 on the second coating side so that the coating amount after drying was 1 g/m ² .

<Example 13>
An aluminum alloy material of Example 13 was obtained in the same manner as Example 4 except that an aqueous solution containing 0.1% by mass of bistriethoxysilylpropylamine (BTSA) was used instead of the BTSE aqueous solution. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 13 on the second coating side so that the coating amount after drying was 1 g/m ² .

<Example 14>
An aluminum alloy material of Example 14 was obtained in the same manner as in Example 4 except that an aqueous solution containing 0.1% by mass of bistriethoxysilylpropyl tetrasulfide (BTSS) was used instead of the BTSE aqueous solution. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Example 14 on the side of the second coating so that the coating amount after drying was 1 g/m ² .

<Comparative Example 1>
An aluminum alloy material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 2.3% by mass. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Comparative Example 1 on the second coating side so that the coating amount after drying was 1 g/m ² .

<Comparative example 2>
An aluminum alloy material of Comparative Example 2 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.0061% by mass and the concentration of the BTSE aqueous solution was 0.025%. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Comparative Example 2 on the second coating side so that the applied amount after drying was 1 g/m ² .

<Comparative example 3>
An aluminum alloy material of Comparative Example 3 was obtained in the same manner as in Example 1 except that an aqueous TEOS solution containing 0.1% by mass of TEOS and 0.1% by mass of silica sol having a particle diameter of 4 nm was added. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Comparative Example 3 on the second coating side so that the coating amount after drying was 1 g/m ² .

<Comparative example 4>
An aluminum alloy material of Comparative Example 4 was obtained in the same manner as in Example 1 except that the treatment with the BTSE aqueous solution was not performed. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Comparative Example 4 on the first film side so that the applied amount after drying was 1 g/m ² .

<Comparative Example 5>
An aluminum alloy material of Comparative Example 5 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.13 mass% and the degreasing/pickling treatment before the treatment with the TEOS aqueous solution was not performed. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Comparative Example 5 on the second coating side so that the applied amount after drying was 1 g/m ² .

<Comparative example 6>
An aluminum alloy material of Comparative Example 6 was obtained in the same manner as in Example 1 except that the concentration of the TEOS aqueous solution was 0.13% by mass and the pickling treatment before the treatment with the TEOS aqueous solution was performed for 300 seconds. Further, a press oil diluted with toluene was applied to the surface of the aluminum alloy material of Comparative Example 6 on the second coating side so that the applied amount after drying was 1 g/m ² .

(IR spectrum measurement)
FT-IR (Fourier transform infrared spectrophotometer: Nicona Magna-750 spectrometer) analysis was performed on the aluminum alloy material having the first coating before formation of the second coating using parallel polarized light with an incident angle of 75°. By doing so, the IR spectrum was measured, and the absorption band existing in the wave number range of 1000 to 1300 cm ⁻¹ was read in the difference spectrum before and after the film treatment. Table 1 shows the maximum points of absorption in each absorption band.

<Measurement of first film component>
The first coating was measured by high-frequency glow discharge emission spectroscopy (GD-OES: Horiba Jobin Yvon Co., Ltd. Model JY-5000RF) while sputtering in the film thickness direction, and aluminum (Al), magnesium (Mg), and copper were measured. Each component of metal elements such as (Cu), iron (Fe) and titanium (Ti) and elements such as oxygen (O), nitrogen (N), carbon (C), silicon (Si) and sulfur (S) The quantity was measured. Regarding magnesium (Mg), copper (Cu) and silicon (Si), the maximum concentration in the first coating was defined as the coating concentration in the coating. Regarding aluminum (Al), since the base material is affected in the vicinity of the interface between the base material and the first coating, the concentration of the outermost surface was defined as the aluminum (Al) coating concentration. Here, in the calculation of the concentrations of these elements, oxygen (O) and carbon (C) are particularly susceptible to contamination on the outermost surface and in the vicinity thereof. From the above, in the calculation of the concentration of each element, the concentration was calculated excluding oxygen (O) and carbon (C). Oxygen (O) is likely to be affected by contamination on the outermost surface and in the vicinity thereof, and it is difficult to measure an accurate concentration, but the film 1 of all samples contains oxygen (O). It was clear.

<Measurement of etching amount>
The etching amount is the amount of dissolution of the oxide film or the base material containing the oxide film, and the amount of reduction in weight before and after the etching treatment was measured and estimated as the thickness (film thickness). For the sake of convenience, the conversion of the weight reduction amount into the film thickness was performed by using the aluminum density: 2.7 g/cm ³ and calculating it as the aluminum thickness.

<Measurement of coating amount of first and second coating>
The coating amounts of the first and second coatings formed by the treatment with the silicate and silane compound aqueous solution were measured by fluorescent X-ray. Specifically, the amount of silicon in the first film after the silicate treatment and the amount of silicon in the second film after the silane compound treatment were measured by fluorescent X-rays, and the intensity of the fluorescent X-rays and the amount of the film were converted using the calibration curve. Each was calculated by carrying out. The results are shown in Table 1.

<Cohesive failure rate (bonding durability)>
9A and 9B are diagrams schematically showing the method for measuring the cohesive failure rate, FIG. 9A is a side view, and FIG. 9B is a plan view. As shown in FIGS. 9A and 9B, the end portions of two test materials 31a and 31b (25 mm width) having the same structure are wrapped with a thermosetting epoxy resin adhesive resin in a wrap length of 10 mm (bonding area: 25 mm×10 mm). ) Was pasted and pasted.
The adhesive resin 35 used here is a thermosetting epoxy resin-based adhesive resin (bisphenol A type epoxy resin amount 40 to 50% by mass). Further, a small amount of glass beads (particle size 250 μm) was added to the adhesive resin 35 to adjust the thickness of the adhesive resin 35 to 250 μm.
After overlapping, they were dried at room temperature for 30 minutes and then heated at 170° C. for 20 minutes to carry out a thermosetting treatment. Then, it left still at room temperature for 24 hours, and produced the adhesion test body.

The produced adhesion test body was immersed in an aqueous sodium chloride solution having a concentration of 5% at 40° C. for 20 days, and then pulled at a speed of 50 mm/min by a tensile tester to evaluate the cohesive failure rate of the adhesive resin in the bonded portion. The cohesive failure rate was calculated based on the following mathematical formula 1. In the following mathematical formula 1, one side of the adhesion test body after being pulled was designated as a test piece a and the other side was designated as a test piece b.

Three pieces were produced under each test condition, and the cohesive failure rate was an average value of the three pieces. In addition, the evaluation criteria are that the cohesive failure rate is less than 60% is poor (x), 60% or more and less than 70% is slightly good (△), 70% or more and less than 90% is good (◯), and 90% or more is excellent. (◎). The results are shown in Table 1.

As shown in Table 1, in the aluminum alloy material of Comparative Example 1, the Si concentration in the first coating was higher than the range specified in the present invention, and the adhesion durability was poor.
In the aluminum alloy material of Comparative Example 2, the Si concentration in the first coating was lower than the range specified in the present invention, and one of the absorption bands was out of the wave number range specified in the present invention, so that the adhesion durability was improved. I was poor in sex.
Further, in the aluminum alloy material of Comparative Example 3, one of the absorption bands of the first coating was out of the wave number range specified in the present invention, and the adhesion durability was poor.
Further, in the aluminum alloy material of Comparative Example 4, the press oil is applied on the first film, which has poor solubility in the press oil, without forming the second film. As a result, the adhesion durability was poor.
The aluminum alloy material of Comparative Example 5 had a Mg concentration in the first coating higher than the range specified in the present invention, and was poor in adhesion durability.
Further, the aluminum alloy material of Comparative Example 6 had a Cu concentration in the first coating higher than the range specified in the present invention, and was poor in adhesion durability.

On the other hand, the aluminum alloy materials of Examples 1 to 14 satisfying the requirements stipulated in the present invention had good wet durability in a high temperature and high humidity environment.

DESCRIPTION OF SYMBOLS 1 1st film 2 2nd film 3 Base material 4 Adhesive resin layer 5,35 Adhesive resin 6,10 Aluminum alloy material 11 Aluminum alloy material with an adhesive resin layer 7 Resin molded body 20, 21a, 21b, 22, 23a, 23b Bonding Body 31a, 31b Test material

Claims (16)

Aluminum alloy base material,
A first coating formed on at least a part of the surface of the aluminum alloy substrate, the first coating including an oxide of aluminum containing silicon;
An aluminum alloy material having a second coating formed on at least a part of the first coating and containing a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof. And
The first film has two absorption bands in the wave number range of 1000 to 1300 cm ⁻¹ in the difference spectrum before and after the film treatment, which is obtained by injecting parallel polarized light with an incident angle of 75° by Fourier transform infrared spectroscopy. However, the two absorption bands are in the ranges of wave numbers of 1080 to 1140 cm ⁻¹ and wave numbers of 1180 to 1240 cm ⁻¹ , and the first coating contains Si of 15 atomic% or more and less than 70 atomic% and Mg of 0.1 or less. An aluminum alloy material containing not less than 30 atomic% and not less than 30 atomic% and Cu regulated to less than 0.6 atomic %. The aluminum alloy material according to claim 1, wherein the first coating does not substantially include a particulate inorganic compound having a diameter of 1 nm or more. The aluminum alloy material according to claim 2, wherein the amount of Si in the first coating is 20 atomic% or more and less than 65 atomic %. The aluminum alloy material according to claim 3, wherein the amount of Si in the first coating is 30 atomic% or more and less than 60 atomic %. The aluminum according to any one of claims 1 to 4, wherein the second coating further contains a silane coupling agent having a reactive functional group capable of chemically bonding with an organic resin component, a hydrolyzate thereof, or a polymer thereof. Alloy material. The aluminum alloy material according to claim 1, wherein the coating amount of the second coating is 0.01 to 30 mg/m ² . The aluminum alloy material according to claim 6, wherein the coating amount of the second coating is 0.2 to 20 mg/m ² . The aluminum alloy material according to claim 7, wherein the coating amount of the second coating is 0.5 to 10 mg/m ² . The aluminum alloy base material comprises an Al-Mg-based alloy, an Al-Cu-Mg-based alloy, an Al-Mg-Si-based alloy, or an Al-Zn-Mg-based alloy. The described aluminum alloy material. An aluminum alloy material with an adhesive resin layer, wherein an adhesive resin layer is formed on the second coating of the aluminum alloy material according to any one of claims 1 to 9. The aluminum alloy material with an adhesive resin layer according to claim 10, wherein the adhesive resin layer contains at least one selected from an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, and an acrylic resin. A first film forming step of forming a first film made of an oxide of aluminum containing silicon on at least a part of the surface of the aluminum alloy substrate;
Second film forming step of forming a second film containing a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof or a polymer thereof on at least a part of the first film With and
The first film forming step includes a heat treatment step of forming an oxide film on the surface of the aluminum alloy base material, an etching treatment step and a silicate treatment step after the heat treatment step, and the silicate treatment step includes the etching. After the treatment step or at the same time as the etching treatment step, and as the silicate treatment step, the oxide film is treated with a first aqueous solution containing 0.005% by mass to 2% by mass of a tetraalkyl silicate or an oligomer thereof.
In the second film forming step, the first film is treated with a second aqueous solution containing a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof. Method for manufacturing alloy material. The method for manufacturing an aluminum alloy material according to claim 12, wherein the etching amount in the etching step is controlled to be less than 700 nm. The said 1st film formation process WHEREIN: The said silicate process step is after the said etching process step, At least 1 of an acid treatment and an alkaline solution process is performed as the said etching process step, The claim 12 or 13 is described. Manufacturing method of aluminum alloy material. The method for manufacturing an aluminum alloy material according to claim 12 or 13, wherein in the first film forming step, the silicate treatment step is the same as the etching treatment step. An adhesive resin layer forming step of forming an adhesive resin layer on the second coating of the aluminum alloy material produced by the method for producing an aluminum alloy material according to claim 12. A method for manufacturing an aluminum alloy material with a resin layer.