KR20130090371A - Aluminum alloy plate, and bonding material and member for automobile using the same - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is to provide an aluminum alloy sheet having excellent adhesion durability, and a bonded body and an automobile member using the same, which are less likely to cause interfacial peeling at the bonding interface of the adhesive even when exposed to a high temperature and wet environment, and thus the adhesive strength is less likely to decrease. It is.
The aluminum alloy plate 10 includes an aluminum alloy substrate 1 and a surface oxide film 2 formed on the surface of the aluminum alloy substrate 1, wherein the aluminum alloy substrate 1 contains Mg and Cu. The ratio of Mg and Cu [Mg / Cu (mass% ratio)] is 50 or less, the surface oxide film 2 contains Zr and Cu, and the ratio of Zr and Cu [Atomic% ratio]] Is 0.02 or more.

Description

Aluminum alloy plate, and joined body and automobile member using the same {ALUMINUM ALLOY PLATE, AND BONDING MATERIAL AND MEMBER FOR AUTOMOBILE USING THE SAME}

TECHNICAL FIELD This invention relates to an aluminum alloy plate, and relates to the aluminum alloy plate which can be used suitably for vehicles, such as an automobile, a ship, and an aircraft, especially an automobile panel, and the member for joining bodies and a differential vehicle using the same.

DESCRIPTION OF RELATED ART Conventionally, various aluminum alloy plates are common for each alloy according to each characteristic as a member of transporters, such as an automobile, a ship, and an aircraft. In particular, in recent years, in consideration of global environmental problems such as CO ₂ emissions, it is required to improve fuel efficiency by lightening the members, and the specific gravity is about one third of iron, and the use of aluminum alloy plates having excellent energy absorption is increased. Doing.

For example, Mg containing aluminum alloy plates, such as an Al-Mg type alloy plate of JIS5000 type | system | group and the Al-Mg-Si type | system | group alloy plate of JIS6000 type, are mentioned as an aluminum alloy plate used as an automotive member. As a joining method of these aluminum alloy plates, welding, the adhesion by an adhesive agent, or both are used together. While welding is bonded by dots or lines, since the adhesive is bonded to the entire surface, the bonding strength is much higher, which is advantageous in terms of collision safety of automobiles.

On the other hand, in the case of an aluminum alloy automobile member bonded with an adhesive, moisture, oxygen, chloride ions, etc. intrude into the bonding portion during use, and the interface between the adhesive layer and the aluminum alloy plate gradually deteriorates, causing interface peeling, resulting in an adhesive strength. There was a problem of deterioration.

As a method of improving the adhesion durability of an aluminum alloy automotive member having an adhesive layer, a mechanically weak oxide film present near the surface of an aluminum alloy plate and causing interfacial peeling is preliminarily subjected to acid washing before applying the adhesive. (See Patent Document 1, for example), anodizing the vicinity of the surface of the aluminum alloy plate to give a surface shape that causes the anchoring effect to the oxide film, and heating the surface of the aluminum alloy plate by The method of adjusting the Mg amount and OH amount of an oxide film (for example, refer patent document 2, 3) is generally known among those skilled in the art.

Japanese Patent Application Laid-open No. Hei 6-256881 Japanese Patent Application Publication No. 2006-200007 Japanese Patent Application Publication No. 2007-217750

In the method of carrying out the acid washing described in Patent Document 1, since the mechanically weak oxide film containing a large amount of Mg as the alloy component is removed, the initial interface peeling is prevented and the adhesive strength is improved. However, when exposed to a deteriorating environment of a high temperature and wet environment where moisture, oxygen, chloride ions and the like penetrate, copper as an alloy component is concentrated on the surface of the oxide film removal, which causes the deterioration of the adhesive layer to accelerate. A phenomenon called (銅 害) occurs. As a result, moisture or the like may penetrate into the body (substrate) of the aluminum alloy plate, and there is a problem that the interface deteriorates, the interface peels off, and the adhesive strength decreases.

In addition, in the method of anodic oxidation, in order to prevent deterioration and peeling of the interface, it is necessary to form a thick oxide film that is provided with a surface form for sufficiently improving the adhesion durability. There is a problem that this goes bad.

In addition, in the method of performing the hot water treatment described in Patent Documents 2 and 3, the initial adhesive strength and the secondary adhesion after wetting are improved, but when exposed to a high temperature and wet environment, deterioration of the interface is caused by hydration of the interface and dissolution of the substrate. There exists a problem that it advances and an interface peeling arises and adhesive strength falls.

The present invention is to solve the above problems, and even when exposed to a high temperature and wet environment, the interface peeling at the bonding interface of the adhesive hardly occurs, and therefore, the aluminum alloy plate having excellent adhesion durability, which is unlikely to lower the adhesive strength, and the use thereof. It is a subject to provide a joined body and a member for automobiles.

In order to solve the said subject, the aluminum alloy plate which concerns on this invention is an aluminum alloy plate provided with an aluminum alloy substrate and the surface oxide film formed in the surface of this aluminum alloy substrate, and the said aluminum alloy substrate contains Mg and Cu, The ratio [Mg / Cu (mass% ratio)] (hereinafter referred to as Mg / Cu ratio) of this Mg and Cu is 50 or less, The said surface oxide film contains Zr and Cu, and this Zr and Cu The ratio [Zr / Cu (atomic% ratio)] (hereinafter, appropriately referred to as Zr / Cu ratio) is characterized by being 0.02 or more.

According to such a structure, since an aluminum alloy substrate (henceforth a board | substrate) contains copper of predetermined ratio with respect to the magnesium amount of an alloy component, when aluminum alloy plate is joined by an adhesive member, even if it exposes to a high temperature and wet environment, aluminum Concentration of magnesium on the surface of the alloy substrate is suppressed. In addition, since the surface oxide film contains zirconium in a predetermined ratio with respect to copper in the surface oxide film, copper damage is suppressed by coating of copper of zirconium. As a result, the production of mechanically weak oxides due to magnesium on the surface of the aluminum alloy substrate is reduced, and interfacial peeling can be suppressed, and further, interfacial peeling by the East Sea can be suppressed, so that a decrease in adhesive strength can be suppressed. have.

It is preferable that the aluminum alloy plate which concerns on this invention further includes the adhesive bond layer which consists of adhesives on the surface of the said surface oxide film. According to such a structure, since an aluminum alloy plate is previously provided with an adhesive bond layer, when manufacturing a joined body or an automotive member using an aluminum alloy plate, the formation work of the adhesive member in the surface of an aluminum alloy plate can be skipped.

In the aluminum alloy sheet according to the present invention, it is preferable that the aluminum alloy substrate is made of an Al-Mg alloy, an Al-Cu-Mg alloy, an Al-Mg-Si alloy, or an Al-Zn-Mg alloy.

According to such a configuration, when the aluminum alloy substrate is composed of an alloy type having a relatively high magnesium content, magnesium is concentrated on the surface of the substrate, so that a weak boundary layer is likely to occur at the bonding interface, but is suitable for the magnesium content of the aluminum alloy component. By controlling the copper as much as an alloy component in a predetermined range, magnesium concentrated on the substrate surface can be suppressed. Specifically, magnesium added to the substrate surface can be suppressed by adding a predetermined ratio of copper to the substrate. In addition, by controlling the amount of zirconium suitable for copper present in the surface oxide film in a predetermined range in the surface oxide film, the copper sea can be suppressed. Specifically, by providing a predetermined ratio of zirconium with respect to copper in a surface oxide film, a copper sea can be suppressed. Therefore, even if it consists of alloy types with comparatively large magnesium content in an aluminum alloy substrate, interface peeling can be suppressed and the fall of adhesive strength can be suppressed.

The bonded body according to the present invention is a bonded body in which the aluminum alloys not provided with the adhesive layer are bonded through an adhesive member made of an adhesive, and the adhesive member is bonded to the surface oxide film side of the two aluminum alloy plates. Each of the surface oxide films of the two aluminum alloy plates is disposed to face each other via the adhesive member.

Moreover, the joined body which concerns on this invention is a joined body which the 2nd aluminum alloy plate which consists of aluminum alloy joined to the 1st aluminum alloy plate which consists of said aluminum alloy plate which is not equipped with an adhesive bond layer through the adhesive member which consists of adhesive agents. The adhesive member is bonded to the surface oxide film side of the first aluminum alloy plate.

Moreover, the joined body which concerns on this invention is a joined body which the said aluminum alloy plate which does not have an adhesive bond layer was bonded to the adhesive bond layer side of the said aluminum alloy plate provided with an adhesive bond layer, and the surface oxide film of two said aluminum alloy plates Each of them is arranged to face each other via the adhesive layer.

Moreover, the joined body which concerns on this invention is a joined body which the 2nd aluminum alloy plate which consists of aluminum alloy joined to the 1st aluminum alloy plate which consists of the said aluminum alloy plate provided with an adhesive bond layer, The said 2nd aluminum alloy plate is the said 1st It is bonded to the adhesive bond layer side of an aluminum alloy plate, It is characterized by the above-mentioned.

According to such a structure, it is comprised from the aluminum alloy board which has the aluminum oxide board | substrate containing a predetermined ratio with respect to the amount of magnesium of an alloy component, and the surface oxide film which contains a predetermined ratio with zirconium with respect to copper in a surface oxide film. The adhesive member or the adhesive layer is bonded to the surface oxide film side of the aluminum alloy plate (first aluminum alloy plate). Therefore, when the joined body is used for an automobile member, even when exposed to a high temperature and wet environment, the concentration of magnesium at the substrate interface between the adhesive member or the adhesive layer and the surface oxide film can be suppressed, and the oxide layer is mechanically weak. Can be minimized. Moreover, since zirconium covers copper, deterioration of the adhesive member or adhesive bond layer by a copper sea can be suppressed. As a result, interfacial peeling can be suppressed and the fall of adhesive strength is suppressed.

The member for automobiles which concerns on this invention is characterized by being manufactured from the said joined body.

According to such a structure, since it is manufactured with the above-mentioned joined body, even in the case where the automobile member is exposed to a high temperature and wet environment, in the joined body which constitutes the automobile member, at the interface between the adhesive member or the adhesive layer and the surface oxide film Hydration can be suppressed, and elution of an aluminum alloy substrate can be suppressed. As a result, interfacial peeling can be suppressed and the fall of adhesive strength can be suppressed.

According to the present invention, even when exposed to a high temperature and wet environment, interfacial peeling at the bonding interface of the adhesive hardly occurs, and thus the adhesive strength is less likely to decrease, and the adhesive durability thereof is not affected by the type of adhesive. An aluminum alloy plate and a joined body using the same can be provided. In addition, it is possible to provide an automobile member having excellent adhesion durability.

FIG.1 (a), (b) is sectional drawing which shows typically the structure of the aluminum alloy plate which concerns on this invention.
FIG. 2 is a process flowchart showing a method for manufacturing the aluminum alloy plate of FIGS. 1A and 1B.
FIG.3 (a)-(d) is sectional drawing which shows typically the structure of the joined body which concerns on this invention.
Fig. 4 shows the shape of the adhesive test body produced in the examples, (a) is a side view, and (b) is a plan view.

<< aluminum alloy plate >>

Hereinafter, the aluminum alloy plate which concerns on this invention is demonstrated concretely with reference to FIG. 1 (a). As shown in FIG. 1A, the aluminum alloy plate 10 includes an aluminum alloy substrate 1 (hereinafter referred to as a substrate) and a surface oxide film 2 formed on the surface of the substrate 1. Equipped. Moreover, by adding copper to a board | substrate, suppressing the magnesium concentrate | concentration on the board | substrate surface, the oxide film which suppressed magnesium is formed, and the formed oxide film is then surface-treated with the zirconium salt aqueous solution. As a result, zirconium dioxide adheres or enters the surface oxide film, thereby forming an oxide film covering the copper or copper compound included in the surface oxide film.

In addition, here, the surface of the board | substrate 1 means at least 1 surface of the surface of the board | substrate 1, and what is called one side and both surfaces are included. Hereinafter, each structure of the aluminum alloy plate 10 is demonstrated.

<Substrate>

The board | substrate 1 consists of aluminum alloy, the aluminum alloy component contains magnesium and copper, and the non-heat treatment type aluminum alloy whose ratio of Mg and Cu [Mg / Cu (mass% ratio)] is below a predetermined ratio, or It is a heat treatment aluminum alloy. In addition, the non-heat treatment aluminum alloy has pure aluminum (1000 series), Al-Mn-based alloy (3000 series), and Al-Si-based alloy (4000 series) in which Mg / Cu (mass% ratio) is below a predetermined ratio. ) And Al-Mg-based alloy (5000-based) is appropriately selected depending on the appropriate use. In addition, the heat-treated aluminum alloy has an Al-Cu-Mg-based alloy (2000 series), an Al-Mg-Si-based alloy (6000 series), and an Al-Zn-Mg-based alloy having a Mg / Cu (mass% ratio) of a predetermined ratio or less. (7000 series) is suitably selected according to a suitable use.

For example, when using the aluminum alloy plate 10 for automobiles, it is preferable that it is a high strength board | substrate whose 0.2% yield strength is 10 OMPa or more. As the aluminum alloy constituting the substrate satisfying these characteristics, a general-purpose alloy containing a relatively large amount of magnesium, such as 2000 series, 5000 series, 6000 series, and 7000 series, which is generally used for structural members of this kind, and has a relatively high strength. The aluminum alloy whose Mg / Cu (mass% ratio) is below a predetermined ratio is preferable as a component ratio. In addition, in view of excellent aging hardening ability and a relatively small amount of alloying elements, and excellent in recyclability and formability of scrap, an aluminum alloy having a 6000-based aluminum alloy as a component ratio of Mg / Cu (mass% ratio) or less is preferable. .

[Mg / Cu ratio (mass% ratio)]

The board | substrate 1 contains magnesium and copper in an aluminum alloy component, and the ratio [Mg / Cu (mass% ratio)] of this Mg and Cu is 50 or less. By containing copper so that Mg / Cu (mass% ratio) may be 50 or less, magnesium contained in an alloy is hard to spread externally to a board | substrate surface, and the concentration on the board | substrate surface is suppressed. As a result, generation of a mechanically weak oxide film made of magnesium is suppressed. As a result, the adhesion durability of the aluminum alloy plate is improved. However, when Mg / Cu ratio (mass% ratio) is too small, most Cu will exist in a surface oxide film and it will cause a copper sea. Therefore, it is necessary to balance Zr / Cu ratio by increasing the amount of zirconium mentioned later. Therefore, it is preferable that Mg / Cu ratio (mass% ratio) is 0.2 or more. Moreover, it is preferable that it is 0.2-1.5 mass% as an amount of magnesium in the board | substrate 1, and 0.02-1 mass% as an amount of copper. Moreover, Mg / Cu ratio (mass% ratio) becomes like this. Preferably it is 35 or less, More preferably, it is 20 or less.

<Surface oxide film>

The surface oxide film 2 contains Zr and Cu, and the ratio [Zr / Cu (atomic% ratio)] of this Zr and Cu is 0.02 or more. In other words, the zirconium and copper Zr / Cu ratios (atomic% ratio) present in the surface oxide film 2 have a predetermined ratio or more in order to improve the adhesion durability even when the surface oxide film 2 is exposed to a high temperature and wet environment. It is made of an oxide film. In addition, formation of the surface oxide film 2 is carried out after formation of the oxide film on the surface of the board | substrate 1 by heat processing in surface oxide film formation process S2 (refer FIG. 2) mentioned later here, The surface oxide film 2 is formed in the whole of the oxide film which surface-treated with the zirconium salt aqueous solution.

In addition to the above-described elements (zirconium, magnesium, copper), the surface oxide film (aluminum oxide film) 2 is made of oxygen, aluminum, and impurities such as halogen and phosphorus. Preferable content of oxygen and aluminum is 15-80 atomic%, respectively. Moreover, if impurities other than halogen and phosphorus are C less than 10 atomic%, if N, less than 15 atomic%, and other impurities, content of less than 7 atomic% is permissible.

[Zr / Cu ratio (atomic%)]

The surface oxide film 2 has a Zr / Cu ratio (atomic% ratio) of zirconium and copper present in the surface oxide film 2 of 0.02 or more. By setting it as the surface oxide film 2 which makes a Zr / Cu ratio (atomic% ratio) 0.02 or more, dynamic seam is suppressed at the interface of an adhesive agent and the surface oxide film 2, As a result, adhesive durability improves. There is no upper limit to the Zr / Cu ratio (atomic% ratio) in the surface oxide film 2, but the effect is saturated when the Zr / Cu ratio (atomic% ratio) exceeds 500. Therefore, the Zr / Cu ratio (atomic% ratio) is preferably 500 or less. The concentration of copper is preferably 0.02 to 2 atomic%, and the concentration of zirconium is preferably 0.02 to 40 atomic%. Moreover, Zr / Cu ratio (atomic%) becomes like this. Preferably it is 0.05 or more, More preferably, it is 0.1 or more.

The Zr / Cu ratio is the amount of zirconium and the same amount (atomic%) of all the metal elements in the surface oxide film 2 (or all metals containing silicon (Si) when containing silicon (Si)). It is ratio, for example, when it contains silicon (Si), it is a ratio of the amount of zirconium and the amount (atomic%) with respect to the amount of silicon and a containing metal.

As a method of containing zirconium in the surface oxide film 2, for example, zirconium nitrate (formal name: zirconium dinitrate, common name: zirconium oxynitrate, zirconyl nitrate, zircon nitrate, etc.), zirconium sulfate, zirconium such as zirconium acetate And surface-treating the surface oxide film 2 with an aqueous solution of salt. In addition, the amount of zirconium of the surface oxide film 2 can be adjusted so that it may become desired Zr / Cu ratio by adjusting the processing time of a surface treatment, temperature, the density | concentration of surface treatment liquid, and pH.

(Elemental content measurement method in surface oxide film)

The amount of elements (the amount of zirconium, the amount of copper, the amount of magnesium, the amount of aluminum, the amount of silicon, etc.) in the surface oxide film 2 formed on the surface of the substrate 1 is GD-OES (Glow Discharge Optical Emission Spectroscopy). ] And the maximum measurement of a predetermined element with respect to the amount of silicon (Si) and the metal contained when measured to a depth where the measured value of the amount of oxygen in the depth direction profile of the surface oxide film 2 is 15 atomic% or less. The value was made into elemental quantity (atomic%). In addition, of course, an element amount can be made into the average value of several measurement results on the surface of the surface oxide film 2, of course.

As shown in FIG. 1B, the aluminum alloy plate 10A according to the present invention preferably further includes an adhesive layer 3 made of an adhesive on the surface of the surface oxide film 2.

<Adhesive Layer>

It does not specifically limit as an adhesive agent which comprises this adhesive bond layer 3, The adhesive agent conventionally used when joining an aluminum alloy plate can be used. For example, a thermosetting epoxy resin, an acrylic resin, a urethane resin, etc. are mentioned. Although the thickness of the adhesive bond layer 3 is not specifically limited, 10-500 micrometers is preferable and 50-400 micrometers is more preferable. When the thickness of the adhesive bond layer 3 is less than 10 micrometers, the aluminum alloy plate 10A and the aluminum alloy plate 10 (refer FIG. 1 (a)) which does not have another adhesive bond layer are used for the adhesive bond layer 3 It may not be able to join by high adhesive durability through the intervening. That is, the adhesive durability of the joined body 20B of FIG. 3C mentioned later may fall. When the thickness of the adhesive bond layer 3 exceeds 50 micrometers, adhesive strength may become small.

<< manufacturing method of aluminum alloy plate >>

Next, the manufacturing method of said aluminum alloy plate is demonstrated with reference to FIG. Moreover, about the structure of an aluminum alloy plate, refer to FIG.1 (a), (b).

The manufacturing method of the aluminum alloy plate 10 includes board | substrate preparation process S1 and surface oxide film formation process S2. Hereinafter, each step will be described.

<Substrate manufacturing process>

Substrate preparation step S1 is a step of producing the substrate 1 by rolling. Specifically, it is preferable to produce the substrate 1 in the following order.

An aluminum alloy having a predetermined composition is dissolved and cast by continuous casting to produce an ingot (dissolution casting step), and the homogenization heat treatment is performed on the produced ingot (homogenization heat treatment step). Next, a hot rolled sheet is produced by hot rolling on the homogenized heat-treated ingot (hot rolling step). Subsequently, the hot rolled sheet is subjected to initial annealing or intermediate annealing at 300 to 580 ° C., and cold rolling at least once of a final cold rolling ratio of 5% or more is performed to produce a cold rolled sheet [substrate 1] having a predetermined sheet thickness. (Cold rolling process). By setting the temperature of the initial annealing or the intermediate annealing to 300 ° C or more, the effect of improving the moldability is further exhibited, and by setting it to 580 ° C or less, it is easy to suppress the deterioration of the moldability due to burning. By making final cold rolling rate into 5% or more, the effect of a moldability improvement is exhibited further. Moreover, the conditions of homogenization heat processing and hot rolling are not specifically limited, What is necessary is just the conditions at the time of obtaining a hot rolled sheet normally. In addition, intermediate annealing does not have to be performed.

<Surface Oxide Formation Process>

Surface oxide film formation process S2 is a process of forming surface oxide film 2 in the surface of the board | substrate 1 produced by the previous process S1. For example, it is a process of adjusting the Zr / Cu ratio of the surface oxide film 2 to a predetermined range by heat-processing the board | substrate 1 and continuing surface treatment.

(Heat treatment)

In the heat treatment, the substrate 1 is heated to 400 to 580 ° C. to form an oxide film constituting the surface oxide film 2 on the surface of the substrate 1. In addition, heat processing also adjusts the intensity | strength of the aluminum alloy plate 10. FIG. Moreover, it is preferable to make heat processing rapid heating of a heating rate of 100 degreeC / min or more.

And heat processing is solution treatment when the board | substrate 1 consists of a heat treatment aluminum alloy, and heat processing in annealing (final annealing) when the board | substrate 1 consists of a non-heat treatment type aluminum alloy.

By rapidly heating to the heating temperature of 400 degreeC or more, the intensity | strength of the aluminum alloy plate 10 and the intensity | strength after heating (baking) after the aluminum alloy plate 10 are further increased. By rapidly heating to the heating temperature of 580 degrees C or less, the fall of the moldability by burn generation is suppressed.

(Surface treatment)

Surface treatment is to perform a surface treatment on the surface of the substrate 1 on which the oxide film is formed, and by this surface treatment, the oxide film formed by the heat treatment, that is, Zr / Cu of the surface oxide film 2 on which the oxide film is surface treated The ratio is adjusted to a predetermined range.

In surface treatment, as a surface treatment liquid, the zirconium salt aqueous solution of 0.01-15 mass% and pH less than 5 is used. In addition, in surface treatment, you may add acids, such as nitric acid and a sulfuric acid, in order to adjust pH. Moreover, in surface treatment, a treatment temperature is 10-90 degreeC and a treatment time is 1-30 second. This is followed by water washing and drying. This surface treatment is performed by spraying a zirconium salt aqueous solution by showering or spraying, for example, passing through a zirconium salt aqueous solution, or immersing in a zirconium salt aqueous solution, for example, to the substrate 1 on which the oxide film was formed. ) Can be surface treated. In addition, it is preferable to use the thing which does not contain halogen and phosphorus as surface treatment liquid.

By using 0.01-15 mass% zirconium salt aqueous solution as a surface treatment liquid, the Zr / Cu ratio of the surface oxide film 2 becomes 0.02 or more. When the concentration of the zirconium salt aqueous solution is less than 0.01% by mass, the amount of zirconium in the surface oxide film 2 is small, so that the amount of zirconium suitable for copper present in the surface oxide cannot be ensured, and the adhesion durability of the aluminum alloy plate 10 is achieved. Cannot be secured. On the other hand, when the concentration of the zirconium salt aqueous solution exceeds 15 mass%, the amount of zirconium in the surface oxide film 2 increases, and the effect of improving the adhesion durability is saturated. Therefore, the concentration of the zirconium salt aqueous solution is 0.01-15 mass%.

When pH of the zirconium salt aqueous solution as a surface treatment liquid is five or more, stability of a surface treatment liquid will fall and precipitation will arise easily in a surface treatment liquid. If precipitation occurs in the surface treatment liquid, precipitation is pressed into the surface of the plate of the aluminum alloy plate 10 as foreign matter, which is not preferable because of poor appearance. The pH of the zirconium salt aqueous solution as the surface treatment liquid is preferably less than 5.

When the treatment temperature of the zirconium salt aqueous solution as the surface treatment liquid is less than 10 ° C. or the treatment time is less than one second, the amount of zirconium in the surface oxide film 2 is small, and the amount of zirconium suitable for the copper present in the surface oxide can be ensured. It is impossible to secure the adhesion durability of the aluminum alloy plate 10. On the other hand, if the treatment temperature of the zirconium salt aqueous solution exceeds 90 ° C or the treatment time exceeds 30 seconds, the amount of zirconium suitable for the copper present in the surface oxide can be sufficiently secured, and the effect of improving the adhesion durability is Saturate. Therefore, the processing temperature of the zirconium salt aqueous solution is 10-90 degreeC, and a processing time shall be 1-30 second.

In addition, since the present invention can reduce the surface concentration of magnesium by copper in the substrate 1, prior to the surface treatment in the zirconium salt aqueous solution, the surface using an acid such as nitric acid or sulfuric acid as the pretreatment of the substrate 1. There is no need to perform the treatment or so-called acid washing in particular. However, it is also possible to obtain more stable adhesiveness by further reducing the amount of surface magnesium by performing pretreatment. And as conditions of acid washing | cleaning, acid concentration is 0.5-6 N, pH is less than 1, 20-80 degreeC of washing | cleaning temperature, and 1 to 100 second of washing time are preferable.

Next, the manufacturing method of 10 A of aluminum alloy plates provided with the adhesive bond layer 3 is demonstrated. The manufacturing method of 10 A of aluminum alloy plates includes board | substrate preparation process S1, surface oxide film formation process S2, and adhesive bond layer formation process S3. Since board | substrate preparation process S1 and surface oxide film formation process S2 are as above-mentioned, description is abbreviate | omitted.

<Adhesive Layer Forming Step>

Adhesive layer formation process S3 is a process of forming the adhesive bond layer 3 which consists of an adhesive agent on the surface of the surface oxide film 2 formed in said process S2. The method for forming the adhesive layer 3 is not particularly limited, but for example, when the adhesive is a solid, after dissolving it in a solvent to form a solution, and when the adhesive is a liquid, the surface oxide film 2 is left as it is. The method of spraying or apply | coating to the surface of) is mentioned.

Although the manufacturing methods of the aluminum alloy plates 10 and 10A are as described above, in the production of the aluminum alloy plates 10 and 10A, the process is performed before or after each of the above steps in a range that does not adversely affect the above steps. In addition, you may include another process. For example, you may provide the preliminary aging treatment process of preliminary aging treatment after the said surface oxide film formation process S2 or adhesive bond layer formation process S3. The preliminary aging treatment is preferably performed by heating at 40 to 120 ° C. for 8 to 36 hours at low temperature within 72 hours. By preliminary aging on these conditions, moldability and the strength after baking can be aimed at. In addition, you may include the foreign material removal process of removing the foreign material on the surface of the board | plate of the aluminum alloy plate 10, 10A, the defective article removal process, etc. which remove the defective goods which generate | occur | produced in each process, for example.

In the manufactured aluminum alloy plates 10 and 10A, press oil is applied to the surface of the aluminum alloy plates 10 and 10A before the fabrication of the joined body or before molding the automotive member. Press oil is mainly used containing an ester component. Next, the method of apply | coating press oil to the aluminum alloy plates 10 and 10A which concerns on this invention is demonstrated. As a coating method of press oil, it is sufficient only to immerse the aluminum alloy plates 10 and 10A in the press oil containing ethyl oleate as an ester component, for example. The method and conditions of apply | coating the press oil containing an ester component are not specifically limited, The method and conditions of apply | coating normal press oil are widely applicable. In addition, the ester component is not limited to ethyl oleate, and various things, such as butyl stearate and sorbitan mono stearate, can be used.

<< conjugate >>

Next, the joined body which concerns on this invention is demonstrated. In addition, below, the aluminum alloy plates 10 and 10A are demonstrated by providing the surface oxide film 2 in one surface (refer FIG. 1 (a), (b)). As shown in FIG. 3A, the joined body 20 includes two aluminum alloy plates 10 and 10 and an adhesive member 11. Specifically, in the joined body 20, aluminum alloy plates 10 and 10 are joined to each other via the adhesive member 11. And the adhesive member 11 is joined to the surface oxide film 2 side of one aluminum alloy plate 10 on one surface, and to the surface oxide film 2 side of the other aluminum alloy plate 10 on one surface. have. As a result, each of the surface oxide films 2 and 2 of the two aluminum alloy plates 10 and 10 is disposed so as to face each other via the adhesive member 11.

<Aluminum alloy plate>

Since the aluminum alloy plate 10 is as described above, its description is omitted.

<Adhesive member>

The adhesive member 11 consists of an adhesive agent, and is the same as the adhesive agent layer 3 mentioned above. Specifically, the adhesive member 11 consists of adhesives, such as a thermosetting epoxy resin, an acrylic resin, and a urethane resin. In addition, the thickness of the adhesive member 11 is although it does not specifically limit, Preferably it is 10-500 micrometers, More preferably, it is 50-200 micrometers.

In the bonded body 20, as described above, the surface oxide film 2 in which the substrate 1 having a copper and magnesium content in a predetermined ratio is used, and both surfaces of the adhesive member 11 have a zirconium and copper content in a predetermined ratio. When the bonded body 20 is used for an automobile member, even if it is exposed to a high temperature and wet environment, the fall of the adhesive strength of the interface of the adhesion member 11 and the surface oxide film 2 is suppressed, Adhesion durability is improved. In addition, the adhesion durability at the interface is improved in the overall adhesive used conventionally for joining the aluminum alloy plate without being affected by the type of adhesive constituting the adhesive member 11.

As shown in Fig. 3B, the joined body 20A is a second aluminum alloy on one of the two aluminum alloy plates 10 and 10 (see Fig. 3A) of the joined body 20. The plate 12 was used. Specifically, the second aluminum alloy plate 12 made of an aluminum alloy is bonded to the first aluminum alloy plate 10a made of the aluminum alloy plate 10 via the adhesive member 11, and the adhesive member 11 is bonded thereto. ) Is bonded to the surface oxide film 2 side of the first aluminum alloy plate 10a. In addition, since the 1st aluminum alloy plate 10a consists of the aluminum alloy plate 10, and the aluminum alloy plate 10 is as above-mentioned, description is abbreviate | omitted.

<2nd aluminum alloy plate>

The second aluminum alloy plate 12 is the same as the substrate 1 described above, and is specifically made of various non-heat treatment aluminum alloys or heat treatment aluminum alloys defined in JIS or approximating JIS.

In the bonding body 20A, since one surface of the bonding member 11 is bonded to the surface oxide film 2 side, similarly to the bonding body 20 described above, when the bonding body 20A is used for an automobile member, high-temperature wetting Even when exposed to the environment, the adhesion durability at the interface is improved, and the adhesion durability is not affected by the kind of the adhesive.

As shown in FIG. 3C, the bonded body 20B includes an aluminum alloy plate 10A (see FIG. 1B) provided with the adhesive layer 3, and an adhesive layer 3. The aluminum alloy plate 10 which is not provided is provided. Specifically, the surface oxide film 2 of the aluminum alloy plate 10 is bonded to the adhesive layer 3 side of the aluminum alloy plate 10A. As a result, each of the surface oxide films 2 and 2 of the two aluminum alloy plates 10A and 10 is disposed to face each other via the adhesive layer 3 of the aluminum alloy plate 10A. In addition, since it is as above-mentioned about two aluminum alloy plates 10A and 10, description is abbreviate | omitted.

In the bonded body 20B, since both surfaces of the adhesive layer 3 are bonded to the surface oxide film 2 side, similarly to the bonded body 20 described above, when the bonded body 20B is used for an automobile member, a high temperature and wet environment is used. Even if exposed to, the adhesion durability at the interface is improved, and the adhesion durability is not affected by the kind of adhesive.

As shown in Fig. 3D. 20 C of bonding bodies used the 2nd aluminum alloy plate 12 instead of the aluminum alloy plate 10 (refer FIG.3 (c)) which is not equipped with the adhesive bond layer 3 of the bonding body 20B mentioned above. will be. Specifically, the second aluminum alloy plate 12 made of the aluminum alloy is bonded to the first aluminum alloy plate 10Aa made of the aluminum alloy plate 10A provided with the adhesive layer 3, and the second aluminum The alloy plate 12 is joined to the adhesive bond layer 3 side of the 1st aluminum alloy plate 10Aa. In addition, since the first aluminum alloy plate 10Aa is made of the aluminum alloy plate 10A, and the aluminum alloy plate 10A is as described above, description thereof is omitted. In addition, since the 2nd aluminum alloy plate 12 is as above-mentioned, it abbreviate | omits description.

In the bonding body 20C, since one surface of the adhesive layer 3 is bonded to the surface oxide film 2 side, similarly to the bonding body 20 described above, when the bonding body 20C is used for an automobile member, a high temperature is produced. The adhesion durability at the interface is improved even when exposed to a wet environment, and the adhesion durability is not affected by the kind of adhesive.

Conventionally well-known joining methods are used for the manufacturing method of the bonding bodies 20, 20A-20C, specifically, a joining method. And although the formation method of the adhesive member 11 is not specifically limited, For example, you may use the adhesive member 11 previously produced with the adhesive, and spray or apply an adhesive to the surface of the surface oxide film 2, for example. You may form by making it. In addition, similarly to the aluminum alloy plates 10 and 10A, the joined bodies 20 and 20A to 20C may be coated with press oil on the surface of the joined body before molding the automotive member.

Although not shown in the bonded bodies 20, 20A to 20C, when the aluminum alloy plates 10 and 10A (first aluminum alloy plates 10a and 10Aa) are provided with the surface oxide film 2 on both surfaces. The aluminum alloy plates 10 and 10A (first aluminum alloy plates 10a and 10Aa) or the second aluminum alloy plate 12 are further bonded to each other via the adhesive member 11 or the adhesive layer 3. It becomes possible.

<< member for car >>

Next, the automobile member which concerns on this invention is demonstrated.

Although not shown, the automobile member is made of the above-described bonded bodies 20, 20A to 20C. And the automotive member is, for example, an automotive panel. In addition, the manufacturing method of the member for automobiles is although it does not specifically limit, A conventionally well-known manufacturing method is used. For example, the above-mentioned joined bodies 20, 20A to 20C are subjected to cutting work, press working, or the like to manufacture a member for automobile of a predetermined shape. In addition, since the automotive member is made of the above-described bonded bodies 20 and 20A to 20C, the adhesion durability at the interface is improved even when exposed to a high temperature and wet environment.

<Examples>

Next, the aluminum alloy plate of the present invention will be specifically described in contrast with Examples meeting the requirements of the present invention and Comparative Examples without the requirements of the present invention.

6022 standard (Mg: 0.65 mass%, Si: 1.05 mass%, Cu: 0.01 mass%) of JIS standard, 6016 standard (Mg: 0.57 mass%, Si: 1.11 mass%, Cu: 0.12 mass%), 6111 standard ( The aluminum alloy cold-rolled sheet (plate thickness 1mm) was produced by the above-mentioned manufacturing method using 6000 type aluminum alloy of Mg: 0.71 mass%, Si: 0.97 mass%, Cu: 0.73 mass%). And this cold rolled sheet was cut into length 100mm x width 25mm, and it was set as the board | substrate. Alkali-degreasing this board | substrate, heat-processing and cooling a board | substrate to the substance | attainment | attainment temperature 550 degreeC, and cooling at 10-80 degreeC in the aqueous solution containing 0.01-15 mass% of zirconium nitrate which adjusted the pH to less than 4 by adding nitric acid. By immersing for 2 to 20 seconds, the aluminum alloy plate in which the surface oxide film in which the amount of zirconium, the amount of magnesium, and the amount of nitrogen were controlled on both surfaces of the board | substrate was formed was produced. Subsequently, water washing and drying were performed to obtain a test providing material (Nos. 1 to 7).

The above-described test providing materials (Nos. 1 to 7) were subjected to high frequency glow discharge emission spectroscopy analysis [GD-OES (Horiba Joban Corporation, Model JY-500ORF)] to form aluminum (Al) of the surface oxide film, Si containing metal elements, such as magnesium (Mg), zirconium (Zr), and copper (Cu), and Si were measured. Table 1 shows the amount of zirconium and the amount (atomic%) of the amount of silicon (Si) and the contained metal. In addition, each element amount was made into the maximum value in oxide film.

Next, the following evaluation was performed using test provision materials (No. 1-7). The results are shown in Table 1.

Coagulation Fracture Rate (Adhesion Durability)

As shown to Fig.4 (a), (b), the edge part of two test provision materials (25 mm width) with the same structure is made into 13 mm of wrap lengths by the thermosetting epoxy resin adhesive (adhesion area: 25) It was piled up so that it might become (mm * 13mm). Adhesive A used here is a thermosetting epoxy resin adhesive (30-40% of bisphenol A type epoxy resin, barium ferrite addition), and adhesive B is a thermosetting epoxy resin adhesive (40-50% of bisphenol A type epoxy resin, barium) No ferrite addition). And a trace amount of glass beads (particle size 150 micrometers) was added and adjusted to the adhesive agent so that the film thickness of an adhesive bond layer might be 150 micrometers. After foaming, the mixture was dried at room temperature for 30 minutes, then heated at 170 ° C. for 20 minutes, and subjected to a thermosetting treatment. Then, it left still at room temperature for 24 hours and produced the adhesion test body.

The prepared adhesive test body was initially stretched at a rate of 50 mm / min by a tensile tester under two test conditions after 15 days of holding at 50 ° C. in a high-temperature wet environment having a relative humidity of 95% for 15 days, thereby Cohesive failure rate was evaluated. Cohesive failure rate was calculated | required as following formula (1). In Formula (1), the test piece A and the other one were the test piece B for the tension | pulling of the adhesion test body.

Cohesive Fracture Rate (%) = 100-{(Interfacial Peeling Area of Test Piece A / Adhesive Area of Test Piece A) × 100} + {(Interfacial Peeling Area of Test Piece B / Adhesive Area of Test Piece B) × 100} One)

In addition, all three test conditions were produced, and the aggregation failure rate was made into three average values. In addition, evaluation criteria are less than 70% of cohesive failure rate "x", 70% or more, less than 80%, slightly poor "△", 80% or more, less than 90% is good "o", excellent in more than 90% "◎" I did it.

As shown in Table 1, in the first to fourth embodiments, the Mg / Cu ratio, which is the component ratio of the substrate, and the Zr / Cu ratio of Zr and Cu contained in the surface oxide film, satisfy the specified range, and cohesive failure after high temperature wetting. The rate was good, and the result was more than "(circle)". The amount of Mg in the oxide film at that time was 20.8 atomic% in the first example, 20.4 atomic% in the second example, 26.3 atomic% in the third example, and 25.4 atomic% in the fourth example.

In the first comparative example, since the copper in the substrate was small and the magnesium in the substrate was much higher than the copper, it was larger than the prescribed Mg / Cu ratio, so that the concentration on the substrate surface was increased, and the cohesive failure rate after high temperature wetting was slightly poor. It became. Further, in the second and third comparative examples, the Zr / Cu ratio of Zr and Cu contained in the surface oxide film is smaller than the specified value, and the copper damage occurs due to Cu, and the coagulation fracture rate after high temperature wetting is slightly poor. It became defective "x". In addition, the amount of Mg in the oxide film at that time was 42.0 atomic% in the 1st comparative example, 22.1 atomic% in the 2nd comparative example, and 27.3 atomic% in the 3rd comparative example.

As mentioned above, although the embodiment and the Example were demonstrated and demonstrated in detail about the aluminum alloy plate which concerns on this invention, and the joined body and automobile member using this, the meaning of this invention is not limited to the above-mentioned content, It should be interpreted based on the description of the claims. In addition, of course, the content of this invention can be changed, changed, etc. based on said description.

1: aluminum alloy substrate (substrate)
2: surface oxide film
3: adhesive layer
10, 10A: aluminum alloy plate
10a, 10Aa: first aluminum alloy plate
11: adhesive member
12: second aluminum alloy plate
20, 20A, 20B, 20C: conjugate

Claims (8)

An aluminum alloy plate provided with an aluminum alloy substrate and the surface oxide film formed in the surface of this aluminum alloy substrate,
The aluminum alloy substrate contains Mg and Cu, and the ratio [Mg / Cu (mass% ratio)] between the Mg and Cu is 50 or less,
The aluminum oxide plate, wherein the surface oxide film contains Zr and Cu, and the ratio [Zr / Cu (atomic% ratio)] of the Zr and Cu is 0.02 or more. The aluminum alloy plate according to claim 1, further comprising an adhesive layer made of an adhesive on the surface of the surface oxide film. The aluminum alloy substrate according to claim 1 or 2, wherein the aluminum alloy substrate is made of an Al-Mg alloy, an Al-Cu-Mg alloy, an Al-Mg-Si alloy, or an Al-Zn-Mg alloy. Aluminum alloy plate. The aluminum alloy plate of Claim 1 is the joined body joined together through the adhesive member which consists of an adhesive agent,
The said adhesive member is joined to the surface oxide film side of two said aluminum alloy plates, and each of the surface oxide films of two said aluminum alloy plates is arrange | positioned so as to oppose each other via the said adhesive member, Conjugate. It is a joined body in which the 2nd aluminum alloy plate which consists of aluminum alloy was joined to the 1st aluminum alloy plate which consists of an aluminum alloy plate of Claim 1 via the adhesive member which consists of adhesives,
The said bonding member is joined to the surface oxide film side of the said 1st aluminum alloy plate, The joined body characterized by the above-mentioned. It is a joined body in which the aluminum alloy plate of Claim 1 was joined to the adhesive bond layer side of the aluminum alloy plate of Claim 2,
Each of the surface oxide films of the two aluminum alloy plates is disposed to face each other via the adhesive layer. It is a joined body in which the 2nd aluminum alloy plate which consists of aluminum alloy was joined to the 1st aluminum alloy plate which consists of an aluminum alloy plate of Claim 2,
The said 2nd aluminum alloy plate is joined by the adhesive bond layer side of a said 1st aluminum alloy plate, The joined body characterized by the above-mentioned. It is manufactured with the joined body in any one of Claims 4-7, The member for automobiles characterized by the above-mentioned.

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