JP6880531B2 - Silicon-containing aluminum alloy resin composite material and its manufacturing method - Google Patents

Description

The present invention relates to a silicon-containing aluminum alloy resin composite material and a method for producing the same.

Conventionally, it has been known that by combining metal and resin, it is possible to design parts that take advantage of the advantages of metal and resin, such as home appliances, mobile phones, automobile parts, personal computers and electronic parts. In various fields of the above, a metal material and a resin material are joined or integrated. As a method of joining such a metal material and a resin material, for example, joining by welding, joining by an adhesive, mechanical fixing and the like are known. However, there is a problem that the strength of the joint portion is not sufficient in the joining by welding, and the degree of freedom of the joining is small in the mechanical fixing. Further, in the case of bonding with an adhesive, the strength of the bonded portion changes depending on the adhesive used, so it is necessary to select an appropriate adhesive, and further, the adhesive deteriorates depending on the usage conditions and the bonding strength decreases. There was a problem.

Therefore, in recent years, as a method of joining or integrating a metal material and a resin material, a technique of processing the surface of the metal material and joining the resin material on the surface has been proposed. For example, in Japanese Patent Application Laid-Open No. 2015-136890 (Patent Document 1), an anodic oxide film is formed on the surface of pure aluminum or an aluminum alloy, and a resin film containing an epoxy resin as a main component is formed on the anodic oxide film. A resin-coated aluminum plate is described. Further, Patent Document 1 also describes that a silane coupling agent is applied to the surface of the anodic oxide film to improve the adhesion between the anodic oxide film and the resin film.

Further, in Japanese Patent Application Laid-Open No. 2016-522310 (Patent Document 2), the height, cross-sectional area, peripheral length, and number are specified as a metal-resin composite material in which an aluminum base material and a resin are more firmly bonded. A metal-resin composite material comprising an aluminum base material having an aluminum oxide film having a porous surface layer in which columnar bodies satisfying the above conditions are dispersed and arranged on the surface, and a resin bonded via the aluminum oxide film. Are listed.

On the other hand, according to Japanese Patent Application Laid-Open No. 2012-41579 (Patent Document 3), as a method for surface-treating a metal having excellent adhesiveness to a resin or the like, a metal of Sn or the like and zinc is formed on the surface of a material made of aluminum or an aluminum alloy. A method in which a surface film containing a carrier as a main component is formed by a displacement plating method and then zinc and the material are selectively dissolved by an etching treatment to form a porous etching layer on the surface of the material to roughen the surface. Are listed. However, when a material made of an aluminum alloy containing silicon is used as the material, in order to bond with a resin or the like, the material roughened by the above method is subjected to desmat treatment to reduce the silicon content on the surface of the material. I had to do it.

Japanese Unexamined Patent Publication No. 2015-136890 Special Table 2016-522310 Japanese Unexamined Patent Publication No. 2012-415579

However, in the resin-coated aluminum plate described in Patent Document 1, the adhesion between the anodic oxide film and the resin film is not always sufficiently high. Further, in the metal-resin composite material described in Patent Document 2, when an aluminum alloy base material containing silicon is used as the aluminum base material, the bonding strength with the resin is high, but the durability is not always sufficient. It wasn't a thing.

The present invention has been made in view of the above-mentioned problems of the prior art, and is a silicon-containing aluminum alloy resin composite in which a silicon-containing aluminum alloy base material and a resin are firmly bonded to each other and have excellent durability. It is an object of the present invention to provide a material and a method for producing the same.

As a result of intensive research to achieve the above object, the present inventors have made a case of joining a silicon-containing aluminum alloy base material (hereinafter, abbreviated as "Si-containing Al alloy base material") and a resin. , An aluminum oxide film having a porous surface layer in which columnar bodies having specific conditions such as height and cross-sectional area are dispersed and arranged is formed on the surface of the Si-containing Al alloy base material, and further, the aluminum oxide is formed. It has been found that by subjecting the coating film to a silane coupling treatment, the Si-containing Al alloy base material and the resin are firmly bonded to each other and the durability thereof is further improved, and the present invention has been completed.

That is, the silicon-containing aluminum alloy resin composite material of the present invention comprises silicon having a silicon-containing aluminum alloy base material having an aluminum oxide film on its surface and a resin bonded via the aluminum oxide film and a silane coupling agent. Containing aluminum alloy resin composite material
The silicon content in the silicon-containing aluminum alloy base material is 4 to 14% by mass with respect to all metal elements.
The aluminum oxide film has a porous surface layer in which columnar bodies having an average height of 10 to 100 nm are dispersed and arranged.
The average value of the total cross-sectional area of the columnar body in the field of view of 400 nm square randomly selected from the porous surface layer is 8000 to 128000 nm ² .
The average number of columns in a 400 nm square field of view of the porous surface layer randomly sampled is 10 to 430.
It is characterized by that.

In the silicon-containing aluminum alloy resin composite material of the present invention, the aluminum oxide film further has a porous intermediate layer having fine recesses between the porous surface layer and the silicon-containing aluminum alloy base material. It is preferable that the average pore diameter of the fine recesses is 5 to 50 nm, and the average distance between the centers of the fine pores is 5 to 90 nm.

Further, the method for producing a silicon-containing aluminum alloy resin composite material of the present invention is described.
A porous surface formed by anodizing a silicon-containing aluminum alloy base material having a silicon content of 4 to 14% by mass with respect to all metal elements, and dispersing columns with an average height of 10 to 100 nm. The average value of the total cross-sectional areas of the columnar bodies in a randomly selected 400 nm square visual field is 8000 to 128000 nm ² , and the above is a randomly selected 400 nm square visual field. Anodizing step of forming an aluminum oxide film having the porous surface layer having an average number of columns of 10 to 430 on the surface of the silicon-containing aluminum alloy base material.
A silane coupling treatment step of applying a surface treatment to the aluminum oxide film having a porous surface layer using a silane coupling agent, and a silane coupling treatment step.
A joining step of joining the silicon-containing aluminum alloy base material and the resin via the aluminum oxide film having the porous surface layer and the silane coupling agent.
It is characterized by including.

In the anodizing treatment step, the porous surface layer and the porous intermediate layer having fine recesses between the porous surface layer and the silicon-containing aluminum alloy base material, which are the fine recesses. An aluminum oxide film having a porous intermediate layer having an average pore diameter of 5 to 50 nm and an average pore center distance of the fine recesses of 5 to 90 nm is formed on the surface of the silicon-containing aluminum alloy base material. It is preferable to do so.

Further, in the silane coupling treatment step, it is preferable to use a silane coupling agent solution having a concentration of 0.5 to 5% by mass.

The reason why the Si-containing Al alloy base material and the resin are firmly bonded by the present invention and the durability thereof is improved is not necessarily clear, but the present inventors presume as follows. That is, when an aluminum oxide film having a porous surface layer in which columnar bodies having specific conditions such as height and cross-sectional area are dispersed and arranged is formed on the surface of a Si-containing Al alloy base material by anodizing treatment, it is extremely difficult. A metal joint surface with a large surface area is created. When the Si-containing Al alloy base material having such a metal bonding surface and the resin are bonded, the fine columnar bodies on the metal bonding surface fit (bite) into the resin layer, so that the Si-containing Al alloy group is formed by the anchor effect. It is presumed that the material and resin are firmly bonded. However, since the metal bonding surface having a fine columnar body is not formed on the surface of the Si-containing Al alloy base material where silicon exists, it is presumed that the anchor effect as described above cannot be obtained and the bonding durability is lowered. Will be done.

In the present invention, a silane coupling agent is attached (preferably bonded) to a portion of the surface of the Si-containing Al alloy base material where silicon is present, and the surface of the Si-containing Al alloy base material is interposed via the silane coupling agent. Since the part where silicon is present and the resin are bonded, it is presumed that the bonding durability is improved.

According to the present invention, the silicon-containing aluminum alloy base material and the resin are firmly bonded to each other, and it is possible to obtain a silicon-containing aluminum alloy resin composite material having excellent durability.

It is a graph which shows the tensile shear strength of the composite material obtained in Examples 1 to 3 and Comparative Examples 1 and 2. It is a graph which shows the relationship between the hot water immersion time and the tensile shear strength of the composite material obtained in Example 1 and Comparative Example 1. 6 is a graph showing the relationship between the number of thermal cycles of the composite materials obtained in Example 2 and Comparative Example 1 and the tensile shear strength. 6 is a graph showing the relationship between the number of thermal cycles of the composite material obtained in Reference Example 1 and the tensile shear strength.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof.

[Silicon-containing aluminum alloy resin composite material]
First, the silicon-containing aluminum alloy resin composite material of the present invention will be described. The silicon-containing aluminum alloy resin composite material of the present invention is bonded to a silicon-containing aluminum alloy base material (Si-containing Al alloy base material) having an aluminum oxide film on the surface via the aluminum oxide film and a silane coupling agent. It is equipped with the resin that is used.
The silicon content in the silicon-containing aluminum alloy base material is 4 to 14% by mass with respect to all metal elements.
The aluminum oxide film has a porous surface layer in which columnar bodies having an average height of 10 to 100 nm are dispersed and arranged.
The average value of the total cross-sectional area of the columnar body in the field of view of 400 nm square randomly selected from the porous surface layer is 8000 to 128000 nm ² .
The average number of the columnar bodies in the field of view of 400 nm square extracted at random of the porous surface layer is 10 to 430.

(Si-containing Al alloy base material)
In the present invention, the Si-containing Al alloy base material is not particularly limited as long as it has a silicon content within a predetermined range and can form an aluminum oxide film, and is a No. 4000 series specified by JIS. (Al—Si alloy type) can be used. Also, die-cast grade products can be used. The shape of such a Si-containing Al alloy base material is not particularly limited, and for example, one processed into a desired shape by a known metal processing method such as cutting, pressing, cutting, or grinding can be used.

The silicon content of such a Si-containing Al alloy base material is 4 to 14% by mass. When the silicon content is less than the above lower limit, the aluminum base material and the resin are firmly bonded by the method described in Japanese Patent Application Laid-Open No. 2016-522310 (Patent Document 2), and the aluminum resin having excellent durability thereof. A composite material can be obtained. On the other hand, when the silicon content exceeds the upper limit, the amount of resin bonded via the aluminum oxide film (particularly, the columnar body of the porous surface layer) decreases, and the bonding strength decreases. The silicon content is preferably 10 to 14% by mass from the viewpoint of further improving the decrease in bonding durability.

The Si-containing Al alloy base material used in the present invention has an aluminum oxide film on its surface. Further, this aluminum oxide film has a porous surface layer in which columnar bodies having an average height of 10 to 100 nm are dispersed and arranged. As a result, the Si-containing Al alloy base material and the resin are firmly bonded. If the average height of the columnar body is less than the lower limit, it becomes difficult to control the height of the columnar body, and the fitting (biting) into the resin layer becomes insufficient. On the other hand, if the upper limit is exceeded, The anodizing treatment time for forming the columnar body becomes long, and the manufacturing cost increases. The average height of such a columnar body is preferably 10 to 80 nm, more preferably 20 to 70 nm, from the viewpoint of bonding strength and productivity.

The average height of the columnar body of the porous surface layer can be measured as follows in accordance with the method described in Japanese Patent Application Laid-Open No. 2016-522310. That is, the longitudinal cross section of the porous surface layer of the aluminum oxide coating is photographed by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Based on the obtained SEM image or TEM image, the upper end (surface of the porous surface layer) and the lower end (porous surface layer and porous intermediate layer (aluminum group if there is no porous intermediate layer) of the porous surface layer Measure the maximum and minimum values of the distance to the interface) with the material). The arithmetic mean value of the maximum value and the minimum value is calculated, and a normal distribution in which the difference between the obtained arithmetic mean value and the minimum value is three times the standard deviation σ (3σ) is obtained. The average value in this normal distribution is taken as the average height of the porous surface layer, that is, the average height of the columnar bodies.

Further, in the porous surface layer, it is necessary that the average value of the total cross-sectional areas of the columnar bodies in a randomly sampled 400 nm square field of view is 8000 to 128000 nm ^2. If the average value of the total cross-sectional area of the columnar body is less than the lower limit, the columnar body becomes too thin and the strength of the columnar body itself is insufficient, while if it exceeds the upper limit, the space on the side surface of the columnar body is exceeded. Is narrowed, and the size of the space in which the resin can enter is insufficient. Further, the average value of the total cross-sectional area of such a columnar body is preferably 16000 to 104000 nm ^{2 and} more preferably ^{32000 to 80,000 nm 2} from the viewpoint of securing the strength of the columnar body and the space for the resin to penetrate. ..

Further, in the porous surface layer, the average value of the number of the columnar bodies in a randomly selected 400 nm square field of view needs to be 10 to 430. When the average value of the number of columnar bodies is less than the lower limit, the surface area to be fitted (bite) into the resin layer is insufficient, while when the upper limit is exceeded, the space through which the resin can enter is insufficient. Further, the average value of the number of such columnar bodies is preferably 50 to 350, preferably 80 to 250, from the viewpoint of securing the surface area to be fitted (bite) into the resin layer and the space for the resin to invade. More preferred.

Further, in the porous surface layer, the average value of the total circumference of the cross section of the columnar body in a randomly selected 400 nm square field of view is preferably 1000 to 27000 nm, preferably 3000 to 23000 nm. More preferably, it is particularly preferably 5000 to 20000 nm. When the average value of the total circumference of the cross section of the columnar body is less than the lower limit, the columnar body tends to be too thin and the strength of the columnar body itself tends to be insufficient, while when the upper limit is exceeded, the columnar body tends to be insufficient. The space on the side surface of the body tends to be narrowed, and the size of the space through which the resin can enter tends to be insufficient.

The average value of the number of columns in the porous surface layer, the average value of the total area of the cross sections of the columns, and the average value of the total circumference of the cross sections of the columns are shown in Japanese Patent Application Laid-Open No. 2016-522310. According to the method described in the above, image analysis can be performed and measured as follows.

That is, first, the cross section of the porous surface layer of the aluminum oxide film is photographed by SEM or TEM. After removing noise from the obtained SEM image or TEM image, the obtained image is binarized. Specifically, in the image after noise removal, a brightness value (threshold value) for distinguishing between the columnar body portion and other parts is set, and a region having a brightness value equal to or higher than this threshold value is extracted to obtain a binary image. obtain. Next, the obtained binary image is subjected to a separation process of the extracted region. This separation process can be performed, for example, by a Watershed subdivision process. Specifically, based on the binary image, an Euclidean distance map (EDM) is created, extreme erosion points (UEPs, maximums or vertices of EDM) are found, and each UEP is located in the region of the UEP as much as possible. The extracted region is separated by extending until it reaches the edge (edge) or until it reaches the edge of another (next) (growing) UEP region. From the separated regions, the minimum size that can be recognized as the cross section of the columnar body is determined, and the region larger than this minimum size is extracted as the columnar body region.

By obtaining the number, area, and perimeter of the columnar region extracted in this way, the average value of the number of columnar bodies in the porous surface layer, the average value of the total cross-sectional area of the columnar body, and the columnar body The perimeter of the cross section of is obtained.

Specifically, in the SEM image or TEM image of the cross section of the porous surface layer, a field of view of 400 nm square is randomly extracted, and in this field of view, the columnar region is extracted according to the above method. The extracted columnar body region is counted, and this is taken as the number of columnar bodies in a field of view of 400 nm square. The number of columns is determined in a 400 nm square field of view at five randomly selected locations, and the average value thereof is taken as the average value of the number of columns in the 400 nm square field of view.

Further, the area of each extracted columnar body region is obtained, and this is used as the cross-sectional area of the columnar body to obtain the total cross-sectional area of the columnar body in a field of view of 400 nm square. The total cross-sectional area of the columnar body is calculated in five randomly selected 400 nm square visual fields, and the average value thereof is taken as the average value of the total cross-sectional areas of the columnar body in the 400 nm square visual field. ..

Further, the perimeter of the extracted columnar region is determined, and this is used as the perimeter of the cross section of the columnar body to obtain the total perimeter of the cross section of the columnar body in a field of view of 400 nm square. The total perimeter of the cross section of the columnar body is calculated in five randomly selected 400 nm square visual fields, and the average value thereof is the perimeter of the perimeter of the cross section of the columnar body in the 400 nm square visual field. The average value of the total.

It should be noted that such image analysis can be performed by one image analysis software or by combining a plurality of image analysis software and various analysis processing software. Examples of such image analysis software include ImageJ (image processing software developed by the National Institutes of Health) and the like.

Further, in the silicon-containing aluminum alloy resin composite material of the present invention, the aluminum oxide film further has a porous intermediate layer having fine recesses between the porous surface layer and the Si-containing Al alloy base material. It is preferable that it is one. As a result, the Si-containing Al alloy base material and the resin tend to be more firmly bonded. Further, such a porous intermediate layer may be composed of one layer or two or more layers.

In such a porous intermediate layer, the average pore diameter of the fine recesses is preferably 5 to 50 nm, more preferably 5 to 30 nm, and particularly preferably 10 to 20 nm. When the average pore diameter of the fine recesses is less than the lower limit, the anchor effect due to the intrusion of the resin tends not to be sufficiently obtained, while when the average pore diameter exceeds the upper limit, the homogeneity of the porous intermediate layer tends to decrease. ..

Further, in the porous intermediate layer, the average distance between the centers of the fine pores is preferably 5 to 90 nm, more preferably 10 to 70 nm, and particularly preferably 20 to 50 nm. When the average distance between the centers of the pores of the fine recesses is less than the lower limit, it tends to be difficult to obtain a homogeneous wall surface forming the recessed pores, while when the distance exceeds the upper limit, the unit area of the surface of the porous intermediate layer The number of per-pores tends to decrease, and the size of the space in which the resin can penetrate tends to be insufficient.

The average pore diameter and the average distance between the centers of the fine pores of the porous intermediate layer can be measured as follows in accordance with the method described in Japanese Patent Application Laid-Open No. 2016-522310. That is, an SEM image of the surface of the porous intermediate layer of the aluminum oxide film is photographed by SEM or TEM. In the obtained SEM image or TEM image, pores are randomly sampled, the maximum length in the cross section of the pores is measured, and this is taken as the pore diameter. The pore diameter is measured in five randomly selected pores, and the average value thereof is taken as the average pore diameter of the fine recesses.

In addition, the distance between the center of the randomly sampled pore and the center of the pore closest to the pore is measured, and this is defined as the distance between the centers of the pores. The distance between the centers of the pores is measured in five randomly selected pores, and the average value thereof is taken as the average distance between the centers of the pores of the fine recesses.

The average thickness of the porous intermediate layer is preferably 300 nm to 20 μm, more preferably 300 nm to 15 μm, and particularly preferably 500 nm to 10 μm. When the average thickness of the porous intermediate layer is less than the lower limit, it tends to be difficult to obtain a homogeneous porous intermediate layer, while when the average thickness exceeds the upper limit, anodizing treatment for forming the porous intermediate layer is performed. The time tends to increase and the manufacturing cost tends to increase.

The average thickness of the porous intermediate layer can be measured as follows in accordance with the method described in Japanese Patent Application Laid-Open No. 2016-522310. That is, the vertical cross section of the porous intermediate layer of the aluminum oxide film is photographed by SEM or TEM. Based on the obtained SEM image or TEM image, the upper end of the porous intermediate layer (the interface between the porous surface layer and the porous intermediate layer (or the surface of the porous intermediate layer if there is no porous surface layer)) Measure the distance from the lower end (the interface between the porous intermediate layer and the aluminum substrate). This distance is measured at 5 randomly selected points, and the average value is taken as the average thickness of the porous intermediate layer.

Further, as the form of the fine recesses in the porous intermediate layer, the performance of the porous intermediate necessary for realizing the performance (particularly bonding strength and bonding durability) of the target silicon-containing aluminum alloy resin composite material is obtained. There is no particular limitation as long as it is expressed. For example, a Si-containing Al alloy base material having an orientation grown in a direction perpendicular to the surface of the Si-containing Al alloy base material or a direction having a certain angle, or a Si-containing Al alloy base material. Non-oriented material that grows in a random direction with respect to the surface (for example, a nest-like structure of ants, a three-dimensional network structure in which concave holes are entwined in a three-dimensional network, a random-shaped structure), straight And there is no orientation.

(Silane coupling agent)
The silane coupling agent used in the present invention is not particularly limited, and examples thereof include various silane coupling agents such as amino-based, epoxy-based, methacrylic-based, acrylic-based, and mercapto-based. Of these, amino-based silane coupling agents and mercapto-based silane coupling agents are preferable from the viewpoint of high affinity with resins, and amino-based silane coupling agents are extremely stable in aqueous solutions. Is more preferable.

(resin)
The resin used in the present invention is preferably a resin that can be used for general resin molding such as injection molding and hot press molding, but is not particularly limited, and is, for example, general-purpose plastic, general-purpose engineering plastic, and super-engineering plastic. Examples thereof include thermoplastic resins such as, and thermosetting resins, which can be appropriately selected according to various uses. Such a thermoplastic resin or a thermosetting resin may be used alone or in combination of two or more.

Examples of the general-purpose plastic include polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-acrylonitrile-styrene copolymer (MAS resin), and methyl methacrylate-acrylonitrile. Acrylovinyl-based resins such as -butadiene-styrene copolymer (MABS resin) and styrene-butadiene-styrene copolymer (SBS resin); polymethylmethacrylate, polymethylacrylate, polymethacrylic acid, copolymers thereof, acrylic Acrylic resins such as rubber; vinyl cyanide resins such as polyacrylonitrile, acrylonitrile-methylacrylate copolymer, acrylonitrile-butadiene copolymer; polyethylene, polypropylene, polyisoprene, polybutadiene, ethylene-propylene-diene monomer rubber, ethylene-propylene Polyvinyl chloride resins such as rubber; polyvinyl chloride, polyvinylidene chloride and the like; polyvinyl alcohol, polyethylene terephthalate and the like can be mentioned.

Examples of the general-purpose engineering plastic include polyamides such as nylon 6, nylon 66, and nylon 12, polyacetal (polyoxymethylene), polycarbonate, modified polyphenylene ether, polybutylene terephthalate, and ultra-high molecular weight polyethylene.

Examples of the super engineering plastic include polyarylene sulfides such as polysulfone, polyethersulfone, and polyphenylene sulfide, polyarylates, acrylate polyarylates, thermoplastic polyamideimides, polyetherimides, polyether ether ketones, thermoplastic polyimides, and liquid crystal polyesters. Liquid crystal polymer: Fluororesin such as polytetrafluoroethylene, fluorinated ethylene propylene, polychlorotrifluoroethylene, polyfluorovinylidene, and polyvinyl fluoride can be mentioned.

Other thermoplastic resins include impact resistant polystyrene (HIPS), acid or acid anhydride-modified polyolefin resin, epoxy-modified polyolefin resin, cyclic polyolefin, acid or acid anhydride-modified acrylic elastomer, and epoxy-modified acrylic elastomer. , Silicone rubber, fluororubber, natural rubber, imide group-containing vinyl resin, poly 1,4-cyclohexanedimethylterephthalate, polylactic acid, polyether ketone ketone, polyether amide and the like.

The thermosetting resin is not particularly limited, but is an epoxy resin, a phenol resin, a melamine resin, a thermosetting polyimide resin, a thermosetting polyamideimide, a thermosetting silicone resin, a urea resin, an unsaturated polyester resin, and the like. Examples thereof include urea resin, benzoguanamine resin, alkyd resin, and urethane resin.

(Silicon-containing aluminum alloy resin composite material)
The silicon-containing aluminum alloy resin composite material of the present invention comprises a Si-containing Al alloy base material having the aluminum oxide film on its surface, and the resin bonded to the aluminum oxide film via the silane coupling agent. To prepare.

In the silicon-containing aluminum alloy resin composite material of the present invention, it is sufficient that the Si-containing Al alloy base material and the resin are bonded via an aluminum oxide film and a silane coupling agent, and the Si-containing Al alloy base material or the resin may be bonded. , Other layers (for example, other resin layers, inorganic layers, etc.) may be laminated. The configuration of such other layers is not particularly limited, and the design can be appropriately changed depending on the use of the silicon-containing aluminum alloy resin composite material and the like.

In addition, various additives can be added to the resin in the metal resin composite material of the present invention as long as the effects of the present invention are not impaired. By adding additives, the elasticity of the resin is improved (effect of inorganic fillers such as carbon fiber and glass fiber), polarity change (effect of rubber, elastomer, and other resins), deterioration suppression, and delay of decomposition reaction (effect of decomposition reaction). Due to the effects of antioxidants, etc.), the bonding strength is further improved, the wettability of the resin-metal interface is further improved, the interfacial adhesiveness is further improved, and long-term stability (heat resistance, moist heat resistance, water resistance, etc.) ) Can be expected to improve.

Such additives are not particularly limited, but for example, flame retardants, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants, mold release agents, crystals. Surface treatment agents such as nucleating agents, viscosity modifiers, coloring agents, dyes, antibacterial agents, silane coupling agents; graphite, carbon nanofibers, carbon nanotubes, carbon nanoplatelets, graphene, multi-layer graphene, nanographite (graphene nanoribbon) Etc.), carbon-based nanofillers such as nanographene, carbon nanohorn, carbon nanocone, carbon nanocoil, fullerene, synthetic fibers such as glass fiber, carbon fiber, and aramid fiber, and fibrous substances such as natural fibers such as cellulose, chitin, and chitosan; Layered silicates such as (mica) minerals and kaolin minerals, inorganic fillers such as calcium carbonate, calcium phosphate, titanium oxide, silica, whiskers, alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, diamond, zinc oxide, etc. Be done. Note that adding a large amount of these additives may cause a decrease in impact strength. Further, an organic additive such as a rubber, an elastomer, a soft resin component and / or a plasticizer may be added. However, it should be noted that adding a large amount of organic additives may cause a decrease in high-temperature rigidity and deflection temperature under load.

The type of such an additive is not particularly limited, but the compatibility is improved by a component whose compatibility with the resin does not extremely decrease, or by chemical modification or addition of a compatibility agent even if the compatibility decreases. Ingredients are preferred. In addition, such additives may be used alone or in combination of two or more.

The method for blending such an additive is not particularly limited as long as the additive can be dispersed in the resin. For example, a method of mixing the resin and the additive in a solvent, a uniaxial method, or a method of mixing the additive in a solvent. Conventionally known methods such as a method of melt-kneading the resin and the additive using an extruder having a multi-screw solvent, a rubber roll machine, a Banbury mixer, or the like can be adopted. When a low-viscosity thermosetting resin is used as the resin, it can be mixed by performing a compounding treatment using a self-revolution mixer.

[Manufacturing method of silicon-containing aluminum alloy resin composite material]
Next, a method for producing the silicon-containing aluminum alloy resin composite material of the present invention will be described. The method for producing a silicon-containing aluminum alloy resin composite material of the present invention comprises the porous surface layer obtained by subjecting the Si-containing Al alloy base material to anodization treatment and dispersing and arranging columnar bodies satisfying predetermined conditions. The Si-containing aluminum oxide film (preferably an aluminum oxide film further comprising a porous intermediate layer having fine recesses satisfying predetermined conditions between the porous surface layer and the Si-containing Al alloy base material). Anodization process formed on the surface of Al alloy base material and
A silane coupling treatment step of applying a surface treatment to the aluminum oxide film having a porous surface layer using a silane coupling agent, and a silane coupling treatment step.
A joining step of joining the silicon-containing aluminum alloy base material and the resin via the aluminum oxide film having the porous surface layer and the silane coupling agent.
It is a method including.

(Anodizing process)
In the anodic oxidation treatment step according to the present invention, as an anodic oxidation treatment method, aluminum oxide having the porous surface layer in which columnar bodies satisfying predetermined conditions are dispersed and arranged on the surface of the Si-containing Al alloy base material. Any method may be used in which a coating film (preferably an aluminum oxide coating film further comprising a porous intermediate layer having fine recesses satisfying a predetermined condition is formed between the porous surface layer and the Si-containing Al alloy base material). However, there is no particular limitation, but a method of subjecting the surface of the Si-containing Al alloy base material to a plurality of anodic oxidation treatments is preferable. For example, electrolysis is performed in an electrolytic solution using the Si-containing Al alloy base material as an anode and an insoluble electrode as a cathode (electrolysis method), and the surface of the Si-containing Al alloy base material is subjected to a plurality of anodization treatments. Therefore, an aluminum oxide film (anodic oxide film) having the porous surface layer (preferably further having the porous intermediate layer) can be formed.

Further, in the anodizing treatment step according to the present invention, a known anodizing treatment can be adopted for each of the plurality of anodizing treatments. Electrolytic treatment conditions such as the electrolytic method performed in such anodization treatment, the cathode and electrolytic solution used in this electrolytic method, the concentration and temperature of this electrolytic solution, the current density in the electrolytic method, the voltage, and the electrolytic treatment time are particularly limited. The shape and structure of the target aluminum oxide film, that is, the shape and structure of the target porous surface layer, the shape and structure of the target porous intermediate layer, and the like can be formed. The processing method and conditions can be appropriately selected.

The electrolysis method is not particularly limited, and for example, a cyclic method, a constant current method, a constant potential method, a pulse constant potential method, a pulse constant current method, or the like can be adopted. The cathode is not particularly limited as long as it does not react with an electrolytic solution or has extremely low conductivity. For example, an insoluble conductive plate made of platinum, lead, stainless steel, carbon or the like can be used, and among them, a platinum plate. Is preferable.

The electrolytic solution is not particularly limited, and examples thereof include acidic solutions such as phosphoric acid, chromic acid, oxalic acid, and sulfuric acid, and among them, oxalic acid solution and sulfuric acid solution are preferable. These acidic solutions may be used alone or in combination of two or more. The concentration of such an electrolytic solution is appropriately selected depending on other conditions such as the type of the electrolytic solution to be used, the shape and structure of the porous surface layer and the porous intermediate layer to be formed, and the like, and is, for example, 0. It is preferably 0.01 to 10 mol / L, more preferably 0.01 to 1 mol / L. The temperature of the electrolytic solution is preferably −10 to 80 ° C., more preferably −10 to 60 ° C. By carrying out the anodizing treatment at a temperature within the above range, the porous surface layer and the porous intermediate layer can be easily formed on the surface of the Si-containing Al alloy base material. On the other hand, when the temperature of the electrolytic solution is less than the lower limit, it tends to be difficult to form the porous surface layer and the porous intermediate layer made of columnar bodies satisfying a predetermined condition, and on the other hand, the upper limit may be exceeded. Since the formed aluminum oxide film is dissolved again, it tends to be difficult to form the porous surface layer and the porous intermediate layer made of columnar bodies satisfying predetermined conditions.

The current density in such an electrolysis method is not particularly limited, and for example, 0.002 to 2.5 A / dm ² is preferable, 0.002 to 1.0 A / dm ² is more preferable, and 0.002 to 0. 5A / dm ² is particularly preferable. When the current density is less than the lower limit, the formation rate of the porous surface layer and the porous intermediate layer tends to be very slow, while when the current density exceeds the upper limit, the formed aluminum oxide film is dissolved again. The porous surface layer and the porous intermediate layer made of a columnar body satisfying the above conditions tend to be difficult to form.

The voltage in the electrolysis method is preferably 1.0 to 30 V, more preferably 1.0 to 20 V, and particularly preferably 1.0 to 10 V. The electrolysis treatment time is preferably 30 seconds to 100 minutes, more preferably 30 seconds to 60 minutes, and particularly preferably 30 seconds to 30 minutes.

In the anodizing treatment step according to the present invention, when the anodizing treatment is performed a plurality of times, the treatment conditions for each treatment are set to [thickness of the layer formed by the second and subsequent anodizing treatments] ≥ [first anodizing. It is preferable to set so as to satisfy the [thickness of the layer formed by the treatment], [the treatment conditions for the second and subsequent anodization (current density and / or voltage)]> [the treatment conditions for the first and subsequent anodization]. (Current density and / or voltage)] is more preferable, and [the second and subsequent anodizing treatment conditions (current density and / or voltage)] is [the first and subsequent anodizing treatment conditions. (Current density and / or voltage)] is particularly preferable. As a result, an aluminum oxide film having the porous surface layer made of a columnar body satisfying a predetermined condition (preferably, fine particles satisfying the predetermined condition between the porous surface layer and the Si-containing Al alloy base material). An aluminum oxide film (aluminum oxide film further including a porous intermediate layer having recesses) can be easily formed on the surface of the Si-containing Al alloy base material.

Further, as the conditions in the first anodic oxidation treatment, the concentration of the electrolytic solution is 0.01 to 10 mol / L (more preferably 0.01 to 1 mol / L), and the temperature of the electrolytic solution is −10 to 60. ° C., current density 0.002 to 1.0 A / dm ² (more preferably 0.002 to 0.5 A / dm ² ), voltage 1.0 to 30 V (more preferably 1.0 to 1.0 to dm 2). It is 10V), and the electrolytic treatment time is preferably 30 seconds to 100 minutes (more preferably 30 seconds to 30 minutes), and the conditions for the second and subsequent anodic oxidation treatments are that the concentration of the electrolytic solution is 0. It is 0.01 to 10 mol / L (more preferably 0.01 to 1 mol / L), the temperature of the electrolytic solution is −10 to 60 ° C., and the current density is 0.002 to 1.0 A / dm ² (more preferably). Is 0.002 to 0.5 A / dm ² ), the voltage is 1.0 to 30 V (more preferably 1.0 to 20 V), and the electrolysis treatment time is 30 seconds to 100 minutes (more preferably 30 seconds). ~ 60 minutes). As a result, an aluminum oxide film having the porous surface layer made of a columnar body satisfying a predetermined condition (preferably, fine particles satisfying the predetermined condition between the porous surface layer and the Si-containing Al alloy base material). An aluminum oxide film (aluminum oxide film further including a porous intermediate layer having recesses) can be more easily formed on the surface of the Si-containing Al alloy base material.

In the method for producing a silicon-containing aluminum alloy resin composite material of the present invention, prior to such anodizing treatment, pretreatment (buffing treatment, hairline treatment, satin finish / pattern) usually performed before the conventional anodizing treatment is performed. Appropriate treatment) and pretreatment (surface cleaning / melting treatment such as degreasing treatment, etching treatment, electrolytic polishing treatment, etc.) can be appropriately applied to the treated surface of the Si-containing Al alloy base material. Further, after the anodizing treatment, a post-treatment (washing treatment, sealing treatment, etc.) usually performed after the conventional anodizing treatment can be appropriately performed. Further, after the anodizing treatment, the aluminum oxide film may be treated with a phosphoric acid solution. In the method for producing a silicon-containing aluminum alloy resin composite material of the present invention, since the silane coupling treatment described later is performed, a desmat treatment is performed to reduce the Si content on the surface of the Si-containing Al alloy base material. No need.

The degreasing treatment can be carried out using, for example, a normal degreasing bath containing sodium hydroxide, sodium carbonate, sodium phosphate, a surfactant and the like, and the treatment conditions are an immersion temperature of 15 to 55 ° C. The temperature is preferably 25 to 40 ° C., the immersion time is preferably 1 to 10 minutes, and the immersion time is more preferably 3 to 6 minutes.

The etching treatment can be performed using, for example, an alkaline aqueous solution of sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ) or the like, and the treatment conditions include an alkaline aqueous solution. The concentration is preferably 20 to 200 g / L, more preferably 50 to 150 g / L, the immersion temperature is preferably 30 to 70 ° C, more preferably 40 to 60 ° C, and soaking. The time is preferably 0.5 to 5 minutes, more preferably 1 to 3 minutes. Further, the acid etching treatment can be performed using an acid aqueous solution such as hydrochloric acid, nitric acid, sulfuric acid, or phosphoric acid, and the treatment conditions are preferably such that the concentration of the acid aqueous solution is 20 to 200 g / L, and the immersion temperature is high. The temperature is preferably 30 to 70 ° C, more preferably 40 to 60 ° C, and the immersion time is preferably 0.5 to 5 minutes, more preferably 1 to 3 minutes.

The electrolytic polishing treatment can be performed using, for example, an aqueous solution of phosphoric acid, phosphoric acid-sulfuric acid, phosphoric acid-sulfuric acid-chromic acid, perchloric acid-anhydrous acetic acid, perchloric acid-ethanol, nitric acid, etc. As conditions, the current density is ^{preferably 1} to 10 A / dm 2, the bath voltage is preferably 20 to 30 V, and the processing time is preferably 1 to 5 minutes.

In the water washing treatment, for example, it is preferable to wash the Si-containing Al alloy base material on which the aluminum oxide film is formed at a temperature of 5 to 60 ° C. (more preferably 10 to 50 ° C.). More specifically, it is preferable to wash with tap water at room temperature a plurality of times and then with water at about 50 ° C. for about 30 seconds.

As described above, by forming the aluminum oxide film having the porous surface layer made of a columnar body satisfying a predetermined condition on the surface of the Si-containing Al alloy base material, the surface of the Si-containing Al alloy base material and the resin In addition to facilitating contact (adhesion) with the porous surface layer, the resin in contact with the porous surface layer is entangled with the columnar body, and the invasion of the aluminum oxide film into the fine recesses is promoted. Since the columnar body fits (bites) into the resin layer, the Si-containing Al alloy base material and the resin can be easily and firmly bonded to each other.

(Silane coupling treatment process)
In the silane coupling treatment step according to the present invention, the silane coupling treatment method is not particularly limited, and a conventionally known method can be adopted. The silane coupling agent used in the silane coupling treatment method is also not particularly limited, and known silane coupling agents such as amino-based, epoxy-based, methacrylic-based, acrylic-based, and mercapto-based are mentioned. Amino-based silane coupling agents and mercapto-based silane coupling agents are preferable from the viewpoint of high affinity with the above, and amino-based silane coupling agents are more preferable from the viewpoint of being extremely stable in an aqueous solution.

Such a silane coupling agent is usually used in the state of a solution (preferably an aqueous solution). For example, the silane coupling agent solution is applied to the surface of the aluminum oxide film of the Si-containing Al alloy base material, or the oxidation is performed. The silane coupling agent is adhered to the surface of the aluminum oxide film by immersing the Si-containing Al alloy base material having the aluminum film in the silane coupling agent solution. At this time, the silane coupling agent adheres to the portion of the surface of the Si-containing Al alloy base material where Si exists, that is, the portion of the aluminum oxide coating in which the columnar body is not formed, and the silane coupling agent is applied. Since the portion of the aluminum oxide film in which the columnar body is not formed and the resin are firmly adhered to each other, the Si-containing Al alloy base material and the resin can be easily and firmly bonded to each other. Its durability is also improved.

The concentration of the silane coupling agent solution is not particularly limited. For example, when the Si-containing Al alloy base material is immersed in the silane coupling agent solution, the Si-containing Al alloy base material and the resin are mixed. From the viewpoint of stronger bonding, 0.5 to 5% by mass is preferable, 1 to 3% by mass is more preferable, and 1.5 to 2.5% by mass is particularly preferable.

(Joining process)
In the bonding step according to the present invention, as a method of bonding the Si-containing Al alloy base material and the resin, an aluminum oxide film having the porous surface layer formed by the anodic oxidation treatment and the silane coupling treatment are used. The method is not particularly limited as long as the method can bond the Si-containing Al alloy base material and the resin via the silane coupling agent adhering to the surface of the aluminum oxide film, and is, for example, an injection molding method or compression molding. A known method for molding a resin, such as a method, a melt crimping method, and a pressure pressing method, can be appropriately adopted, and among them, an injection molding method is preferable.

As the injection molding method, for example, the Si-containing Al alloy base material having the aluminum oxide coating treated with the silane coupling is mounted on a predetermined injection molding mold, and then the porous surface of the aluminum oxide coating is attached. A method of joining the Si-containing Al alloy base material and the resin by injecting a molten resin into a desired region on the surface of the layer and then cooling the mold to solidify the resin can be mentioned. The resin temperature at the time of injection is not particularly limited as long as it is equal to or higher than the temperature at which the resin on the surface of the porous surface layer can flow. Further, as for other injection conditions, known conditions corresponding to each resin can be adopted.

Further, as another injection molding method, for example, the Si-containing Al alloy base material having the silane coupling-treated aluminum oxide film is inserted into an injection molding die as an insert component, the mold is closed, and then the mold is closed. A method of joining the Si-containing Al alloy base material and the resin by injecting the molten resin into a mold under high temperature and high pressure and performing insert molding, and then opening the mold to release the mold can be mentioned. Conditions such as molding pressure and injection speed can be appropriately set depending on the injection molding machine used, the type of resin, and the shape to be molded.

As the melt pressure bonding method, for example, a resin is preformed into a predetermined shape by a known molding method such as injection molding or extrusion molding, and the preformed resin material and the silane coupling-treated aluminum oxide film are formed. The Si-containing Al alloy base material having the above-mentioned Si-containing Al alloy base material is superposed at a desired position on the surface of the porous surface layer of the aluminum oxide film, and then press-molded while heating to form the Si-containing Al alloy having the aluminum oxide film. A method of joining the Si-containing Al alloy base material and the resin by melt-pressing a resin material to a base material and cooling the melt-bonded press-molded product can be mentioned. The heating temperature at the time of melt pressure bonding is not particularly limited as long as it is at least a temperature at which the resin on the surface of the porous surface layer can flow. Further, as for other melt crimping conditions, known conditions corresponding to each resin can be adopted.

As the pressure pressing method, for example, the resin is arranged at a desired position on the surface of the porous surface layer of the aluminum oxide coating of the Si-containing Al alloy base material having the aluminum oxide coating treated with the silane coupling. There is a method of pressurizing (pressing). The pressure at the time of pressurization is not particularly limited, but from the viewpoint of being able to bond the Si-containing Al alloy base material and the resin more firmly, 10 to 3000 kPa is preferable, and 100 to 1000 kPa is more preferable. As described above, the pressure press method does not require pressing at high pressure and is useful as a simple method.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. The average height of the columnar bodies in the porous surface layer, the average value of the number of columnar bodies, the average value of the total area of the columnar body cross sections, the average value of the total circumference of the columnar body cross sections, and the porosity. The average thickness of the quality intermediate layer, the average pore diameter of the fine recesses, and the average distance between the centers of the pores were measured as follows in accordance with the method described in Japanese Patent Application Laid-Open No. 2016-522310.

<Average height of columnar body of porous surface layer>
An SEM image of a vertical cross section of the porous surface layer of the aluminum oxide film was taken. Based on the obtained SEM image, the upper end (surface of the porous surface layer) and the lower end (porous surface layer and porous intermediate layer (aluminum base material if there is no porous intermediate layer) of the porous surface layer The maximum and minimum values of the distance to the interface) were measured. The arithmetic mean value of the maximum value and the minimum value was calculated, and a normal distribution was obtained in which the difference between the obtained arithmetic mean value and the minimum value was 3 times (3σ) the standard deviation σ. The average value in this normal distribution was taken as the average height of the porous surface layer, that is, the average height of the columnar bodies.

<Average value of the number of columns in the porous surface layer, average value of the total area of the columnar cross section, and average value of the total circumference of the columnar cross section>
An SEM image (8-bit image, gray scale) of the cross section of the porous surface layer of the aluminum oxide film was taken. After removing noise from the obtained SEM image, binarization processing was performed using image analysis software ImageJ1.47. That is, 170 was selected as the brightness value (threshold value) of the boundary where the SEM image could be visually recognized as a columnar body, and a region having a brightness value of 170 or more was extracted from the SEM image to create a binary image.

The binary image was subjected to Watershed subdivision processing, and the extracted region was separated. That is, based on the binary image, an Euclidean distance map (EDM) is created, extreme erosion points (UEPs) are found, and each UEP is reached as much as possible until it reaches the edge of the region of the UEP. Alternatively, the extracted region was separated by extending until it reached the edge of another (next) (growing) UEP region. From the separated regions, the minimum size that can be recognized as the cross section of the columnar body was determined, and the region larger than this minimum size was defined as the columnar body region.

In the SEM image of the cross section of the porous surface layer, a field of view of 400 nm square was randomly extracted, and in this field of view, a columnar region was extracted according to the above method. The extracted columnar region was counted and used as the number of columnar bodies in a 400 nm square field of view. The number of columnar bodies was determined in a 400 nm square field of view at five randomly selected locations, and the average value thereof was taken as the average value of the number of columnar bodies in the 400 nm square field of view.

In addition, the area of each extracted columnar region was determined using image analysis software ImageJ1.47, and the total cross-sectional area of the columnar body in a 400 nm square field of view was determined as the cross-sectional area of the columnar body. The total cross-sectional area of the columnar body was calculated in five randomly selected 400 nm square visual fields, and the average value thereof was taken as the average value of the total cross-sectional area of the columnar body in the 400 nm square visual field. ..

Further, the perimeter of the extracted columnar region was determined using the image analysis software ImageJ1.47, and this was set as the perimeter of the columnar cross section, which was the perimeter of the perimeter of the columnar cross section in a 400 nm square field of view. The total length was calculated. The total perimeter of the cross section of the columnar body is calculated in five randomly selected 400 nm square visual fields, and the average value thereof is the perimeter of the perimeter of the cross section of the columnar body in the 400 nm square visual field. The average value of the total was used.

<Average thickness of porous intermediate layer>
An SEM image of a vertical cross section of the porous intermediate layer of the aluminum oxide film was taken. Based on the obtained SEM image, the upper end (the interface between the porous surface layer and the porous intermediate layer (the surface of the porous intermediate layer if there is no porous surface layer)) and the lower end (porous) of the porous intermediate layer. The distance between the quality intermediate layer and the aluminum substrate) was measured. This distance was measured at 5 randomly sampled sites, and the average value was taken as the average thickness of the porous intermediate layer.

<Average pore diameter and average distance between the centers of the fine recesses in the porous intermediate layer>
A flaky sample with an exposed surface of the porous intermediate layer was prepared using an ultramicrotome. Using this flaky sample, an SEM image of the surface of the porous intermediate layer of the aluminum oxide film was taken. In the obtained SEM image, pores were randomly extracted, and the maximum length of the pores in the cross section was measured and used as the pore diameter. The pore diameter was measured in 5 randomly selected pores, and the average value thereof was taken as the average pore diameter of the fine recesses.

In addition, the distance between the center of the randomly sampled pore and the center of the pore closest to the pore was measured and used as the distance between the center of the pore. The distance between the centers of the pores was measured in five randomly selected pores, and the average value thereof was taken as the average distance between the centers of the pores of the fine recesses.

(Example 1)
[Solvent degreasing process]
An aluminum die-cast material (JIS standard, ADC12, Si content 9.6 to 12.0% by mass) was used as the Si-containing Al alloy base material. The surface of this Si-containing Al alloy base material (18 mm × 45 mm × 1.5 mm thick) was degreased with acetone and then degreased with hexane.

[Anodizing process]
The Si-containing Al alloy base material after the degreasing treatment was anodized according to the method described in Japanese Patent Application Laid-Open No. 2016-522310 (Patent Document 2). That is, 5 to 10% by mass of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 96 to 98%) aqueous solution is used as the electrolytic solution, the Si-containing Al alloy base material after the degreasing treatment is used as an anode, and the platinum plate is used as a cathode. The insoluble electrode) was used, the voltage was adjusted within the range of 10 to 5 V, and the treatment time was adjusted within the range of 5 to 15 minutes, and the anodizing treatment was performed two or more times to obtain the desired surface of the Si-containing Al alloy base material. An aluminum oxide film was formed. Then, the Si-containing Al alloy base material having the aluminum oxide film was washed with ion-exchanged water and dried.

[Phosphoric acid treatment process]
The Si-containing Al alloy base material having the aluminum oxide film was immersed in an aqueous phosphoric acid solution, stirred at room temperature for 5 minutes, and then washed with ion-exchanged water. This operation was repeated multiple times. With respect to the obtained Si-containing Al alloy base material having an aluminum oxide film, according to the above method, the average height of the columnar bodies of the porous surface layer, the average value of the number of columnar bodies, the average value of the area of the columnar body cross section, The average value of the total circumference of the columnar cross section, the average thickness of the porous intermediate layer, the average pore diameter of the fine recesses, and the average distance between the centers of the pores were measured. The results are shown in Table 1.

[Silane coupling treatment process]
3-Aminopropyltrimethoxysilane and ion-exchanged water were mixed to prepare an aqueous solution of a silane coupling agent having a concentration of 1% by mass. The Si-containing Al alloy base material having the aluminum oxide film surface-treated with an aqueous phosphoric acid solution is immersed in the aqueous solution of a silane coupling agent for 3 minutes, air-dried, and further in a vacuum dryer at 130 ° C. for 30 minutes. It was heated and sintered.

[Joining process]
The Si-containing Al alloy base material having the aluminum oxide film surface-treated with a silane coupling agent was mounted on an injection molding die. This mold is mounted on an injection molding device (small injection molding machine "C. Mobile" manufactured by Shinko Selvik Co., Ltd.), and polyphenylene sulfide is used under the conditions of a resin temperature of 330 ° C., a mold temperature of 120 to 150 ° C., and a holding time of 30 seconds. (PPS resin "Sustil SGX120" manufactured by Toso Co., Ltd., GF 20%, melting point 281 ° C.) is injected onto the surface of the aluminum oxide film of the Si-containing Al alloy base material to form the Si-containing Al alloy base material (18 mm ×). A composite material was obtained in which the PPS resin (10 mm × 45 mm × 3 mm thickness) and the PPS resin (10 mm × 45 mm × 3 mm thickness) were joined (overlapping portion 10 mm × 5 mm).

(Example 2)
A composite material in which the Si-containing Al alloy base material and the PPS resin are bonded in the same manner as in Example 1 except that the concentration of 3-aminopropyltrimethoxysilane in the aqueous solution of the silane coupling agent is changed to 2% by mass. Was produced.

(Example 3)
A composite material in which the Si-containing Al alloy base material and the PPS resin are bonded in the same manner as in Example 1 except that the concentration of 3-aminopropyltrimethoxysilane in the aqueous solution of the silane coupling agent is changed to 5% by mass. Was produced.

(Comparative Example 1)
A composite material in which the Si-containing Al alloy base material and the PPS resin were bonded was produced in the same manner as in Example 1 except that the silane coupling treatment was not performed.

(Comparative Example 2)
A Si-containing Al alloy base material having an aluminum oxide film was produced in the same manner as in Example 1 except that one anodizing treatment was performed under the conditions of a voltage of 10 V and a treatment time of 15 minutes. With respect to the obtained Si-containing Al alloy base material having an aluminum oxide film, according to the above method, the average height of the columnar bodies of the porous surface layer, the average value of the number of columnar bodies, the average value of the area of the columnar body cross section, The average value of the total circumference of the columnar cross section, the average thickness of the porous intermediate layer, the average pore diameter of the fine recesses, and the average distance between the centers of the pores were measured. The results are shown in Table 1.

Next, using the Si-containing Al alloy base material having the aluminum oxide film, the same procedure as in Example 1 was carried out except that the concentration of 3-aminopropyltrimethoxysilane in the silane coupling agent aqueous solution was changed to 2% by mass. , A composite material in which the Si-containing Al alloy base material and the PPS resin were bonded was produced.

(Reference example 1)
Instead of the Si-containing Al alloy base material, an aluminum base material having an Al purity of 99.5% by mass or more (JIS standard, A1050, Si content of 0.25% by mass or less, 18 mm × 45 mm × 1.5 mm thickness. An Al base material having an aluminum oxide film was produced in the same manner as in Example 1 except that "Al base material" was used. With respect to the obtained Al substrate having an aluminum oxide film, the average height of the columns of the porous surface layer, the average number of columns, the average area of the column cross section, and the column cross section were obtained according to the above method. The average value of the total circumferences of the particles, the average thickness of the porous intermediate layer, the average pore diameter of the fine recesses, and the average distance between the centers of the pores were measured. The results are shown in Table 1.

Next, using the Al base material having the aluminum oxide film, a composite material in which the Al base material and the PPS resin were bonded was produced in the same manner as in Example 1 except that the silane coupling treatment was not performed. ..

<Measurement of tensile shear strength>
A tensile shear test (n = 3) was performed on the obtained composite material using an Instron type universal testing machine (“Instron 5566” manufactured by Instron) under the conditions of a chuck-to-chuck distance of 50 mm, a tensile speed of 10 mm / min, and a load cell of 10 kN. And the tensile shear strength was measured. The results are shown in Table 2 and FIG.

As shown in Table 2 and FIG. 1, it is an aluminum oxide film having a porous surface layer in which predetermined columnar bodies are dispersed and arranged, and the surface thereof is provided with an aluminum oxide film having a silane coupling treatment. It was confirmed that the Si-containing Al base material (Examples 1 to 3) was firmly bonded to the resin. Further, a Si-containing Al substrate (Comparative Example 1) having an aluminum oxide film having a porous surface layer in which predetermined columnar bodies are dispersed and arranged and having an aluminum oxide film not subjected to silane coupling treatment on the surface is also available. , It was found that it was firmly bonded to the resin. On the other hand, it is a Si-containing Al substrate (Comparative Example 2) which is an aluminum oxide film which does not have a porous surface layer in which columnar bodies are dispersed and arranged, and whose surface is provided with an aluminum oxide film whose surface is silane-coupled. ) Was found to be inferior in bonding strength to the resin as compared with Examples 1 to 3 and Comparative Example 1.

<Hot water immersion test>
The composite materials obtained in Example 1 and Comparative Example 1 were immersed in ion-exchanged water adjusted to 80 ° C. using a constant temperature water tank (“BK500” manufactured by Yamato Scientific Co., Ltd.). The tensile shear strength of the composite material after immersion for a predetermined time was measured by the above method. FIG. 2 shows the ratio of the tensile shear strength after immersion for a predetermined time to the start of immersion (hot water immersion time: 0 hours).

As is clear from the results shown in FIG. 2, it is an aluminum oxide film having a porous surface layer in which predetermined columnar bodies are dispersed and arranged, and an aluminum oxide film whose surface is silane-coupled is applied to the surface. It was found that the composite material (Example 1) in which the Si-containing Al base material and the resin were bonded did not decrease in tensile shear strength even when immersed in warm water at 80 ° C. for 500 hours, and was excellent in bonding durability. It was. On the other hand, a Si-containing Al base material having an aluminum oxide film having a porous surface layer in which predetermined columnar bodies are dispersed and arranged, and having an aluminum oxide film not subjected to silane coupling treatment on the surface and a resin are bonded to each other. The tensile shear strength of the composite material (Comparative Example 1) decreases as the hot water immersion time increases, and when immersed in warm water at 80 ° C. for 500 hours, the tensile shear strength decreases to about 35% at the start of immersion, resulting in joint durability. It turned out to be inferior.

<Cold impact test>
The composite materials obtained in Example 2, Comparative Example 1 and Reference Example 1 were subjected to a small thermal shock test device (“TSE-11-A” manufactured by ESPEC CORPORATION) at a low temperature: −40 ° C. for 20 minutes. At high temperature: A thermal shock test was conducted at 80 ° C. for 20 minutes. The tensile shear strength of the composite material after the elapse of a predetermined cycle was measured by the above method. FIG. 3 shows the ratio of the tensile shear strength of the composite materials obtained in Example 2 and Comparative Example 1 after being subjected to a predetermined number of thermal shocks with respect to the start of the test (cold thermal cycle: 0 times). Further, FIG. 4 shows the tensile shear strength of the composite material obtained in Reference Example 1 at the start of the test (cold heat cycle: 0 times) and after 600 times of cold shock.

As is clear from the results shown in FIG. 3, it is an aluminum oxide film having a porous surface layer in which predetermined columnar bodies are dispersed and arranged, and an aluminum oxide film whose surface is silane-coupled is applied to the surface. The composite material (Example 2) in which the Si-containing Al base material and the resin are bonded does not reduce the tensile shear strength even when a cold shock (heat shock) is applied 600 times, and is excellent in bonding durability. all right. On the other hand, a Si-containing Al base material having an aluminum oxide film having a porous surface layer in which predetermined columnar bodies are dispersed and arranged, and having an aluminum oxide film not subjected to silane coupling treatment on the surface and a resin are bonded to each other. In the composite material (Comparative Example 1), the tensile shear strength decreases as the thermal cycle increases, and when a thermal shock (heat shock) is applied 600 times, the tensile shear strength decreases to about 80% at the start of immersion, and the joining durability is reduced. It turned out to be inferior to.

As is clear from the results shown in FIG. 4, an aluminum oxide film having a porous surface layer in which predetermined columnar bodies are dispersed and arranged, and an aluminum oxide film not subjected to silane coupling treatment is applied to the surface. The composite material (Reference Example 1) in which the provided Al base material and the resin are bonded has excellent bonding durability without lowering the tensile shear strength even when a cold shock (heat shock) is applied 600 times. all right. That is, if the aluminum base material containing no silicon forms an aluminum oxide film having a porous surface layer in which predetermined columnar bodies are dispersed and arranged on the surface, the resin can be used without silane coupling treatment. It was confirmed that the joint was strong and stable.

As described above, according to the present invention, the silicon-containing aluminum alloy base material and the resin are firmly bonded to each other, and it is possible to obtain a silicon-containing aluminum alloy resin composite material having excellent durability. Become. Therefore, the silicon-containing aluminum alloy resin composite material of the present invention is useful as a metal resin composite material used in various fields such as home appliances, mobile phones, automobile parts, personal computers, and electronic parts.

Claims (5)

A silicon-containing aluminum alloy resin composite material comprising a silicon-containing aluminum alloy base material having an aluminum oxide film on its surface and a resin bonded via the aluminum oxide film and a silane coupling agent.
The silicon content in the silicon-containing aluminum alloy base material is 4 to 14% by mass with respect to all metal elements.
The aluminum oxide film has a porous surface layer in which columnar bodies having an average height of 10 to 100 nm are dispersed and arranged.
The average value of the total cross-sectional area of the columnar body in the field of view of 400 nm square randomly selected from the porous surface layer is 8000 to 128000 nm ² .
The average number of columns in a 400 nm square field of view of the porous surface layer randomly sampled is 10 to 430.
A silicon-containing aluminum alloy resin composite material. The aluminum oxide film further has a porous intermediate layer having fine recesses between the porous surface layer and the silicon-containing aluminum alloy base material.
The average pore diameter of the fine recess is 5 to 50 nm, and the average pore diameter is 5 to 50 nm.
The average distance between the centers of the pores of the fine recesses is 5 to 90 nm.
The silicon-containing aluminum alloy resin composite material according to claim 1. A porous surface formed by anodizing a silicon-containing aluminum alloy base material having a silicon content of 4 to 14% by mass with respect to all metal elements, and dispersing columns with an average height of 10 to 100 nm. The average value of the total cross-sectional areas of the columnar bodies in a randomly selected 400 nm square visual field is 8000 to 128000 nm ² , and the above is a randomly selected 400 nm square visual field. Anodizing step of forming an aluminum oxide film having the porous surface layer having an average number of columns of 10 to 430 on the surface of the silicon-containing aluminum alloy base material.
A silane coupling treatment step of applying a surface treatment to the aluminum oxide film having a porous surface layer using a silane coupling agent, and a silane coupling treatment step.
A joining step of joining the silicon-containing aluminum alloy base material and the resin via the aluminum oxide film having the porous surface layer and the silane coupling agent.
A method for producing a silicon-containing aluminum alloy resin composite material, which comprises. In the anodizing process,
The porous surface layer and the porous intermediate layer having fine recesses between the porous surface layer and the silicon-containing aluminum alloy base material, and the average pore diameter of the fine recesses is 5 to 50 nm. 3. The third aspect of the present invention is that an aluminum oxide film having a porous intermediate layer having an average pore-center distance of 5 to 90 nm of the fine recesses is formed on the surface of the silicon-containing aluminum alloy base material. The method for producing a silicon-containing aluminum alloy resin composite material according to. The method for producing a silicon-containing aluminum alloy resin composite material according to claim 3 or 4, wherein a silane coupling agent solution having a concentration of 0.5 to 5% by mass is used in the silane coupling treatment step.

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