JP2019005927A - Laminate aluminum alloy and method for producing the same, and laminate - Google Patents

Abstract

To provide a laminate aluminum alloy that can improve bond strength between an aluminum alloy and a resin.SOLUTION: A laminate aluminum alloy has a porous layer having a porous shape on the surface. A thickness of the porous layer in the cross sectional direction of the laminate aluminum alloy is 0.5 μm or more and 8.0 μm or less.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a laminated aluminum alloy, a method for producing the same, and a laminated body.

  Conventionally, various techniques for joining a metal alloy and a resin are known. One of them is a method of bonding them via an adhesive, and many adhesives have been developed for that purpose. As such an adhesive, for example, an adhesive that can join them at room temperature or by heating is known.

  On the other hand, a technique for joining a metal alloy and a resin without using an adhesive has also been studied. For example, a method is known in which a high-strength thermoplastic engineering resin is integrated by injection or the like without using an adhesive with respect to a light metal alloy such as magnesium or aluminum and an iron alloy such as stainless steel.

  As a technique for joining a metal alloy and a resin through those adhesives or without using an adhesive, a technique for making the surface of the metal alloy porous has been proposed in order to enhance the joining properties thereof. . For example, in Patent Document 1, the metal alloy and the adherend are bonded via an adhesive with the intention of providing a bonded body in which the metal alloy and the adherend are firmly bonded via an unsaturated polyester adhesive. The surface of the metal alloy is etched so that the average interval between the valleys (RSm) is 0.8 to 10 μm and the maximum height roughness (Rz) is 0.2 to 5 μm. In the surface having the roughness of micron order, ultra fine irregularities with a period of 5 to 500 nm are formed in the surface having the roughness, and the surface layer is a thin layer of metal oxide or metal phosphate. Yes, the adhesive is mainly composed of unsaturated polyester resin or vinyl ester resin, and the adhesive penetrates into the ultra-fine irregularities, so that the metal alloy and the adherend are firmly bonded. Metal alloy and adherend characterized by that The joined body is disclosed.

International Publication No. 2009/093668

  However, in the conventional techniques including those described in the cited document 1, the bonding strength between a metal alloy such as an aluminum alloy and a resin is not sufficient, and there is room for further improvement.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminated aluminum alloy that can increase the bonding strength between an aluminum alloy and a resin, a manufacturing method thereof, and a laminate including the laminated aluminum alloy. And

  As a result of intensive studies to achieve the above object, the present inventors have joined a predetermined laminated aluminum alloy having a porous layer having a porous shape on the surface with a resin layer. The inventors have found that the strength can be increased and have completed the present invention.

That is, the present invention is as follows.
[1] A laminated aluminum alloy comprising a porous layer having a porous shape on the surface, wherein the thickness of the porous layer in the cross-sectional direction of the laminated aluminum alloy is 0.5 μm or more and 8.0 μm or less. Aluminum alloy.
[2] The laminated aluminum alloy according to [1], wherein the porous layer contains magnesium and aluminum.
[3] The laminated aluminum according to [2], wherein the porous layer contains 10% by mass to 18% by mass of magnesium and 10% by mass to 28% by mass of aluminum with respect to the total amount of the porous layer. alloy.
[4] The laminated aluminum alloy according to any one of [1] to [3], wherein the porous shape is a porous shape in which an alloy portion in the porous layer has orientation in a thickness direction.
[5] A laminated aluminum alloy comprising a porous layer having a porous shape on the surface, which is obtained by bringing the surface of the aluminum alloy into contact with an aqueous solution having a pH exceeding 13.0.
[6] The aqueous solution includes a compound represented by the following formula (1), a hydrate of a compound represented by the following formula (1), and a salt of a compound represented by the following formula (1) and an inorganic acid. The laminated aluminum alloy according to [5], comprising one or more selected from the group consisting of:
(In formula (1), each R is independently a hydrogen atom, a methyl group, an ethyl group, or a monovalent group represented by the following formula (1a), and X is a hydroxy group or an amino group.
_{-C (NH 2) = NH (} 1a))
[7] Prior to contacting the aluminum alloy with the aqueous solution, the aluminum alloy has a surface from which an oxide film has been removed by contacting the aluminum alloy with an aqueous solution containing sodium borohydride and / or sodium hydroxide. The laminated aluminum alloy according to [5] or [6].
[8] A method for producing a laminated aluminum alloy comprising a porous layer having a porous shape on the surface, the method comprising a step of bringing the surface of the aluminum alloy into contact with an aqueous solution having a pH exceeding 13.0.
[9] The aqueous solution includes a compound represented by the following formula (1), a hydrate of the compound represented by the following formula (1), and a salt of the compound represented by the following formula (1) and an inorganic acid. The production method according to [8], including one or more selected from the group consisting of:
(In formula (1), each R is independently a hydrogen atom, a methyl group, an ethyl group, or a monovalent group represented by the following formula (1a), and X is a hydroxy group or an amino group.
_{-C (NH 2) = NH (} 1a))
[10] A laminate comprising the laminated aluminum alloy according to any one of [1] to [7], and a resin layer bonded to the surface of the porous layer having a porous shape of the laminated aluminum alloy. .

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body provided with the laminated aluminum alloy which can make the joint strength of an aluminum alloy and a resin layer high, its manufacturing method, and the laminated aluminum alloy can be provided.

2 is an SEM image showing the surface of the laminated aluminum alloy of Example 1. FIG. 3 is a SEM image showing a cross section of the laminated aluminum alloy of Example 1. FIG. 3 is a SEM image showing the surface of the laminated aluminum alloy of Example 2. 3 is a SEM image showing a cross section of the laminated aluminum alloy of Example 2. 4 is a SEM image showing the surface of the laminated aluminum alloy of Example 3. 4 is a SEM image showing a cross section of the laminated aluminum alloy of Example 3. FIG. 4 is an SEM image showing the surface of the laminated aluminum alloy of Example 4. It is a SEM image which shows the cross section of the laminated aluminum alloy of Example 4. 4 is a SEM image showing the surface of a treated aluminum alloy of Comparative Example 1. 6 is a SEM image showing the surface of a treated aluminum alloy of Comparative Example 2. It is a SEM image which shows the cross section of the processed aluminum alloy of the comparative example 2. 6 is a SEM image showing the surface of a treated aluminum alloy of Comparative Example 3.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. However, the present invention is limited to the following embodiment. It is not a thing. The present invention can be variously modified without departing from the gist thereof.

  The laminated aluminum alloy of the present embodiment includes a porous layer having a porous shape on the surface, and the thickness of the porous layer in the cross-sectional direction of the laminated aluminum alloy is 0.5 μm or more and 8.0 μm or less. is there. In this laminated aluminum alloy, the porous layer and the underlying aluminum alloy are directly joined and may be formed integrally. By providing such a porous layer in the laminated aluminum alloy, when the resin layer is joined to the laminated aluminum alloy from the porous layer side, the resin in the resin layer enters the pores of the porous layer. As a result, since the resin layer is engaged with the porous layer by the anchor effect, the adhesive strength between the laminated aluminum alloy and the resin layer can be increased.

  The aluminum alloy used as the raw material for the laminated aluminum alloy is not particularly limited as long as it is an aluminum alloy. Examples of the aluminum alloy include a pure aluminum-based aluminum alloy having an aluminum content of 99% by mass or more, an aluminum mainly containing copper in addition to aluminum-a copper-based aluminum alloy, and an aluminum mainly containing manganese in addition to aluminum- Examples thereof include manganese-based aluminum alloys and aluminum-magnesium alloys mainly containing magnesium in addition to aluminum. More specifically, pure aluminum-based A1100 alloy, A1085 alloy, A1050 alloy, aluminum-copper-based A2024 alloy, aluminum-manganese-based aluminum alloys that are aluminum alloys for extending as defined by Japanese Industrial Standards (JIS). All alloys such as A3003 alloy, aluminum-magnesium-based A5052 alloy, A1000 series to 7000 series (corrosion-resistant aluminum alloy, high-strength aluminum alloy, heat-resistant aluminum alloy, etc.), ADC1-12 types (aluminum alloy for die casting), etc. The aluminum alloy for casting is mentioned. The aluminum alloy used as the raw material for the laminated aluminum alloy preferably has no porous shape on the surface, and has no porous shape not only on the surface but also inside (that is, a non-porous aluminum alloy). More preferred.

  As the composition of the aluminum alloy as the raw material, for example, the content of each element is 1.5% by mass or less for silicon (Si), 1.0% by mass or less for iron (Fe), and 8 for copper (Cu). 0.0 mass% or less, manganese (Mn) is 2.0 mass% or less, magnesium (Mg) is 6.0 mass% or less, chromium (Cr) is 0.50 mass% or less, and zinc (Zn) is 8.0 mass%. Mass% or less, titanium (Ti) 0.30 mass% or less, vanadium (V) 0.25 mass% or less, bismuth (Bi) 1.0 mass% or less, lead (Pb) 1.0 mass% The remainder is aluminum (Al) and inevitable impurities. Although the composition of an aluminum alloy is illustrated in Table 1, a composition is not limited to these.

  The laminated aluminum alloy may be a casting alloy, a part molded into a predetermined shape by a die casting method, or a part machined into a predetermined shape. Further, the wrought alloy may be an intermediate material such as a plate material that is formed into a predetermined shape by machining such as hot pressing. Further, the shape of the laminated aluminum alloy is not particularly limited, and may be, for example, a plate shape and a column shape, and any shape suitable for the application.

The laminated aluminum alloy of this embodiment is obtained by bringing the surface of the aluminum alloy into contact with an aqueous solution having a pH exceeding 13.0. The aqueous solution is preferably a compound represented by the following formula (1), a hydrate of a compound represented by the following formula (1), and a salt of a compound represented by the following formula (1) and an inorganic acid. 1 type or more chosen from the group which consists of. By including such a compound in the aqueous solution, the chemical bonding properties of the laminated aluminum alloy with the resin layer containing a resin such as an epoxy resin are higher, and coupling is performed when the laminated aluminum alloy and the resin layer are joined. This is preferable because the necessity of using a bonding material such as an agent is reduced.
Here, in formula (1), each R is independently a hydrogen atom, a methyl group, an ethyl group or a monovalent group represented by the following formula (1a), and X is a hydroxy group or an amino group. is there.
_{-C (NH 2) = NH (} 1a)

  More specifically, examples of the compound represented by the formula (1) include hydroxylamine, dimethylhydroxylamine, diethylhydroxylamine, N-propylhydroxylamine, and aminoguanidine. These are used singly or in combination of two or more. Of these, hydroxylamine, diethylhydroxylamine and aminoguanidine are preferred, and aminoguanidine is more preferred from the viewpoint of more effectively and reliably achieving the effects of the present invention.

  Moreover, as an inorganic acid which forms a salt with the compound represented by the said Formula (1), hydrochloric acid, a sulfuric acid, nitric acid, and carbonic acid are mentioned, for example. These are used singly or in combination of two or more. Of these, carbonic acid is preferred from the viewpoint of more effectively and reliably achieving the effects of the present invention.

  More specifically, as the compound represented by the above formula (1), its hydrate and its salt with inorganic acid, hydroxylamine, dimethylhydroxylamine, diethylhydroxylamine, N-propylhydroxylamine, hydroxylamine Examples include hydrates, hydroxylamine hydrochloride, hydroxylamine sulfate and aminoguanidine carbonate. These are used singly or in combination of two or more. Among these, hydroxylamine monohydrate, diethylhydroxylamine, and aminoguanidine carbonate are preferable from the viewpoint of more effectively and reliably achieving the effects of the present invention.

  The concentration of the compound represented by the above formula (1) in the aqueous solution, its hydrate and its salt with an inorganic acid is not particularly limited as long as it is a concentration that can achieve the object of the present invention, but is 0.1% by mass. The content is preferably 5.0% by mass or less. When the concentration is 0.1% by mass or more and 5.0% by mass or less, a porous layer is formed by forming a porous shape on the surface of the aluminum alloy and in the vicinity thereof, more effectively and reliably, and The thickness of the porous layer can be 0.5 μm or more and 8.0 μm or less. In addition, by setting the concentration in the above range, a porous shape in which the alloy portion in the porous layer (that is, the portion other than the pores) has orientation in the thickness direction can be obtained more effectively and reliably. This is also preferable. From the same viewpoint, the concentration is more preferably 1.0% by mass or more and 4.0% by mass or less. Here, “having orientation in the thickness direction” means that the hole extends in the thickness direction but does not extend as much in the thickness direction in the plane direction (direction perpendicular to the thickness direction). Say.

  The pH of the aqueous solution when the aluminum alloy and the aqueous solution are brought into contact exceeds 13.0, but is preferably 13.3 or more, more preferably 13.5 or more, and 13.7 or more. More preferably. When the pH exceeds 13.0, a porous shape can be obtained by forming a porous shape on the surface of the aluminum alloy and in the vicinity thereof, and the thickness of the porous layer is 0.5 μm or more and 8 0.0 μm or less. As a result, the effect by this invention can be show | played. In addition, when the pH of the aqueous solution exceeds 13.0, the porous shape of the porous layer can be more easily formed into a desired shape as described later. As a result, the effect of the present invention can be more effectively and reliably achieved. Can play. In addition, the upper limit of pH of aqueous solution is not specifically limited, That is, 14.0 may be sufficient. In order to adjust the pH of the aqueous solution to the above range, an alkali may be added to the aqueous solution. The alkali is not particularly limited as long as the pH can be adjusted to the above range, and examples thereof include alkali metal hydroxides and alkaline earth hydroxides such as sodium hydroxide, potassium hydroxide and magnesium hydroxide. Is mentioned. These are used singly or in combination of two or more.

  The temperature (liquid temperature) and time for contacting the aluminum alloy and the aqueous solution are not particularly limited as long as the temperature and time can achieve the object of the present invention, but are 20 ° C. or higher and 70 ° C. or lower, and 1 minute or longer. It is preferable that it is 10 minutes or less. When the temperature and time are not less than the above lower limit value and not more than the upper limit value, a porous layer can be obtained by forming a porous shape on the surface of the aluminum alloy and in the vicinity thereof, and more reliably. The thickness of the porous layer can be 0.5 μm or more and 8.0 μm or less. In addition, by setting the concentration in the above range, a porous shape in which the alloy portion in the porous layer (that is, the portion other than the pores) has orientation in the thickness direction can be obtained more effectively and reliably. This is also preferable. From the same viewpoint, the temperature is more preferably 20 ° C. or more and 40 ° C. or less, and the time is more preferably 3 minutes or more and 10 minutes or less.

  The means for bringing the surface of the aluminum alloy into contact with the aqueous solution is not particularly limited. For example, a method of spraying (jet coating) or spraying (spray coating) the aqueous solution toward the surface of the aluminum alloy, or brushing the aqueous solution onto the surface of the aluminum alloy And a method of applying using a blade, a method of rotating an aluminum alloy while dropping the aqueous solution on the surface of the aluminum alloy, and using the centrifugal force to spread the aqueous solution over the entire surface of the aluminum alloy (spin coating), and A method of dipping an aluminum alloy in an aqueous solution bath (dip coating) can be mentioned.

  The aqueous solution according to the present embodiment may contain various additives usually used for the surface treatment of an aluminum alloy as long as the effects of the present invention are not impaired. Examples of such additives include interfacial additives, halide ions, azoles, and pH adjusters. These are used singly or in combination of two or more.

  The laminated aluminum alloy of this embodiment includes a porous layer having a porous shape on the surface. The porous layer has pores and a matrix that is a part other than the pores, thereby forming a porous shape. The porous shape may be, for example, one having open pores on the surface and closed pores inside the porous layer, or a three-dimensional network structure in which the pores or matrix extends from the surface to the inside of the layer. May be formed.

  The porous shape is preferably a porous shape in which the matrix has orientation in the thickness direction. Since the porous layer has such a porous shape, when the laminated aluminum alloy and the resin layer are joined, the resin of the resin layer can penetrate more efficiently and reliably into the porous layer. Their bonding strength can be further increased. As such a porous shape, the porous shape of the porous layer in the laminated aluminum alloy obtained in the below-mentioned Example is mentioned, for example. When such a porous shape is viewed from the surface side of the porous layer, the matrix itself has irregularities and open pores exist. On the other hand, when viewed from the cross section that appears when the porous shape is cut in the stacking direction of the underlying aluminum alloy and the porous layer, the open pores extend in the thickness direction, and the junction with the underlying aluminum alloy There are also open pores (ie, through-holes) that extend to On the other hand, the open pores do not extend in the plane direction compared to the thickness direction. The matrix also extends in the thickness direction compared to the planar direction, that is, has an orientation in the thickness direction.

  Moreover, the thickness of the porous layer is 0.5 μm or more and 8.0 μm or less. When the thickness of the porous layer is 0.5 μm or more, the range in which the resin of the resin layer can enter the porous layer is increased, so that the bonding strength between the laminated aluminum alloy and the resin layer can be increased. . On the other hand, the joining region between the laminated aluminum alloy and the resin layer, that is, the region where the resin has entered the porous layer is broken when a shearing direction force is applied as compared with the resin layer and the aluminum alloy part serving as a base. It's easy to do. From the viewpoint of reducing such a region, the thickness of the porous layer is 8.0 μm or less. From the same viewpoint, the thickness of the porous layer is preferably 0.5 μm or more and 7.0 μm or less, and more preferably 0.6 μm or more and 6.0 μm or less. The thickness of the porous layer can be measured by observing a cross section using a scanning electron microscope.

  The porous layer preferably contains magnesium and aluminum as elements. Thereby, the effect by this invention can be show | played more effectively and reliably. In this case, the magnesium and aluminum may form an alloy, but a part thereof may be a metal magnesium simple substance and / or a metal aluminum simple substance, or may be magnesium oxide and / or aluminum oxide. . The porous layer preferably contains 10% by mass or more and 18% by mass or less of magnesium, and preferably contains 10% by mass or more and 28% by mass or less of aluminum with respect to the total amount of the porous layer. When the content of these elements is equal to or more than the above lower limit value, the effects of the present invention can be achieved more effectively and reliably. On the other hand, when the content of these elements is not more than the above upper limit value, the adhesive force with the resin layer is improved. From the same viewpoint, the porous layer preferably contains 2% by mass to 15% by mass of magnesium, and more preferably 3% by mass to 10% by mass with respect to the total amount of the porous layer. From the same viewpoint, the porous layer preferably contains 1% by mass to 15% by mass of aluminum, and more preferably 3% by mass to 10% by mass with respect to the total amount of the porous layer.

  The porous layer may contain at least one element selected from the group consisting of silicon, iron, copper, manganese, chromium, zinc, titanium, vanadium, bismuth and lead in addition to magnesium and aluminum as an element, and oxygen. May be included.

  The porous layer is provided with an aluminum alloy on the base of the porous layer, and the aluminum alloy that serves as the base may be the one in which the aluminum alloy that is the raw material for producing the laminated aluminum alloy of the present embodiment remains. Good. That is, the material of the aluminum alloy serving as the base may be the same as the aluminum alloy serving as the raw material.

  In order to produce a laminated aluminum alloy provided with the porous layer as described above, for example, the surface of an aluminum alloy containing magnesium is obtained by contacting with an aqueous solution having a pH exceeding 13.0.

  In the laminated aluminum alloy of the present embodiment, the tensile strength with the specific epoxy resin adhesive is preferably 11.0 MPa or more, more preferably 12.0 MPa or more, on the surface of the porous layer. More preferably, it is 0.0 MPa or more. When the tensile strength is 11.0 MPa or more, the bonding strength between the laminated aluminum alloy and the resin layer tends to be higher. The upper limit of this tensile strength is not specifically limited, For example, it is 20.0 Mpa or less. This tensile strength can be measured according to the method described in the Examples, and examples of the specific epoxy resin adhesive include a one-component heat-curable epoxy adhesive. More specifically, the product name “EP106NL” manufactured by Cemedine Co., Ltd. used in the examples can be given.

  The method for producing a laminated aluminum alloy according to the present embodiment includes a step of contacting the surface of the aluminum alloy with an aqueous solution having a pH exceeding 13.0 (hereinafter also referred to as “contacting step”). The aqueous solution is composed of a compound represented by the above formula (1), a hydrate of the compound represented by the above formula (1), and a salt of the compound represented by the above formula (1) and an inorganic acid. It is preferable to include one or more selected from the above. Since the surface of the aluminum alloy is brought into contact with the aqueous solution, that is, the contact step has already been described in detail, the description thereof is omitted here.

  Although the manufacturing method of the laminated aluminum alloy of this embodiment will not be specifically limited if it has a contact process, 1 type chosen from the group which consists of an oxide film removal process, a degreasing process, a pickling process, a water washing process, and a drying process. It is preferable to further include the above steps. Hereinafter, each process is explained in full detail.

  The oxide film removing step is a step of removing the oxide film on the surface of the aluminum alloy by bringing the surface of the aluminum alloy into contact with an aqueous solution containing sodium borohydride and / or sodium hydroxide prior to the contacting step. Prior to the contacting step, the surface of the matrix of the porous layer is more easily roughened by performing the oxide layer removing step of removing the oxide layer existing on the surface of the aluminum alloy. As a result, the operational effects of the present invention can be achieved more effectively and reliably. From the same viewpoint, the total concentration of sodium borohydride and sodium hydroxide in the aqueous solution is preferably 0.1% by mass or more and 5.0% by mass or less.

  In the oxide film removal step, the temperature and time when the aluminum alloy and the aqueous solution are brought into contact with each other are not particularly limited as long as the temperature and time can achieve the object of the present invention. It is preferable that it is not less than 10 minutes and not more than 10 minutes. When the temperature and time are not less than the above lower limit value and not more than the upper limit value, the surface of the matrix of the porous layer is more easily roughened, and as a result, the effects of the present invention are more effectively and reliably achieved. be able to.

  In the oxide film removing step, the means for bringing the surface of the aluminum alloy into contact with the aqueous solution is not particularly limited, for example, a method of spraying (jet coating) or spraying (spray coating) the aqueous solution toward the surface of the aluminum alloy, A method of applying the aqueous solution to the surface of the aluminum alloy by using a brush or a blade, rotating the aluminum alloy while dropping the aqueous solution on the surface of the aluminum alloy, and utilizing the centrifugal force to apply the aqueous solution to the entire surface of the aluminum alloy. And a method of immersing an aluminum alloy in the aqueous solution bath (dip coating).

  The degreasing step is a step of removing fats and oils when the fats and oils are present on the surface of the aluminum alloy that is a raw material of the laminated aluminum alloy, and can be employed in a stage prior to the oxide film removing step. For example, fats and oils existing on the surface of the aluminum alloy can be removed by bringing a commercially available aqueous solution of a degreasing agent for aluminum alloy into contact with the surface of the aluminum alloy. The temperature of the aqueous solution of the degreasing agent brought into contact with the surface of the aluminum alloy is, for example, 50 ° C. or more and 80 ° C. or less, and the contact time is, for example, 5 minutes or more and 10 minutes or less. Examples of the method for bringing the aqueous solution of the degreasing agent into contact with the surface of the aluminum alloy include jet coating, spray coating, coating using a brush or blade, spin coating, and dip coating.

  The pickling process is a process in which the surface of the aluminum alloy that has undergone the degreasing process is brought into contact with an acidic aqueous solution, and can be employed in a stage prior to the oxide film removing process. By adsorbing the acid component to the surface of the aluminum alloy in advance in the pickling step, it becomes easier to obtain a porous layer having a desired thickness and porous shape in the contact step. Examples of the acidic aqueous solution include dilute aqueous solutions of hydrochloric acid, nitric acid, and sulfuric acid. The temperature of the acidic aqueous solution brought into contact with the surface of the aluminum alloy is, for example, 15 ° C. or more and 40 ° C. or less, and the contact time is, for example, 5 minutes or more and 10 minutes or less. Examples of the method of bringing the acidic aqueous solution into contact with the surface of the aluminum alloy include jet coating, spray coating, coating using a brush or a blade, spin coating, and dip coating.

  The water washing step is a step of washing the aluminum alloy with water, and is provided in any one or more of the steps described above and after the contact step. Thereby, the unnecessary component adhering to the surface of the aluminum alloy in the previous step can be appropriately removed. Moreover, a drying process is a process of drying an aluminum alloy, and is provided in any one or more between each said process and after a contact process. 40 degreeC or more and 80 degrees C or less may be sufficient as the drying temperature in a drying process, for example.

  The laminate of this embodiment is a laminate comprising the above-described laminated aluminum alloy of this embodiment and a resin layer bonded to the surface of the porous layer of the laminated aluminum alloy. The resin layer in this laminate may function as an adhesive or may not function as an adhesive. The resin layer is made of a resin composition, and the resin composition may be made of a resin, and may contain various additives in addition to the resin.

  When the resin layer functions as an adhesive, examples of the resin contained in the resin composition include thermosetting resins such as silicone resins, acrylic resins, unsaturated polyester resins, vinyl ester resins, epoxy resins, and urethane resins. Can be mentioned. These are used singly or in combination of two or more. Among these, a silicone resin and an epoxy resin are preferable from the viewpoint of particularly good bondability with the laminated aluminum alloy of the present embodiment.

  When the resin layer does not function as an adhesive, examples of the resin contained in the resin composition include thermoplastic resins such as polyolefin, polyphenylene ether, polyphenylene sulfide, polycarbonate, and polyamide. These are used singly or in combination of two or more. Among these, polyphenylene sulfide is preferable from the viewpoint of particularly good bonding properties with the laminated aluminum alloy of the present embodiment.

  Examples of additives contained in the resin composition include talc, calcium carbonate, clay, glass flakes, inorganic fillers such as silica and alumina, unvulcanized rubber, polyolefin resin particles, polyamide particles, carbon fibers, carbon Organic fillers such as particles and cellulose fibers are included. The resin composition may further contain a solvent.

  The content of the resin in the resin composition is not particularly limited, but is preferably 90% by mass or more and 100% by mass or less with respect to the total amount of the resin composition from the viewpoint of more effectively and reliably performing the function as the resin layer. 95 mass% or more and 100 mass% or less is more preferable.

  As long as the laminated body of this embodiment is provided with the above-mentioned laminated aluminum alloy and a resin layer, what laminated | stacked the other thing further may be sufficient. In particular, when the resin layer functions as an adhesive, the laminate includes a laminated aluminum alloy, a resin layer (that is, an adhesive), and a member (member to be joined) joined to the laminated aluminum alloy via the resin layer. Is preferably provided. Thereby, due to the high bonding strength between the laminated aluminum alloy and the resin layer, the bonding strength between the laminated aluminum alloy and the member to be joined can be further increased. Examples of the member to be joined include a metal member, a ceramic member, a plastic member, a glass member, and a composite material member thereof. From the viewpoint of using the laminated aluminum alloy of the present embodiment, so-called inorganic-organic bonding can be performed with the laminated aluminum alloy with higher bonding strength, the members to be bonded are plastic members and plastics. And a composite member of ceramic, glass or metal. Examples of the composite member include prepreg, and fiber reinforced plastic such as glass fiber reinforced plastic, carbon fiber reinforced plastic, and metal fiber reinforced plastic.

  In the laminate of this embodiment, the tensile strength between the laminated aluminum alloy and the resin layer is preferably 11.0 MPa or more, more preferably 12.0 MPa or more, and further preferably 13.0 MPa or more. . When the tensile strength is 11.0 MPa or more, the bonding strength between the laminated aluminum alloy and the resin layer becomes higher. The upper limit of the tensile strength is not particularly limited and is, for example, 25.0 MPa or less. The tensile strength can be measured according to the method described in the examples.

  When the resin layer functions as an adhesive, the laminate of the present embodiment applies a liquid or paste-like resin composition or a solution of the resin composition to the surface of the porous layer of the laminated aluminum alloy, and then the resin. Can be obtained by curing or drying the solution. Moreover, when a resin layer does not function as an adhesive agent, it joins with a lamination | stacking aluminum alloy by injecting the resin composition contained in a resin layer, etc., and the laminated body of this embodiment is obtained.

  According to this embodiment, in the laminated aluminum alloy, the thickness of the porous layer having a porous shape is 0.5 μm or more and 8.0 μm or less, so that the bonding strength between the laminated aluminum alloy and the resin layer is increased. Can be high.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Various evaluation methods are as follows.

(Tensile test)
An epoxy resin adhesive (product name “EP106NL”, manufactured by Cemedine Co., Ltd.) was applied to the surface of the porous layer of the laminated aluminum alloy (50 mm × 25 mm) within a range of 10 mm × 25 mm from the end of the laminated aluminum alloy. . Next, the laminated aluminum alloy coated with the epoxy resin adhesive was housed in a vacuum dryer heated to 60 ° C., kept in a vacuum state for 3 minutes, and then kept in a normal pressure state for 3 minutes. After holding in the vacuum state and holding in the normal pressure state three times, the laminated aluminum alloy to which the epoxy resin adhesive was adhered was taken out from the vacuum dryer. The two laminated aluminum alloys adhered with the epoxy resin adhesive obtained in this way are stacked so that the surfaces to which the epoxy resin adhesive is adhered face each other, sandwiched between office double clips, and heated to 130 ° C. Housed in a warm vacuum dryer. And the inside of a vacuum dryer was made into the vacuum state, and it hardened at 130 degreeC for 1 hour, and produced the test piece. About the test piece, the tensile strength was measured based on JISK6850 using the tensile testing machine (The product name "AGS-X" by Shimadzu Corporation). The results are shown in Table 2.

(Measurement of magnesium and aluminum contents in porous layer)
A laminated aluminum alloy (5 mm × 5 mm) was placed on a Teflon (registered trademark) mold and embedded in a thermosetting epoxy resin (manufactured by Pearls Petro Products, product name “Petropoxy154”). Next, mechanical polishing was performed using water-resistant abrasive paper, the sample was sectioned, and a test piece was obtained. About the test piece, the element from the cross-sectional direction (lamination direction) of the porous layer was measured using an ultra-high resolution field emission scanning electron microscope / energy dispersive X-ray spectroscopy (manufactured by Hitachi High-Tech Technologies, product name “SU8220”). The content of was measured. The results are shown in Table 2.

(Measurement of porous layer thickness)
Using the ultrahigh resolution field emission scanning electron microscope (product name “SU8220”, manufactured by Hitachi High-Technology Corp.), the test piece subjected to cross-section as described above was porous from the cross-sectional direction (stacking direction). The thickness of the stratum corneum was measured. This thickness is an average value of thicknesses at arbitrary three points. The results are shown in Table 2.

Example 1
An aluminum alloy piece (JIS A5052-H34) having a thickness of 1.0 mm and a size of 50 mm × 25 mm was prepared. Aminoguanidine carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to ion-exchanged water to obtain 80 mL of an aqueous solution having an aminoguanidine carbonate concentration of 3.0% by mass, and then sodium hydroxide (Wako Pure). 4 equivalents) was added to aminoguanidine to adjust the pH of the aqueous solution to 14. Furthermore, 80 mL (pH: 9) of 3 mass% aqueous solution of sodium borohydride (made by Wako Pure Chemical Industries, Ltd.) was prepared. The aluminum alloy piece was first immersed in an aqueous solution of sodium borohydride having a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution and sufficiently washed with ion-exchanged water. Next, the aluminum alloy piece was immersed in an aminoguanidine carbonate aqueous solution at a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution, thoroughly washed with ion-exchanged water, and then heated in a hot air dryer set at 50 ° C. It was dried for 1 hour to obtain a laminated aluminum alloy. FIG. 1 shows the surface SEM image of the porous layer of the laminated aluminum alloy, FIG. 2 shows the cross-sectional SEM image of the laminated aluminum alloy, and Table 2 shows the thickness of the porous layer. In FIG. 2, the portion having the vertical orientation shown in the vicinity of the center in the vertical direction is a porous layer, and the lower portion is an aluminum alloy as a base.

(Example 2)
An aluminum alloy piece (JIS A5052-H34) having a thickness of 1.0 mm and a size of 50 mm × 25 mm was prepared. Further, hydroxylamine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., 50% aqueous solution) was added to ion-exchanged water to obtain 80 mL of an aqueous solution having a concentration of hydroxylamine monohydrate of 3.0% by mass. Thereafter, sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added to adjust the pH of the aqueous solution to 14. Furthermore, 80 mL (pH: 9) of 3 mass% aqueous solution of sodium borohydride (made by Wako Pure Chemical Industries, Ltd.) was prepared. The aluminum alloy piece was first immersed in an aqueous solution of sodium borohydride having a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution and sufficiently washed with ion-exchanged water. Next, the aluminum alloy piece was immersed in a hydroxylamine monohydrate aqueous solution at a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution, sufficiently washed with ion-exchanged water, and dried in warm air set at 50 ° C. It was dried in the machine for 1 hour to obtain a laminated aluminum alloy. FIG. 3 shows a surface SEM image of the porous layer of the laminated aluminum alloy, FIG. 4 shows a cross-sectional SEM image of the laminated aluminum alloy, and Table 2 shows the thickness of the porous layer. In FIG. 4, the portion having the vertical orientation shown in the vicinity of the center in the vertical direction is a porous layer, and the lower portion is an aluminum alloy as a base.

Example 3
An aluminum alloy piece (JIS A5052-H34) having a thickness of 1.0 mm and a size of 50 mm × 25 mm was prepared. Moreover, after adding diethylhydroxylamine (made by Wako Pure Chemical Industries, Ltd.) to ion-exchange water and obtaining 80 mL of aqueous solution whose concentration of diethylhydroxylamine is 3.0 mass%, sodium hydroxide (Wako Pure Chemical Industries stock) The pH of the aqueous solution was adjusted to 14. Furthermore, 80 mL (pH: 9) of 3 mass% aqueous solution of sodium borohydride (made by Wako Pure Chemical Industries, Ltd.) was prepared. The aluminum alloy piece was first immersed in an aqueous solution of sodium borohydride having a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution and sufficiently washed with ion-exchanged water. Next, the aluminum alloy piece was immersed in a diethylhydroxylamine aqueous solution at a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution, washed thoroughly with ion-exchanged water, and washed in a warm air dryer set at 50 ° C. By drying for a time, a laminated aluminum alloy was obtained. FIG. 5 shows a surface SEM image of the porous layer of the laminated aluminum alloy, FIG. 6 shows a cross-sectional SEM image of the laminated aluminum alloy, and Table 2 shows the thickness of the porous layer. In FIG. 6, the portion having the vertical orientation shown in the vicinity of the center in the vertical direction is a porous layer, and the lower portion is an aluminum alloy as a base.

(Example 4)
An aluminum alloy piece (JIS A5052-H34) having a thickness of 1.0 mm and a size of 50 mm × 25 mm was prepared. Moreover, sodium hydroxide (made by Wako Pure Chemical Industries, Ltd.) was added to ion-exchange water, and 80 mL of aqueous solution whose sodium hydroxide density | concentration is 3.0 mass% was obtained (pH: 14). The aluminum alloy piece is immersed in an aqueous sodium hydroxide solution at a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution, sufficiently washed with ion-exchanged water, and dried in a hot air dryer set at 50 ° C. for 1 hour. Thus, a laminated aluminum alloy was obtained. FIG. 7 shows a surface SEM image of the porous layer of the laminated aluminum alloy, FIG. 8 shows a cross-sectional SEM image of the laminated aluminum alloy, and Table 2 shows the thickness of the porous layer. In FIG. 8, the portion having the vertical orientation shown in the vicinity of the center in the vertical direction is a porous layer, and the lower portion is an aluminum alloy as a base.

(Comparative Example 1)
An aluminum alloy piece (JIS A5052-H34) having a thickness of 1.0 mm and a size of 50 mm × 25 mm was prepared. Aminoguanidine carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to ion-exchanged water to obtain 80 mL of an aqueous solution having an aminoguanidine carbonate concentration of 3.0% by mass, and then sodium hydroxide (Wako Pure). The pH of the aqueous solution was adjusted to 12. Furthermore, 80 mL (pH: 9) of 3 mass% aqueous solution of sodium borohydride (made by Wako Pure Chemical Industries, Ltd.) was prepared. The aluminum alloy piece was first immersed in an aqueous solution of sodium borohydride having a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution and sufficiently washed with ion-exchanged water. Next, the aluminum alloy piece was immersed in an aminoguanidine carbonate aqueous solution at a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution, thoroughly washed with ion-exchanged water, and then heated in a hot air dryer set at 50 ° C. It was dried for 1 hour to obtain a treated aluminum alloy. A surface SEM image of the treated aluminum alloy is shown in FIG. The obtained treated aluminum alloy had a roughened surface, and although a slightly porous portion was observed, the thickness could not be measured.

(Comparative Example 2)
An aluminum alloy piece (JIS A5052-H34) having a thickness of 1.0 mm and a size of 50 mm × 25 mm was prepared. Further, hydroxylamine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., 50% aqueous solution) was added to ion-exchanged water to obtain 80 mL of an aqueous solution having a concentration of hydroxylamine monohydrate of 3.0% by mass. (PH: 12). The aluminum alloy piece was first immersed in an aqueous solution of sodium borohydride having a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution and sufficiently washed with ion-exchanged water. Next, the aluminum alloy piece was immersed in a hydroxylamine monohydrate aqueous solution at a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution, sufficiently washed with ion-exchanged water, and dried in warm air set at 50 ° C. It was dried in the machine for 1 hour to obtain a treated aluminum alloy. A surface SEM image of the treated aluminum alloy is shown in FIG. 10, and a cross-sectional SEM image is shown in FIG. The obtained treated aluminum alloy had a roughened surface, and although a slightly porous portion was observed, the thickness could not be measured.

(Comparative Example 3)
An aluminum alloy piece (JIS A5052-H34) having a thickness of 1.0 mm and a size of 50 mm × 25 mm was prepared. Further, diethylhydroxylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added to ion-exchanged water to obtain 80 mL (pH: 8) of an aqueous solution having a diethylhydroxylamine concentration of 3.0% by mass. Furthermore, 80 mL (pH: 9) of 3 mass% aqueous solution of sodium borohydride (made by Wako Pure Chemical Industries, Ltd.) was prepared. The aluminum alloy piece was first immersed in an aqueous solution of sodium borohydride having a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution and sufficiently washed with ion-exchanged water. Next, the aluminum alloy piece was immersed in a diethylhydroxylamine aqueous solution at a liquid temperature of 30 ° C. for 5 minutes, then taken out from the aqueous solution, washed thoroughly with ion-exchanged water, and washed in a warm air dryer set at 50 ° C. After drying for a time, a treated aluminum alloy was obtained. A surface SEM image of the treated aluminum alloy is shown in FIG. The obtained treated aluminum alloy had a roughened surface, and although a slightly porous portion was observed, the thickness could not be measured.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body provided with the laminated aluminum alloy which can make the joint strength of an aluminum alloy and a resin layer high, its manufacturing method, and the laminated aluminum alloy can be provided. Therefore, the present invention has industrial applicability in the field of laminated aluminum alloys that require such characteristics and laminated bodies using the laminated aluminum alloys.

Claims (10)

A laminated aluminum alloy comprising a porous layer having a porous shape on the surface,
A laminated aluminum alloy, wherein the thickness of the porous layer in the cross-sectional direction of the laminated aluminum alloy is 0.5 μm or more and 8.0 μm or less.   The laminated aluminum alloy according to claim 1, wherein the porous layer contains magnesium and aluminum.   The laminated aluminum alloy according to claim 2, wherein the porous layer contains magnesium in an amount of 10% by mass to 18% by mass and aluminum in an amount of 10% by mass to 28% by mass with respect to the total amount of the porous layer.   The laminated aluminum alloy according to any one of claims 1 to 3, wherein the porous shape is a porous shape in which an alloy portion in the porous layer has orientation in a thickness direction. A laminated aluminum alloy comprising a porous layer having a porous shape on the surface,
A laminated aluminum alloy obtained by bringing the surface of an aluminum alloy into contact with an aqueous solution having a pH exceeding 13.0. The aqueous solution comprises a compound represented by the following formula (1), a hydrate of a compound represented by the following formula (1), and a salt of a compound represented by the following formula (1) and an inorganic acid. The laminated aluminum alloy according to claim 5, comprising at least one selected from the group consisting of more than one kind.
(In formula (1), each R is independently a hydrogen atom, a methyl group, an ethyl group, or a monovalent group represented by the following formula (1a), and X is a hydroxy group or an amino group.
_{-C (NH 2) = NH (} 1a))   The aluminum alloy has a surface from which an oxide film has been removed by contacting the aluminum alloy with an aqueous solution containing sodium borohydride and / or sodium hydroxide before contacting the aqueous solution with the aqueous solution. 6. The laminated aluminum alloy according to 6. A method for producing a laminated aluminum alloy comprising a porous layer having a porous shape on the surface,
A production method comprising a step of bringing the surface of an aluminum alloy into contact with an aqueous solution having a pH exceeding 13.0. The aqueous solution comprises a compound represented by the following formula (1), a hydrate of a compound represented by the following formula (1), and a salt of a compound represented by the following formula (1) and an inorganic acid. The manufacturing method of Claim 8 containing 1 or more types chosen from more.
(In formula (1), each R is independently a hydrogen atom, a methyl group, an ethyl group, or a monovalent group represented by the following formula (1a), and X is a hydroxy group or an amino group.
_{-C (NH 2) = NH (} 1a))   A laminated body comprising the laminated aluminum alloy according to any one of claims 1 to 7 and a resin layer bonded to the surface of the porous layer having a porous shape of the laminated aluminum alloy.