JP2017203212A - 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

Abstract

PROBLEM TO BE SOLVED: To provide: an aluminum alloy material which hardly causes deterioration in bond strength even when exposed to a high temperature wet environment and has excellent bond durability; 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.SOLUTION: There is provided an aluminum alloy material which comprises: an aluminum alloy base material; a first coating film comprising an oxide of aluminum containing silicon, which is formed on at least one part of a surface of the aluminum alloy base material; and a second coating film comprising a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof or a polymer thereof, which is formed on at least one part of the first coating film, wherein the first coating film contains 15 atom% or more and less than 80 atom% of Si and 0.1 atom% or more and less than 30 atom% of Mg, with the content of Cu restricted to less than 0.6 atom%, and also contains 0.01 to 25 atom% of at least one alkali metal element selected from Na, K and Li.SELECTED DRAWING: None

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 components used in transportation equipment such as automobiles, ships, and aircraft, development of technologies for joining different materials such as carbon fiber, aluminum alloy, and steel materials with different strengths, materials, and masses has attracted attention. Yes. In particular, adhesive resins (resin adhesives) have been actively researched in recent years because they do not corrode materials due to electrolytic corrosion and can bond various materials without corroding them. However, in a high humidity environment, moisture enters the interface between the metal and the adhesive resin, causing corrosion / deterioration of the metal surface and peeling easily at the interface between the metal and the adhesive resin, resulting in a significant decrease in adhesive strength. . For this reason, 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 affects the adhesive durability.

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

  For example, Patent Document 1 discloses an adhesive formed on a metal such as aluminum by treating it with an aqueous composition containing a tetraalkylsilicate such as tetraethylorthosilicate and a hydrated oxide sol such as silica sol. A method for improving the initial adhesion of the coating film and the long-term stability of the adhesion is described.

  Patent Document 2 discloses that after treating a metal substrate with a first treatment solution consisting essentially of at least one polyfunctional silane having at least two trisubstituted silyl groups, at least one kind of organo A technique for improving the corrosion resistance of a metal by applying a second coating containing a second treatment solution containing a functional silane is described.

  Patent Document 3 describes a technique for improving the corrosion resistance of a metal by treating a metal substrate with a solution containing aminosilane and polysilyl functional silane.

  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 silicate compound and then treating with a silane coupling agent.

  Patent Document 5 discloses that a solution containing a silicate ester, an aluminum inorganic salt and polyethylene glycol and further containing a silane coupling agent is applied onto a galvanized steel sheet and dried to form a film. Thus, a technique for improving paint adhesion and white rust resistance is described.

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

  Further, Patent Document 7 improves corrosion resistance and paint adhesion 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. The method is described.

Japanese National 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 JP 9-510259 gazette

  However, in the method described in Patent Document 1, since the adhesive strength is remarkably reduced by a long-term wet deterioration test, it cannot be said that the adhesion durability is sufficient.

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

  In addition, the methods described in Patent Documents 4 to 7 are intended only for the purpose of preventing corrosion of metal surfaces and improving the adhesion of paints. Therefore, although the formed film is thick, the mechanical film itself has low mechanical strength and becomes brittle with respect to tension and stress, and high adhesive strength cannot be obtained.

  Further, the surface-treated aluminum alloy material is coated with oil after the surface treatment to improve workability, and then molded and bonded. Here, if machine oil such as lubricating oil, press oil or processing oil is included between the surface treatment film and the adhesive, the adhesiveness of the adhesive is greatly reduced, and high adhesive strength cannot be obtained. There is a demand for the development of an aluminum alloy material whose bonding durability does not deteriorate even when machine oil such as press oil or processing oil adheres to the surface.

  In view of the problems as described above, the present invention provides an aluminum alloy material, an aluminum alloy material with an adhesive resin layer, and an aluminum alloy that have excellent adhesion durability, even when exposed to a high-temperature and humid environment. The main object is to provide a method for producing a material and a method for producing an aluminum alloy material with an adhesive resin layer.

  As a result of intensive experiments and studies to solve the above-described problems, the inventor formed a film made of an oxide of aluminum containing silicon by silicate treatment on the surface of the aluminum base material, While forming a film containing a silane compound, a hydrolyzate thereof or a polymer thereof and adjusting the amount of each component in the first film, it was found that excellent adhesion durability was obtained, and the present invention was achieved. .

  That is, the present invention provides an aluminum alloy base material, a first film made of an aluminum oxide containing silicon, formed on at least a part of the surface of the aluminum alloy base material, and at least a part of the first film. An aluminum alloy material provided with a second film containing a silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof, Contains 15 atomic percent or more and less than 80 atomic percent of Si and Mg of 0.1 atomic percent or more and less than 30 atomic percent, Cu is restricted to less than 0.6 atomic percent, and Na, K and Li An aluminum alloy material containing 0.01 to 25 atomic% of at least one alkali metal element selected from:

  Here, the Si amount, Mg amount, Cu amount, Na amount, K amount and Li amount in the first film are values measured by a high-frequency glow discharge emission spectroscopy (GD-OES). It is.

  In the aluminum alloy material of the present invention, the amount of Si in the first coating is preferably 20 atomic percent or more and less than 75 atomic percent, and more preferably 30 atomic percent or more and less than 70 atomic percent.

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

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 further preferably / 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. Also good.

  Moreover, this invention also provides the aluminum alloy material with an adhesive resin layer in which the adhesive resin layer is formed on the 2nd film | membrane of the aluminum alloy material mentioned 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.

The present invention also 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 substrate, and an intramolecular structure in at least a part of the first film. A second film forming step of forming a second film containing a silane compound having two or more hydrolyzable trialkoxysilyl groups, 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, wherein the silicate treatment step is after the etching treatment step. Alternatively, 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 silicate, and the second In the film forming step, the first coating 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. A manufacturing method is also provided.

  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 formation step, the silicate treatment stage is after the etching treatment stage, and at least one of acid treatment and alkaline solution treatment is performed as the etching treatment stage. May be performed.

  In the method for producing an aluminum alloy material of the present invention, in the first film formation step, the silicate treatment stage is the same as the etching treatment stage, and the first aqueous solution is a neutral or alkaline aqueous solution containing silicate. There may be.

  In the method for producing an aluminum alloy material of the present invention, the second aqueous solution is an aqueous solution further containing a silane coupling agent having a reactive functional group capable of chemically bonding to an organic resin component, a hydrolyzate thereof, or a polymer thereof. Also good.

  Furthermore, the present invention includes an adhesive resin layer forming step of forming an adhesive resin layer on the second film of the aluminum alloy material manufactured by the above-described method for manufacturing an aluminum alloy material. A manufacturing method is also provided.

  ADVANTAGE OF THE INVENTION According to this invention, even if it exposes to a high temperature humid environment, the adhesive strength cannot fall easily and the aluminum alloy material excellent in adhesion durability is realizable.

FIG. 1 is a cross-sectional view schematically showing a configuration of an 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 cross-sectional view schematically showing a configuration of an aluminum alloy material with an adhesive resin layer according to a modification of the first embodiment of the present invention. FIG. 4 is a flowchart showing a method of manufacturing the aluminum alloy material with an adhesive resin layer shown in FIG. FIG. 5 is a cross-sectional view schematically showing a configuration example of a joined body according to the second embodiment of the present 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 a cross-sectional view schematically showing another configuration example of the joined body according to the second embodiment of the present 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 a method for measuring the cohesive failure rate. FIG. 9B is a plan view schematically showing a method for measuring the cohesive failure rate.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that 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 film made of an oxide of aluminum containing silicon, formed on at least a part of the surface of the aluminum alloy base material, and the first film. An aluminum alloy material provided with a second film formed on at least a part of the silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof, The first coating contains Si at 15 atomic% or more and less than 80 atomic% and Mg at 0.1 atomic% or more and less than 30 atomic%, Cu is restricted to less than 0.6 atomic%, and Na An aluminum alloy material containing 0.01 to 25 atomic% of at least one alkali metal element selected from K, Li.

  FIG. 1 is a cross-sectional view schematically showing the configuration of the aluminum alloy material of the present embodiment. As shown in FIG. 1, an aluminum alloy material 10 of the present embodiment is made of an oxide of aluminum containing silicon in at least a part of the surface of an aluminum alloy substrate 3 (hereinafter also referred to as a substrate 3). Containing at least 1 atom% and less than 80 atom% and Mg at 0.1 atom% and less than 30 atom%, Cu being restricted to less than 0.6 atom%, and at least one selected from Na, K and Li A first film 1 (hereinafter also referred to as film 1) containing 0.01 to 25 atomic% of an alkali metal element is formed, and a trialkoxysilyl group is formed in at least a part of the first film 1 in the molecule. A second film 2 (hereinafter also referred to as film 2) containing a silane compound having two or more thereof, a hydrolyzate thereof, or a polymer thereof is formed.

[Substrate 3]
The substrate 3 is made of an aluminum alloy. The type of aluminum alloy that forms the base material 3 is not particularly limited, and various non-heat-treatable or heat-treated aluminums that are defined in JIS or approximate to JIS, depending on the use of the processed member. It can be used by appropriately selecting from alloys. 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 an Al—Cu—Mg based alloy (2000 series), an Al—Mg—Si based alloy (6000 series), and an Al—Zn—Mg based alloy (7000 series).

  For example, when the aluminum alloy material 10 of the present embodiment is used for an automobile member, the base material 3 preferably has a 0.2% proof stress of 100 MPa or more from the viewpoint of strength. Aluminum alloys that can form a base material that satisfies such characteristics include those containing relatively large amounts of magnesium, such as 2000 series, 5000 series, 6000 series, and 7000 series, and these alloys are necessary. Depending on the condition, it may be tempered. Among various aluminum alloys, it is preferable to use a 6000 series aluminum alloy because it has excellent age-hardening ability, has a relatively small amount of alloy elements, and is excellent in scrap recyclability and formability.

[First coating 1]
The first film 1 (hereinafter also referred to as film 1) is a film made of an oxide of aluminum containing silicon and formed on at least a part of the surface of the substrate 3. The coating 1 contains 0.1 atomic% or more and less than 30 atomic% of Mg and 15 atomic% or more and less than 80 atomic% of Si, Cu is restricted to less than 0.6 atomic%, and Li, Na, and 0.01 to 25 atomic% of at least one alkali metal element selected from K is contained. The film 1 has excellent corrosion resistance under a high temperature and humidity environment, and is provided to improve the adhesion durability. Hereinafter, the suitable range of each component amount 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 surface of one side of the substrate 3, but the present embodiment is not limited to this. For example, the film 1 may be formed on only a part of the surface of the substrate 3. Further, the coating 1 may be formed on both surfaces of the substrate 3.

<Mg content>
The aluminum alloy constituting the base material of the aluminum alloy material usually contains magnesium (Mg) as an alloy component, and an oxide film that is a composite oxide of aluminum and magnesium is formed on the surface of the base material 3. When formed, magnesium will be present in a concentrated state on the surface. For this reason, when an adhesive resin is formed on the oxide film, the surface magnesium becomes a weak boundary layer of the adhesive interface, and the initial adhesiveness is lowered.

  Further, in a high-temperature and humid environment where moisture, oxygen, chloride ions, etc. penetrate, it causes hydration of the interface with the adhesive resin layer and corrosion of the base material, thereby reducing the adhesion durability of the aluminum alloy material. Specifically, when the Mg content in the oxide film is 30 atomic% or more, the adhesion durability of the aluminum alloy material tends to decrease. Therefore, in the aluminum alloy material 10 of the present embodiment, it is preferable to limit the Mg content in the coating 1 to less than 30 atomic%. Thereby, adhesion durability can be improved. The Mg content of the film 1 is more preferably less than 25 atomic%, more preferably less than 20 atomic%, and still more preferably less than 10 atomic%, from the viewpoint of improving adhesion durability.

  On the other hand, the lower limit of the Mg content of the film 1 is preferably 0.1 atomic% or more from the viewpoint of economy. In addition, Mg content in the film | membrane 1 here can be measured by the high frequency glow discharge emission spectroscopy (GD-OES).

  The method for adjusting the Mg content of the film 1 is not particularly limited. For example, acids or mixed acids such as nitric acid, sulfuric acid and hydrofluoric acid, or potassium hydroxide, sodium hydroxide, silicate and carbonate A method of surface treatment with an alkaline solution containing the above can be applied. This method adjusts the Mg content of the film 1 by dissolving magnesium in an acid or alkali solution, and adjusts the treatment time, temperature, concentration and pH of the surface treatment liquid, and thereby in the film 1. The amount of Mg can be in the range described above. Even if Mg is contained to the extent of an impurity element, Mg may be concentrated in the film 1 when heat treatment is performed at a high temperature, and adjustment by surface treatment with acid or alkali is possible. Is necessary as appropriate. It is also possible to adjust the surface treatment chemical solution by containing Mg ions.

<Si content>
Silicon has the effect of improving the corrosion resistance of the coating 1 and stabilizing it in a wet environment, and also has the effect of improving the adhesion to the second coating (coating 2) described later. For this reason, it becomes possible to improve adhesion durability by making the film 1 contain silicon.

  However, when the Si content in the film 1 is less than 15 atomic%, the above-described effect tends to be small, and when the Si content is 80 atomic% or more, the film becomes thick and brittle. Adhesive strength is greatly reduced. Further, the spot weldability and the uniformity of the chemical conversion treatment tend to decrease. Therefore, in the aluminum alloy material 10 of the present embodiment, the Si content in the coating 1 is preferably 15 atomic percent or more and less than 80 atomic percent.

  From the viewpoint of improving the adhesion durability, the Si content in the coating 1 is preferably 15 atomic% or more, more preferably 20 atomic% or more, and further preferably 30 atomic% or more. Further, from the viewpoint of preventing the decrease in adhesive strength and the uniformity of spot weldability and chemical conversion treatment, the Si content in the film 1 is preferably less than 80 atomic% and more preferably less than 75 atomic%. Preferably, it is less than 70 atomic%.

  In order to control the Si content in the film 1, before forming the second film (film 2), the natural oxide film formed on the surface of the aluminum alloy substrate is treated with silicic acid such as sodium silicate or potassium silicate. It is important to perform treatment (silicate treatment) with an aqueous solution containing a salt (silicate aqueous solution).

<Cu content>
When the substrate 3 is excessively etched by a degreasing process, a pickling process, or the like when forming the film 1, Cu contained in the substrate 3 is concentrated on the surface, and the Cu content of the film 1 is increased. . When Cu is present on the surface of the film 1, the adhesion with the second film (film 2) is reduced.

  Therefore, in the aluminum alloy material of the present embodiment, the Cu content in the coating 1 is preferably restricted to less than 0.6 atomic%. In addition, it is more preferable that the amount of Cu in the film 1 is less than 0.5 atomic% from the viewpoint of improving the adhesion with the second film (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. For example, the same processing method as described in the numerical value 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 of Mg, Si, Cu, Li, Na, and K in the first coating 1 are measured by, for example, a high-frequency glow discharge emission spectroscopy (GD-OES). be able to. In this embodiment, each element except oxygen (O), nitrogen (N), and carbon (C), specifically aluminum (Al), magnesium (in the thickness direction of the base material 3 by GD-OES. Mg, copper (Cu), sodium (Na), lithium (Li), potassium (K), iron (Fe), titanium (Ti) and other metal elements and silicon (Si) and other elements were measured, and the results The value obtained by calculating the content of Mg, Si, Al, Cu, Na, Li, K, etc. as a percentage is taken as the amount of each element.

<Cation content>
As described above, since the film 1 is formed by treating the oxide film on the surface of the aluminum alloy substrate with an aqueous solution containing a silicate compound, it is inevitable as a charge guarantee for silicate ions taken into the oxide film. Contains an alkali metal contained in a silicate compound in the form of a cation (Na ⁺ , K ⁺ , Li ^+, etc.). This cation reacts with carbon dioxide in the atmosphere and precipitates as an alkali component in the film, and also plays a role of enhancing the corrosion resistance of the film. Accordingly, these cations are preferably contained in the coating 1 in an amount of 0.01 atomic% or more, and more preferably 0.02 atomic% or more.

  However, the proportion of cations in the coating 1 has a correlation with the proportion of silicon atoms. When the proportion of the cations in the coating 1 exceeds 25 atomic%, the proportion of silicon atoms in the coating 1 also becomes 80 atomic percent or more. As described above, there is a tendency for problems in adhesion and weldability to occur. As mentioned above, it is preferable that the ratio of the said cation in the membrane | film | coat 1 is 0.01 atomic% or more and 25 atomic% or less.

  In addition, content of these alkali metal elements (Na, K, Li) contained in the film 1 can be measured by GD-OES. Moreover, when multiple types of these cations are contained in the film 1, the total content thereof is preferably within the above range.

<Film thickness>
The film 1 preferably has a thickness of 1 to 30 nm. When the film thickness of the film 1 is less than 1 nm, the ester in the press oil used when producing a joined body or an automobile member from the rust preventive oil or the aluminum alloy material 10 used when the base material 3 is produced. Adsorption of components is suppressed. For this reason, even if it does not provide the membrane | film | coat 1, the degreasing | defatting property, chemical conversion treatment property, and adhesion durability of the aluminum alloy material 10 are securable. 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 inferior and practicality tends to be lowered. Moreover, excessive etching by alkali degreasing or acid causes the Cu contained in the base material 3 to be concentrated on the surface, and 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 unevenness is easily formed on the surface. When the surface of the coating 1 is uneven, for example, chemical conversion spots are likely to occur during the chemical conversion treatment performed before the coating process in automobile applications, leading to a decrease in chemical conversion. The film thickness of the film 1 is preferably 2 nm or more and less than 25 nm, and more preferably 3 nm or more and less than 20 nm, from the viewpoints of chemical conversion and productivity.

The coating amount of the silicate aqueous solution is preferably adjusted so that the coating amount after drying is 0.3 mg / m ² or more and 30 mg / m ² or less from the viewpoint of obtaining a sufficient effect of improving the adhesion durability.
More preferably, the coating amount after drying is adjusted to 0.5 mg / m ² or more and 25 mg / m ² or less, more preferably 1 mg / m ² or more and 20 mg / m ² or less. If the coating amount of the silicate aqueous solution is too small, the amount of silicate is too small, and good adhesion durability may not be obtained. Moreover, when the application amount of the silicate aqueous solution becomes too large, the formed film becomes too thick, peeling occurs in the film, and the adhesion durability may be impaired.

[Second coating 2]
The second film 2 (hereinafter also referred to as film 2) contains, as a main component, a silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof. Silane compounds with multiple hydrolyzable trialkoxysilyl groups in the molecule not only form dense siloxane bonds by self-polymerization, but also form highly chemically reactive bonds with metal oxides. Therefore, the wet durability of the film 1 can be further improved. Moreover, the film containing the silane compound, its hydrolyzate or its polymer has high mutual solubility with organic compounds such as machine oils and adhesives, and even if machine oil adheres to the film, the influence can be mitigated. For this reason, it also plays a role in preventing a decrease in adhesion durability due to oiling. Although the kind of the silane compound is not particularly limited, from the economical viewpoint, a silane compound (bissilane compound) having two hydrolyzable trialkoxysilyl groups in the molecule is preferable. For example, bistrialkoxysilylethane, bistrialkoxy Silylbenzene, bistrialkoxysilylpropylhexane, bistrialkoxysilylpropylamine, bistrialkoxysilylpropyltetrasulfide, and the like can be used. In particular, bistriethoxysilylethane (BTSE) is preferable from the viewpoint of versatility and economy. Here, as said silane compound, its hydrolyzate, or its polymer, only 1 type may be used independently and it may be used in combination of 2 or more type.

  The amount of the silane compound having a plurality of 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. It is more preferable that the content is 0.5% by mass or more. Moreover, although it does not specifically limit as an upper limit, For example, 100 mass% may be sufficient.

  The film 2 further includes a silane coupling agent having a reactive functional group capable of chemically bonding to the organic resin component, a hydrolyzate thereof or a polymer thereof in addition to the silane compound, a hydrolyzate thereof or a polymer thereof. You may go out. 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 above silane compound, its hydrolyzate or its polymer, a chemical bond is formed between the film 2 and the resin, and adhesion durability is improved. It can be further increased. In addition, the functional group of a silane coupling agent is not limited to what was mentioned above, The silane coupling agent which has various functional groups can be selected suitably according to the adhesive resin to be used. Preferable specific examples of the silane coupling agent include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-aminoethyl) -aminopropyltrimethoxysilane, 3- (N- Aminoethyl) -aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxy Examples thereof include propyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. Here, as a silane coupling agent, only 1 type may be used independently and it may be used in combination of 2 or more type.

However, if the coating amount of the coating 2 is too thin, it is easily affected by the elements on the surface of the substrate 3, and if the coating amount of the coating 2 is too large, the coating 2 itself cohesively breaks down, resulting in adhesion durability. May decrease. Therefore, from the viewpoint of improving the adhesion durability, the coating amount after drying of the coating ² is preferably 0.01 mg / m ² or more and less than 30 mg / m ² . Further, the coating amount after drying of the coating 2 is more preferably 0.2 mg / m ² or more and less than 20 mg / m ² , and further preferably 0.5 mg / m ² or more and less than 10 mg / m ² .

[Production method]
Next, the manufacturing method of the aluminum alloy material of this embodiment is demonstrated. FIG. 2 is a flowchart showing a method for manufacturing the aluminum alloy material 10 of the present embodiment shown in FIG.
As shown in FIG. 2, when manufacturing the aluminum alloy material 10 of this embodiment, base material preparation process S1, 1st film formation process S2, and 2nd film formation process S3 are performed. Hereinafter, each step will be described.

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

  In the cold rolling process, it is preferable to set the temperature of rough annealing or intermediate annealing to 300 ° C. or higher, and thereby the effect of improving formability is more exhibited. Moreover, it is preferable that the temperature of rough annealing or intermediate annealing shall be 580 degrees C or less, and this becomes easy to suppress the fall of the moldability by generation | occurrence | production of burning. On the other hand, the final cold rolling rate is preferably 5% or more, and thereby, the effect of improving the formability is more exhibited. In addition, the conditions of homogenization heat processing and hot rolling are not specifically limited, It can carry out on the conditions in the case of obtaining a hot rolled sheet normally. Further, intermediate annealing may not be performed.

<Step S2: First film formation step>
In the first film formation process (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 produced in the base material production process of step S1. In the present embodiment, the first film forming step (step S2) specifically includes, for example, a heat treatment stage in which the base material 3 is heat-treated to form an oxide film on the surface of the base material 3, and the heat treatment stage. A subsequent etching process step and a silicate treatment step. Here, the oxide film formed on the surface of the substrate 3 is treated with an aqueous solution containing silicate as a silicate treatment step. Thereby, preferably, the film 1 is formed so that the Mg amount, the Si amount, the Cu amount, and the total amount of Na, K, and Li in the film 1 are in a specific range.

  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. Further, the heat treatment also has an effect of adjusting the strength of the aluminum alloy material 10. The heat treatment performed here is a solution treatment when the substrate 3 is formed of a heat-treatable aluminum alloy, and is annealed when the substrate 3 is formed of a non-heat-treatable aluminum alloy. It is heat processing in (final annealing).

  This heat treatment is preferably rapid heating at a heating rate of 100 ° C./min or more from the viewpoint of strength improvement. Moreover, the strength of the aluminum alloy material 10 and the strength after heating (baking) of the aluminum alloy material 10 can be further increased by setting the heating temperature to 400 ° C. or higher and performing rapid heating. On the other hand, by setting the heating temperature to 580 ° C. or less and performing rapid heating, it is possible to suppress a decrease in formability due to the occurrence of burning. Furthermore, from the viewpoint of improving 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., for example, an oxide film having a film thickness of 1 to 30 nm is formed on the surface of the base material 3. In addition, you may perform alkali degreasing | defatting etc. as needed before heat processing.

  The surface treatment of the oxide film formed by the above-described method is preferably performed so that the Mg amount, Si amount, Cu amount, and the total amount of Na, K, and Li in the first film are in a specific range.

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

  Also, the chemical solution used for alkali cleaning (alkali degreasing) is not particularly limited, and for example, a solution containing at least one selected from the group selected from sodium hydroxide and potassium hydroxide can be used. . In addition, the conditions for 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 are not particularly limited. Conditions of ° C. and treatment time of 1 to 120 seconds can be applied.

  In addition, when performing alkali cleaning, it is preferable to perform pickling after alkali cleaning. The reason for this is as follows. That is, with alkali cleaning, it is difficult to remove Mg on the substrate surface, and the amount of etching needs to be increased due to the presence of Mg on the substrate surface. However, increasing the etching amount causes the concentration of Cu, so it is necessary to remove Mg by pickling.

  Moreover, it is preferable to perform rinsing after washing with each chemical solution. 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, and ion exchange water.

  In addition, excessive etching of the aluminum alloy containing copper causes copper concentration on the surface, and causes deterioration of the adhesive resin in a high temperature and humid environment which is a deteriorated environment. Accordingly, the processing 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 present specification is the dissolution amount of the oxide film or the base material including the oxide film, and the decrease in weight before and after the etching treatment is measured, and the thickness (film thickness) is measured. ). In addition, the conversion from the weight reduction amount to the film thickness is performed by calculating the aluminum thickness using the aluminum density of 2.7 g / cm ³ for convenience. 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 defined as the etching amount.

  Moreover, the base material 3 which has an oxide film as a silicate process step is processed with the aqueous solution (It is also called silicate aqueous solution or 1st aqueous solution.) Containing a silicate. Here, the treatment with the silicate aqueous solution includes not only the application of the silicate aqueous solution but also the immersion in the silicate aqueous solution. When the treatment with the silicate aqueous solution is performed, hydrogen carbonate and silicon dioxide are generated, and the oxide film becomes a dense film 1, which improves the strength of the film itself and also improves the corrosion resistance. Note that the silicate treatment stage is performed as the final stage of film formation in the film formation process, and no pickling is performed after the silicate treatment. However, when washing and / or drying is performed after the treatment with the silicate aqueous solution, the washing and / or drying is also included in the silicate treatment stage, and the order thereof is not limited.

  Here, the silicate concentration in the aqueous silicate solution is not particularly defined, but from the viewpoint of practicality, it is desirable to treat with an aqueous solution of 0.001% by mass or more. In addition, when rinsing with water after silicate treatment, it is desirable to treat with a silicate aqueous solution having a silicate concentration exceeding 0.01% by mass, and the pH of the silicate aqueous solution is also particularly limited. Although it is not a thing, since it may precipitate in liquids other than alkali, it is preferable to set it as pH9 or more. Further, when rinsing is not performed after the silicate treatment, it is desirable to treat with a silicate aqueous solution having a silicate concentration of 0.001% by mass or more and 0.5% by mass or less, and 0.01% by mass or more. More preferably, it is 0.4 mass% or less.

The type of silicate contained in the silicate aqueous solution is not particularly limited. For example, basic silicates include silicates of alkali metals such as lithium, sodium, and potassium, and ammonium silicates. Can be mentioned. Here, as a silicate, only 1 type may be used independently and may be used in combination of 2 or more type.
Examples of the lithium silicate include lithium silicate.
Examples of sodium silicate (mNa ₂ O · nSiO ₂ can be expressed as n / m in a molar ratio below) include, for example, crystalline sodium orthosilicate (n / m: about 0.5), meta Sodium silicate (n / m: around 1), layered sodium silicate (n / m: in the range of about 2 to 3), or amorphous sodium silicate, or liquid water glass (JIS No. 1, 2 and 3).
As potassium silicate, potassium silicate etc. are mentioned, for example.

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

  Moreover, after processing an oxide film with silicate aqueous solution, you may wash with water (rinsing) as needed.

  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, and still more preferably 90 ° C. or higher. In addition, if the drying temperature is too high, the characteristics of the aluminum alloy are affected. Therefore, 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. Moreover, the said drying time becomes like this. Preferably it is 20 minutes or less, More preferably, it is 5 minutes or less, More preferably, it is 2 minutes or less.

  In the film forming process of step S1 described above, the silicate treatment stage is performed after the etching process stage, but these may be performed in a single process. Specifically, for example, the oxide film may be treated using a neutral or alkaline aqueous solution containing silicate.

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

The coating amount of the silane compound 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 the silane compound with a solvent (water, organic solvent, or a mixture thereof) to reduce the solid content concentration or viscosity, or adjusting the wet coating amount by the coater count It can be easily controlled. The concentration of the silane compound having a plurality of hydrolyzable trialkoxysilyl groups in the molecule, the hydrolyzate thereof or the polymer thereof in the second aqueous solution is not particularly limited, but for example 0.001% by mass to It is 5 mass%, More preferably, it is 0.003 mass%-2 mass%, More preferably, it is 0.005 mass%-1 mass%.

  Moreover, the application | coating method of silane compound aqueous solution is not specifically limited, The existing method can be applied. Specifically, a coating method by dipping, a method using various coating machines such as a roll coater, a bar coater, a gravure coater, a micro gravure coater, a reverse gravure coater, and a dip coater, a spray coating method, and the like can be applied.

  The silane compound aqueous solution is dried by heating after coating. By applying heat 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 further promoted. Densify and stabilize. The heating temperature is preferably 60 ° C. or higher, more preferably 75 ° C. or higher, and still more preferably 90 ° C. or higher. In addition, when the heating temperature is too high, it affects the decomposition of the functional group of the silane compound and the characteristics of the aluminum alloy. Therefore, the heating temperature is preferably 250 ° C. or less, more preferably 200 ° C. or less, and even more preferably 150 ° C. It is as follows. The drying time is preferably 2 seconds or more, more preferably 5 seconds or more, and further preferably 10 seconds or more, although it depends on the heating temperature. Moreover, the said drying time becomes like this. Preferably it is 20 minutes or less, More preferably, it is 5 minutes or less, More preferably, it is 2 minutes or less.

<Other processes>
In the manufacturing process of the aluminum alloy material 10 of the present embodiment, other processes may be included between or before and after each process as long as the processes described above are not adversely affected. For example, you may provide the preliminary aging treatment process which performs a preliminary aging treatment after 2nd film formation process S3. This preliminary aging treatment is preferably performed by heating at 40 to 120 ° C. within a period of 72 hours at a low temperature of 8 to 36 hours. By performing pre-aging treatment under these conditions, it is possible to improve moldability and strength after baking. In addition, for example, a foreign matter removing step for removing foreign matter on the surface of the aluminum alloy material 10 or a defective product removing step for removing defective products generated in each step may be performed.

  And the manufactured aluminum alloy material 10 may apply | coat machine oil, such as press oil, to the surface before preparation of a joined body or before processing to the member for motor vehicles. 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 methods and conditions for applying the normal press oil can be widely applied. For example, a press containing ethyl oleate as an ester component What is necessary is just to immerse the aluminum alloy material 10 in oil. The ester component is not limited to ethyl oleate, and various materials such as butyl stearate and sorbitan monostearate can be used.

  Here, since the aluminum alloy material 10 of this embodiment is provided with the coating 2 rich in the solubility of machine oil on the outermost surface, even after the machine oil is applied, the adhesive resin is satisfactorily bonded thereon. be able to.

  As described above in detail, in this embodiment, the oxide film formed on the surface of the aluminum alloy substrate 3 is silicate-treated to form the film 1 made of an aluminum oxide containing silicon, and then silane. The aluminum alloy material 10 is manufactured by processing the first film with the compound aqueous solution to form the film 2. Thereby, the covalent bond of a silane compound and a metal oxide is formed in the interface of the membrane | film | coat 1 and the membrane | film | coat 2, and the outstanding adhesive durability can be obtained. Moreover, if the amount of Mg in the film 1 is adjusted to a specific range, the formation of an oxide film that is mechanically brittle and has low corrosion resistance can be suppressed, and deterioration of the adhesive resin interface can be suppressed. Further, if the coating 1 contains at least one of a specific amount of Si and a specific amount of Na, K and Li, and the amount of Cu in the coating 1 is regulated to be less than a specific amount, the adhesion between the coating 1 and the coating 2 Will improve. As a result, even when the aluminum alloy material 10 of the present embodiment is exposed to a high-temperature and humid environment, the interfacial peeling is suppressed, and a decrease in adhesive strength can be suppressed over a long period of time.

(Modification of the first embodiment)
Next, an aluminum alloy material with an adhesive resin layer according to a modification of the first embodiment of the present invention will be described. FIG. 3 is a cross-sectional view schematically showing a configuration of an aluminum alloy material with an adhesive resin layer according to this modification. In FIG. 3, the same components as those of the aluminum alloy material 10 shown in FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted. As shown in FIG. 3, the aluminum alloy material 11 with an adhesive resin layer of the present modification is an adhesive resin layer made of an adhesive resin so as to cover the film 1 and the film 2 of the aluminum alloy material of the first embodiment described above. 4 is 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 the adhesive resin layer of the present modification is joined to another member via the adhesive resin layer 4. The other members include another aluminum alloy material in which a film is formed as in the case of the aluminum alloy material 11 with the adhesive resin layer, an aluminum alloy material in which no oxide film is formed, a resin molded body, and the like. .

  The adhesive resin that constitutes the adhesive resin layer 4 is not particularly limited. When an aluminum alloy material such as an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, or an acrylic resin is conventionally joined. The adhesive resin that has been used can be used. Of these, epoxy resins are preferable from the viewpoint of adhesive strength. Further, only one kind of adhesive resin may be used, or a plurality of adhesive resins may be used in combination.

  The thickness of the adhesive resin layer 4 is not particularly limited, but is preferably 10 to 500 μm, and more preferably 50 to 400 μm. When the thickness of the adhesive resin layer 4 is less than 10 μm, the aluminum alloy material 11 with the adhesive resin layer and the 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, the manufacturing method of the aluminum alloy material 11 with the adhesive resin layer of this modification is demonstrated. FIG. 4 is a flowchart showing a method for manufacturing the aluminum alloy material 11 with an adhesive resin layer of the present modification. As shown in FIG. 4, when manufacturing the aluminum alloy material 11 with the adhesive resin layer of this modification, in addition to step S1-S3 mentioned above, adhesive resin layer formation process S4 is performed.

<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, it is heated and pressure-bonded, or dissolved in a solvent to obtain 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.

  Moreover, also in the aluminum alloy material 11 with the adhesive resin layer of this modification, the first film forming step S2, the second film forming step S3, and / or the adhesive resin layer forming step S4, as in the first embodiment described above. After this, a preliminary aging treatment step for performing preliminary aging treatment may be provided.

  In the aluminum alloy material with an 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 producing a joined body or an automobile member. can do. The configuration and effects other than those described above in the aluminum alloy material with an adhesive resin layer of the present modification are the same as those in the first embodiment described above.

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

[Composition structure]
In the joined body of this embodiment, for example, as in the joined body 20 shown in FIG. 5, the two aluminum alloy materials 10 shown in FIG. 1 are opposed to each other on the surfaces on which the film 1 and the film 2 are formed. It can be set as the structure which has arrange | positioned and joined via the adhesive resin 5. FIG. That is, in the bonded body 20, one surface of the adhesive resin 5 is bonded to the film 2 side of one aluminum alloy material 10 and the other surface is bonded to the film 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 adhesive resin layer 4 described above can be used. Specifically, an epoxy resin, a urethane resin, a nitrile resin, a nylon resin, an acrylic resin, or the like can be used as the adhesive resin 5. Moreover, although the thickness of the adhesive resin 5 is not specifically limited, 10-500 micrometers is preferable from a viewpoint of adhesive strength improvement, More preferably, it is 50-400 micrometers.

  As described above, in the joined body 20, both surfaces of the adhesive resin 5 are the film 1 and the film 2 of the aluminum alloy material 10 of the first embodiment. Even if it does, the adhesive strength of the interface of the adhesive resin 5 and the membrane | film | coat 1 and the membrane | film | coat 2 does not fall easily, and adhesion durability improves. Moreover, in the joined body 20 of this embodiment, the adhesive durability at the interface is improved in all adhesive resins conventionally used for joining aluminum alloy materials without being affected by the type of the adhesive resin 5.

  Moreover, like the joined body 21a shown in FIG. 6A or the joined body 21b shown in FIG. 6B, the surface on which the coating 1 and the coating 2 of the aluminum alloy material 10 shown in FIG. It can also be set as the structure which joined the other aluminum alloy material 6 or the resin molding 7 in which the 1st membrane | film | coat and the 2nd membrane | film | coat are not formed.

  Here, as the other aluminum alloy material 6 in which the first film and the second film are not formed, the same material as the base material 3 described above can be used, and specifically, it is defined in JIS. Or what consists of various non-heat processing type | molds or heat processing type aluminum alloys approximate 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 ( A fiber reinforced plastic molded body formed of various fiber reinforced plastics such as DFRP) and Zylon reinforced plastic (ZFRP) can be used. By using these fiber-reinforced plastic molded bodies, it is possible to reduce the weight of the joined body while maintaining a certain strength.

  In addition to the above-mentioned fiber reinforced plastic, the resin molded body 7 includes polypropylene (PP), acrylic-butadiene-styrene copolymer (ABS) resin, polyurethane (PU), polyethylene (PE), and polyvinyl chloride (PVC). , Nylon 6, nylon 6,6, polystyrene (PS), polyethylene terephthalate (PET), polyamide (PA), polyphenylene sulfide (PPS), polybutylene terephthalate (PBT), polyphthalamide (PPA), etc. Not engineering plastics can be used.

  In the joined bodies 21a and 21b shown in FIGS. 6A and 6B, since one surface of the adhesive resin 5 is joined to the coating 1 and the coating 2 side of the aluminum alloy material 10, as in the joined body 20 described above, a member for an automobile. When used in the above, even when exposed to a high temperature and humidity environment, the adhesion durability at the interface is improved without being affected by the type of the adhesive resin. Moreover, since the joined body 21b shown to FIG. 6B has joined the aluminum alloy material 10 and the resin molding 7, it is lightweight compared with the joined body of aluminum alloy materials, By using this joined body 21b, Further weight reduction of the automobile can be realized. The other configurations and effects of the joined bodies 21a and 21b shown in FIGS. 6A and 6B are the same as those of the joined body 20 shown in FIG.

  Furthermore, like the joined body 22 shown in FIG. 7, the aluminum alloy material 11 with the adhesive resin layer provided with the adhesive resin layer 4 shown in FIG. 3, and the aluminum alloy material 10 not provided with the adhesive resin layer 4 shown in FIG. It can also be set as the structure which joined. Specifically, the film 1 and the film 2 side 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 coating 1 and coating 2 side 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 are respectively connected via the adhesive resin layer 4 of the aluminum alloy material 11 with the adhesive resin layer. It is the structure arrange | positioned so that it may mutually oppose.

  In the joined body 22, both surfaces of the adhesive resin layer 4 are joined to the film 1 and film 2 side of the aluminum alloy material 10 and the film 1 and film 2 side of the aluminum alloy material 11 with the adhesive resin layer, respectively. Similar to the body 20, when the joined body 22 is used as a member for an automobile, even if it is exposed to a high-temperature wet environment, the adhesion durability at the interface is improved without being affected by the type of the adhesive resin. In addition, the structure and effect other than the above in the joined body 22 shown in FIG. 7 are the same as those of the joined body 20 shown in FIG.

  Further, as in the joined body 23a shown in FIG. 8A or the joined body 23b shown in FIG. 8B, the first side of the aluminum resin material 11 with the adhesive resin layer 4 provided with the adhesive resin layer 4 shown in FIG. Another aluminum alloy material 6 or a resin molded body 7 such as a fiber reinforced plastic molded body on which the film and the second film are not formed may be joined. In these joined bodies 23a and 23b, since one surface of the adhesive resin layer 4 is joined to the coating 1 and the coating 2 side of the aluminum alloy material 11 with the adhesive resin layer, the joined body 23 is formed in the same manner as the joined body 20 described above. When used for automobile members, even when exposed to a high temperature and humidity environment, the adhesion durability at the interface is improved without being affected by the type of adhesive resin.

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

[Production method]
A conventionally known joining method can be used as the manufacturing method of the joined bodies 20 to 23, particularly the joining method. The method for forming the adhesive resin 5 on the aluminum alloy material is not particularly limited. For example, an adhesive sheet prepared in advance using the adhesive resin 5 may be used, or the adhesive resin 5 may be formed on the surface of the film 2. You may form by spraying or apply | coating to. The bonded bodies 20 to 23 may be coated with press oil on the surfaces thereof before being processed into automobile members, similarly to the aluminum alloy material 10 and the aluminum alloy material 11 with the adhesive layer.

  Although not shown, when an aluminum alloy material in which the film 1 and the film 2 are formed on both sides is used for the joined body of the present embodiment, these aluminum alloy materials are interposed via the adhesive resin 5 or the adhesive resin layer 4. The other aluminum alloy material or the resin molded body on which the film 1 and the film 2 are not formed can be further joined.

(Third embodiment)
Next, the automotive member according to the third embodiment of the present invention will be described. The member for motor vehicles of this embodiment uses the joined object of a 2nd embodiment mentioned above, for example, is a panel for motor vehicles.

  Moreover, although the manufacturing method of the member for motor vehicles of this embodiment is not specifically limited, A conventionally well-known manufacturing method is applicable. For example, the joined members 20 to 23b shown in FIGS. 5 to 8B are cut or pressed to produce a predetermined-shaped automobile member.

  Since the automobile member according to the present embodiment is manufactured from the joined body according to the second embodiment described above, the adhesive resin or the adhesive resin layer and the oxide film (first film) can be formed even when exposed to a high temperature and wet environment. The elution of the aluminum alloy base material can be suppressed with almost no influence of hydration. As a result, in the automotive member of this embodiment, it is possible to suppress interfacial peeling when exposed to a high-temperature and humid environment, and to 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 produced by the following method and conditions, and adhesion durability and the like were evaluated.

<Example 1>
Using a 6000 series aluminum alloy of JIS 6016 (Mg: 0.54 mass%, Si: 1.11 mass%, Cu: 0.14 mass%), an aluminum alloy cold-rolled sheet having a thickness of 1 mm was produced. And this cold-rolled board was cut | disconnected to length 100mm and width 25mm, it was set as the base material, and it heat-processed to the substance ultimate temperature 550 degreeC, and cooled.
Subsequently, the substrate was alkali degreased with an aqueous solution of pH 13 containing potassium hydroxide at 50 ° C. for 40 seconds, and further pickled with a pH 1 solution containing sulfuric acid and hydrofluoric acid at a temperature of 50 ° C. for a treatment time of 40 seconds, and dried. I let you. Thereafter, an aqueous solution containing 0.0122% by mass of sodium metasilicate (sodium metasilicate aqueous solution) was uniformly applied to the surface with a bar coater, and heated and dried at 100 ° C. for 1 minute to form a first film. Further, an aqueous solution (BTSE aqueous solution) containing 0.010% by mass of bistriethoxysilylethane (BTSE) was uniformly applied to the surface on the first film side with a bar coater, and heated and dried at 100 ° C. for 1 minute, A film was formed to produce the aluminum alloy material of Example 1.

Next, after the press oil was diluted with toluene to adjust the concentration, it was applied to the surface on the second film side of the aluminum alloy material of Example 1 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 BTSE aqueous solution was 0.1% by mass. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 2 so that the application quantity after drying might be 1 g / m < ² >.

<Example 3>
An aluminum alloy material of Example 3 was obtained in the same manner as Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.0244 mass% and the concentration of the BTSE aqueous solution was 0.05 mass%. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd membrane | film | coat side of the aluminum alloy material of Example 3 so that the application quantity after drying might be 1 g / m < ² >.

<Example 4>
An aluminum alloy material of Example 4 was obtained in the same manner as Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.24 mass% and the concentration of the BTSE aqueous solution was 0.05 mass%. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 4 so that the application quantity after drying might be 1 g / m < ² >.

<Example 5>
An aluminum alloy material of Example 5 was obtained in the same manner as Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.061% by mass and the concentration of the BTSE aqueous solution was 1% by mass. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd membrane | film | coat side of the aluminum alloy material of Example 5 so that the application quantity after drying might be 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 sodium metasilicate aqueous solution was 0.061 mass% and the concentration of the BTSE aqueous solution was 0.01 mass%. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd membrane | film | coat side of the aluminum alloy material of Example 6 so that the application quantity after drying might be 1 g / m < ² >.

<Example 7>
An aluminum alloy material of Example 7 was obtained in the same manner as Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.061 mass% and the concentration of the BTSE aqueous solution was 0.5 mass%. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 7 so that the application quantity after drying might be 1 g / m < ² >.

<Example 8>
An aluminum alloy material of Example 8 was obtained in the same manner as Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.12% by mass and the concentration of the BTSE aqueous solution was 0.08% by mass. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 8 so that the application quantity after drying might be 1 g / m < ² >.

<Example 9>
Example 1 except that after applying a sodium metasilicate aqueous solution having a concentration of 0.61% by mass, the substrate was washed with water, heated and dried at 100 ° C. for 1 minute, and then a BTSE aqueous solution having a concentration of 0.1% by mass was applied. In the same manner as described above, an aluminum alloy material of Example 9 was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 9 so that the application quantity after drying might be 1 g / m < ² >.

<Example 10>
An aluminum alloy material of Example 10 was obtained in the same manner as Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.024 mass% and the concentration of the BTSE aqueous solution was 0.005 mass%. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 10 so that the application quantity after drying might be 1 g / m < ² >.

<Example 11>
Implementation was performed except that the concentration of the sodium metasilicate aqueous solution was 0.024% by mass, 0.005% by mass of BTSE was added, and 0.05% by mass of 3-aminopropyltriethoxysilane was added. In the same manner as in Example 1, an aluminum alloy material of Example 11 was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 11 so that the application quantity after drying might be 1 g / m < ² >.

<Example 12>
The concentration of the sodium metasilicate aqueous solution was 0.024% by mass, except that a BTSE aqueous solution containing 0.005% by mass of BTSE and further adding 0.05% by mass of 3-glycidoxypropyltriethoxysilane was used. In the same manner as in Example 1, an aluminum alloy material of Example 12 was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 12 so that the application quantity after drying might be 1 g / m < ² >.

<Example 13>
Example 13 was carried out in the same manner as in Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.061% by mass, and an aqueous solution containing 0.05% by mass of bistriethoxysilylbenzene (BTSB) was used instead of the BTSE aqueous solution. An aluminum alloy material was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 13 so that the application quantity after drying might be 1 g / m < ² >.

<Example 14>
Example 1 was carried out in the same manner as in Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.061% by mass, and an aqueous solution containing 0.1% by mass of bistriethoxysilylpropylamine (BTSA) was used instead of the BTSE aqueous solution. 14 aluminum alloy materials were obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 14 so that the application quantity after drying might be 1 g / m < ² >.

<Example 15>
Implementation was carried out in the same manner as in Example 1 except that the concentration of the sodium metasilicate aqueous solution was 0.12% by mass, and an aqueous solution containing 0.15% by mass of bistriethoxysilylpropyltetrasulfide (BTSS) was used instead of the BTSE aqueous solution. The aluminum alloy material of Example 15 was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 15 so that the application quantity after drying might be 1 g / m < ² >.

<Example 16>
As in Example 8, except that kanemite (trade name: Prefeed, manufactured by Tokuyama Siltec Co., Ltd., n / m = 2) was used as the silicate compound in the silicate aqueous solution at a concentration of 0.10% by mass. The aluminum alloy material of Example 16 was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 16 so that the application quantity after drying might be 1 g / m < ² >.

<Example 17>
Example 17 was the same as Example 8 except that No. 3 water glass (manufactured by Wako Pure Chemical Industries, n / m = 3) was used at a concentration of 0.09% by mass as the silicate compound in the silicate aqueous solution. An aluminum alloy material was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of Example 17 so that the application quantity after drying might be 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 sodium metasilicate aqueous solution was 0.61% by mass and the concentration of the BTSE aqueous solution was 0.05% by mass. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd membrane | film | coat side of the aluminum alloy material of the comparative example 1 so that the application quantity after drying might be 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 treatment with the sodium metasilicate aqueous solution was not performed and the concentration of the BTSE aqueous solution was changed to 0.18% by mass. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd membrane | film | coat side of the aluminum alloy material of the comparative example 2 so that the application quantity after drying might be 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 the treatment with the BTSE aqueous solution was not performed. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 1st membrane | film | coat side of the aluminum alloy material of the comparative example 3 so that the application quantity after drying might be 1 g / m < ² >.

<Comparative Example 4>
Comparative Example 4 was carried out in the same manner as in Example 1 except that the alkali degreasing and pickling processes were not performed, the concentration of the sodium metasilicate aqueous solution was 0.061% by mass, and the concentration of the BTSE aqueous solution was 0.10% by mass. An aluminum alloy material was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd film | membrane side of the aluminum alloy material of the comparative example 4 so that the application quantity after drying might be 1 g / m < ² >.

<Comparative Example 5>
The aluminum alloy of Comparative Example 5 was prepared in the same manner as in Example 1 except that the pickling treatment was performed for 360 seconds, the concentration of the sodium metasilicate aqueous solution was 0.061 mass%, and the concentration of the BTSE aqueous solution was 0.10 mass%. The material was obtained. Moreover, the press oil diluted with toluene was apply | coated to the surface by the side of the 2nd membrane | film | coat side of the aluminum alloy material of the comparative example 5 so that the application quantity after drying might be 1 g / m < ² >.

<Measurement of first film component>
For the first film before forming the second film, measurement was performed while sputtering in the film thickness direction by high-frequency glow discharge optical emission spectrometry (GD-OES: model JY-5000RF manufactured by Horiba Joban Yvon), aluminum (Al), Metal elements such as magnesium (Mg), sodium (Na), potassium (K), lithium (Li), copper (Cu), iron (Fe) and titanium (Ti), and oxygen (O), nitrogen (N), The amount of each component was measured for elements such as carbon (C), silicon (Si) and sulfur (S). For magnesium (Mg), sodium (Na), potassium (K), lithium (Li), copper (Cu), and silicon (Si), the maximum concentration in the first film was defined as the film concentration in the film. Since aluminum (Al) is affected by the base material in the vicinity of the interface between the base material and the first film, the concentration of the outermost surface is defined as the film concentration of aluminum (Al). 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 concentration calculation of each element, the concentration was calculated excluding oxygen (O) and carbon (C). Note that oxygen (O) is highly likely to be affected by contamination at the outermost surface and in the vicinity thereof, and it is difficult to measure the exact concentration. However, the first film of all samples contains oxygen (O). It was clear that The results are shown in Table 1.

<Measurement of etching amount>
The amount of etching is the amount of dissolution of the oxide film and the base material including the oxide film, and the amount of decrease in weight before and after the etching treatment was measured and estimated as the thickness (film thickness). In addition, the conversion from the decrease in weight to the film thickness was performed by calculating the aluminum thickness using the aluminum density of 2.7 g / cm ³ for convenience.

<Measurement of coating amount of first and second coatings>
The film amounts of the first and second films formed by the treatment with the silicic acid compound and the silane compound aqueous solution were measured by fluorescent X-rays. Specifically, the amount of silicon in each of the first film after the silicate compound treatment and the second film after the silane compound treatment is measured by fluorescent X-rays, and the calibration curve is used to determine the intensity of the fluorescent X-ray and the film amount. Each was calculated by performing conversion. The results are shown in Table 1.

<Cohesive failure rate (adhesion durability)>
9A and 9B are diagrams schematically showing a method of 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 configuration are wrapped with a thermosetting epoxy resin adhesive resin with a wrap length of 10 mm (adhesion area: 25 mm × 10 mm). ).
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 (average particle size 250 μm) was added to the adhesive resin 35 so that the thickness of the adhesive resin 35 was 250 μm.
After superposition, 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 at 40 ° C. and 5% concentration for 20 days, and then pulled at a rate of 50 mm / min with a tensile tester, and the cohesive failure rate of the adhesive resin at the bonded portion was evaluated. The cohesive failure rate was calculated based on Equation 1 below. In addition, in the following numerical formula 1, the test specimen a was used as one side after the tension of the adhesion test specimen, and the test specimen b was used as the other side.

  Three pieces were prepared for each test condition, and the cohesive failure rate was an average value of the three pieces. The evaluation criteria are that the cohesive failure rate is less than 60% defective (x), 60% or more and less than 70% is slightly good (Δ), 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 film is higher than the range defined in the present invention, and the Na concentration in the first film is defined in the present invention. It was higher than the range, and the adhesion durability was poor.
In addition, the aluminum alloy material of Comparative Example 2 had a poor adhesion durability because the Si concentration in the first film was lower than the range specified in the present invention.
Moreover, the aluminum alloy material of Comparative Example 3 did not have the second film, and had poor adhesion durability.
Moreover, the aluminum alloy material of Comparative Example 4 had a Mg concentration in the first film higher than the range specified in the present invention, and had poor adhesion durability.
Moreover, the aluminum alloy material of Comparative Example 5 had a Cu concentration in the first film higher than the range specified in the present invention, and had poor adhesion durability.

  On the other hand, the aluminum alloy materials of Examples 1 to 17 that satisfy each requirement defined in the present invention had good wet durability under a high temperature and high humidity environment.

DESCRIPTION OF SYMBOLS 1 1st membrane | film | coat 2 2nd membrane | film | coat 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 object 20, 21a, 21b, 22, 23a, 23b Joining Body 31a, 31b Specimen

Claims (16)

An aluminum alloy substrate;
A first coating made of an oxide of aluminum containing silicon, formed on at least part of the surface of the aluminum alloy substrate;
An aluminum alloy material provided with a second film formed on at least a part of the first film, the silane compound having two or more hydrolyzable trialkoxysilyl groups in the molecule, a hydrolyzate thereof, or a polymer thereof. Because
The first coating contains Si at 15 atomic% or more and less than 80 atomic% and Mg at 0.1 atomic% or more and less than 30 atomic%, Cu is restricted to less than 0.6 atomic%, and Na An aluminum alloy material containing 0.01 to 25 atomic% of at least one alkali metal element selected from K, Li.   The aluminum alloy material according to claim 1, wherein the amount of Si in the first coating is 20 atomic percent or more and less than 75 atomic percent.   The aluminum alloy material according to claim 2, wherein the amount of Si in the first coating is 30 atomic% or more and less than 70 atomic%.   The aluminum alloy according to any one of claims 1 to 3, further comprising a silane coupling agent having a reactive functional group capable of chemically bonding to the organic resin component, a hydrolyzate thereof, or a polymer thereof. Wood. Aluminum alloy material according to any one of claims 1 to 4 layer weight of the second coating is a 0.01 to 30 mg / ^{m 2.} The aluminum alloy material according to claim 5, wherein the coating amount of the second coating is 0.2 to 20 mg / m ² . The aluminum alloy material according to claim 6, wherein the coating amount of the second coating is 0.5 to 10 mg / m ² .   The said aluminum alloy base material consists of an Al-Mg type alloy, an Al-Cu-Mg type alloy, an Al-Mg-Si type alloy, or an Al-Zn-Mg type alloy, The any one of Claims 1-7. Aluminum alloy material.   The aluminum alloy material with an adhesive resin layer in which the adhesive resin layer is formed on the said 2nd film | membrane of the aluminum alloy material of any one of Claims 1-8.   The aluminum alloy material with an adhesive resin layer according to claim 9, wherein the adhesive resin layer includes 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;
A 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 in at least a part of the first film; With
The first film forming step includes a heat treatment stage for forming an oxide film on the surface of the aluminum alloy substrate, an etching treatment stage and a silicate treatment stage after the heat treatment stage, and the silicate treatment The step is after the etching treatment step or simultaneously with the etching treatment step, and as the silicate treatment step, the oxide film is treated with a first aqueous solution containing silicate,
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. Manufacturing method of alloy material.   The manufacturing method of the aluminum alloy material of Claim 11 which controls the etching amount in the said etching process step to less than 700 nm.   In the first film formation 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. The manufacturing method of the aluminum alloy material as described in 2.   In the first film formation step, the silicate treatment step is simultaneous with the etching treatment step, and the first aqueous solution is a neutral or alkaline aqueous solution containing silicate. The manufacturing method of the aluminum alloy material of description.   The said 2nd aqueous solution is an aqueous solution which further contains the silane coupling agent which has a reactive functional group which can be chemically combined with an organic resin component, its hydrolyzate, or its polymer, In any one of Claims 11-14 The manufacturing method of the aluminum alloy material of description.   An adhesive resin layer forming step of forming an adhesive resin layer on the second film of the aluminum alloy material manufactured by the method for manufacturing an aluminum alloy material according to any one of claims 11 to 15. A method for producing an aluminum alloy material with a resin layer.