Surface treated aluminum material excellent in resin adhesiveness and manufacturing method therefor, and conjugate of surface treated aluminum material/resin

The present invention relates to a surface-treated aluminum material and a method for producing the same, and more particularly to a surface-treated aluminum material having an aluminum oxide film on the surface and having excellent resin adhesion, and a method for stably producing the same. Further, the present invention relates to this surface-treated aluminum material / resin joint.

A pure aluminum material or an aluminum alloy material (hereinafter referred to as "aluminum material") is lightweight, has appropriate mechanical properties, and has excellent aesthetics, molding processability, corrosion resistance, and the like. , Widely used in various containers, structural materials, machine parts, etc. While these aluminum materials may be used as they are, they are subjected to various surface treatments to provide corrosion resistance, abrasion resistance, resin adhesion, hydrophilicity, water repellency, antibacterial properties, design properties, infrared radioactivity, and high reflection. It is often used by adding and improving functions such as sex.

For example, anodizing treatment (so-called alumite treatment) is widely used as a surface treatment method for improving corrosion resistance and wear resistance. Specifically, as described in Non-Patent Documents 1 and 2, by immersing the aluminum material in an acidic electrolytic solution and performing electrolytic treatment with a direct current, the surface of the aluminum material has a thickness of several to several tens of μm. Various treatment methods have been proposed depending on the intended use, in which an anodic oxide film is formed.

Further, as a surface treatment method for improving resin adhesion, an alkaline AC electrolysis method as in Patent Document 1 has been proposed. That is, it is composed of a porous aluminum oxide film layer having a thickness of 20 to 500 nm on the surface of the aluminum material and a barrier type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the substrate side, and the porous aluminum oxide film layer is formed. Small pores with a diameter of 5 to 30 nm are formed, and the fluctuation range of the total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer on the entire surface of the aluminum material is the arithmetic average of the total thickness. It forms an oxide film within ± 50% of the value. Specifically, using an aluminum electrode and a counter electrode, an alkaline aqueous solution having a pH of 9 to 13 and a liquid temperature of 35 to 80 ° C and a dissolved aluminum concentration of 5 ppm or more and 1000 ppm or less is used as an electrolytic solution, and the frequency is 20. ~ 100Hz, current density 4 ~ 50A / dm²The above oxide film can be obtained by performing AC electrolysis treatment under the condition of electrolysis time of 5 to 60 seconds.

However, in recent years, it has been found that the resin adhesion may not always be improved depending on the configuration of the manufacturing equipment even when the treatment is performed under the same electrolytic conditions using the technique of Patent Document 1. Specifically, when performing the above electrolytic treatment on a long aluminum material such as a coiled aluminum plate or a long extruded aluminum profile, the aluminum material and the counter electrode are used to improve productivity. It has been found that the resin adhesion may not be exhibited in the case of performing the so-called continuous treatment in which the aluminum material is continuously transported and supplied into the electrolytic cell while the electricity is constantly supplied between them.

<p num="0006"><nplcit num="1"><text>Aluminum Handbook 7th Edition, pp. 179-190, 2007, Japan Aluminum Association</text></nplcit><nplcit num="2"><text>Japanese Industrial Standard JIS H8601, "Aluminum and aluminum alloy anodized film" (1999)</text></nplcit></p>

<p num="0007"><patcit num="1"><text>International Publication WO2013 / 118870</text></patcit></p>

<p num="0008"> The present invention has been made in view of the above circumstances, and mainly when a long aluminum material is continuously treated, a surface-treated aluminum material having excellent resin adhesion, a method for producing the same, and the surface-treated aluminum. An object of the present invention is to provide a material / resin joint.</p>

<p num="0009"> As a result of diligent studies to solve the above problems, the present inventors did not necessarily improve the resin adhesion of the continuously treated aluminum material because of the electrolytic current in the aluminum material after the electrolysis was completed. We found that the behavior had an effect. Specifically, an environment in which the current flowing through the aluminum material is gradually attenuated over a long period of time after the aluminum material is electrolyzed under the conditions specified in Patent Document 1, for example, until it is taken out from the electrolytic cell. It has been found that the resin adhesion decreases when exposed to. Such a situation is likely to occur particularly in the case of electrolysis by continuous treatment, and the present inventors have completed the present invention through further studies.</p><p num="0010"> That is, in claim 1, the present invention has an oxide film formed on the surface, and the oxide film has a thickness of a porous aluminum oxide film layer having a thickness of 20 to 500 nm formed on the surface side and a thickness formed on the substrate side. It is composed of a barrier type aluminum oxide film layer having a diameter of 3 to 30 nm, and small pores having a diameter of 5 to 30 nm are formed in the porous aluminum oxide film layer, and the porous aluminum oxide film layer and a barrier type aluminum oxide film are formed. A surface-treated aluminum material having excellent resin adhesion, characterized in that the crack length generated at the boundary with the layer is 50% or less of the boundary length, was used.</p><p num="0011"> Further, the present invention is the method for producing a surface-treated aluminum material according to claim 1, wherein an electrode of the aluminum material continuously transported and supplied into the electrolytic solution and a fixed counter electrode are used. , The electrolytic solution is an alkaline aqueous solution with a pH of 9 to 13 and a liquid temperature of 35 to 85 ° C, a frequency of 10 to 100 Hz, and a current density of 4 to 50 A / dm.²In a method of forming an oxide film on the surface of an aluminum material portion facing the counter electrode by performing an AC electrolysis treatment under a condition of an electrolysis time of 5 to 300 seconds, the aluminum material electrode and the counter electrode are continuously energized. The current density flowing through the electrolyzed aluminum material portion after the electrolysis time is completed is 1 A / dm.²A method for producing a surface-treated aluminum material having excellent resin adhesion, which is characterized in that the time until it becomes less than 10.0 seconds is used.</p><p num="0012"> According to the third aspect of the present invention, the distance between the electrodes of the aluminum material and the counter electrode is 2 to 150 mm.</p><p num="0013"> Further, in claim 4, the present invention comprises the surface-treated aluminum material according to claim 1 and the resin coated on the surface on which the oxide film of the surface-treated aluminum material is formed. It was a material / resin joint.</p>

<p num="0014"> According to the present invention, since an oxide film having high adhesion to a resin or the like is formed on the surface of the aluminum material, a surface-treated aluminum material having excellent resin adhesion can be continuously obtained. Further, the bonded body of the surface-treated aluminum material and the resin has excellent adhesion.</p><p num="0015"> Specifically, the oxide film on the surface of the aluminum material has a two-layer structure consisting of a porous aluminum oxide film layer and a barrier type aluminum oxide film layer. Then, the porous aluminum oxide film layer having a thickness of 20 to 500 nm and having small pores with a diameter of 5 to 30 nm formed on the surface side of the aluminum material suppresses cohesive fracture of itself. By increasing the surface area, the adhesion to the member to be joined such as resin is improved. In addition, a barrier-type aluminum oxide film layer with a thickness of 3 to 30 nm formed on the base side of the aluminum material binds the aluminum base and the porous aluminum oxide film layer while suppressing cohesive failure of itself. Improves adhesiveness and adhesion. At this time, the length of cracks generated at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is suppressed to 50% or less of the boundary length, thereby suppressing the cohesive destruction of the oxide film itself. be able to.</p>

<figref num="1">It is the schematic which shows the manufacturing equipment of the aluminum material which concerns on this invention.</figref>

The details of the present invention will be described below in order. The surface-treated aluminum material according to the present invention has an oxide film formed on its surface, and this oxide film is a porous aluminum oxide film layer formed on the surface side and a barrier type aluminum oxide film layer formed on the substrate side. Consists of. Then, small pores are formed in the porous aluminum oxide film layer.

A. Aluminum material As the aluminum material used in the present invention, pure aluminum (for example, 99.0 mass% or more) or an aluminum alloy is used. The composition of the aluminum alloy is not particularly limited, and various alloys including the alloy specified in JIS can be used. The shape is not particularly limited, but since continuous processing is performed as described later, a long aluminum material such as a coiled aluminum plate or a long extruded aluminum profile is preferably used. Be done. Further, in the aluminum plate, the thickness thereof can be appropriately selected depending on the application, but from the viewpoint of weight reduction and moldability, 0.05 to 2.0 mm is preferable, and 0.1 to 1.0 mm is more preferable.

B. Manufacturing method As a specific content of the present invention, an aluminum electrode that is continuously transported and supplied into the electrolytic solution and a fixed counter electrode are used, and the electrolytic solution is alkaline at pH 9 to 13 and a liquid temperature of 35 to 85 ° C. It is an aqueous solution, with a frequency of 10 to 100 Hz and a current density of 4 to 50 A / dm.²A method of forming an oxide film on the surface of the aluminum material portion facing the counter electrode by performing an AC electrolysis treatment under the condition of an electrolysis time of 5 to 300 seconds, wherein the aluminum material electrode and the counter electrode are continuously connected. The current density that flows through the electrolyzed aluminum material part after the electrolysis time is completed is 1A / dm.²One method is to set the time until it becomes less than 10.0 seconds.

As the aluminum material that is continuously transported and supplied into the electrolytic solution, for example, a long aluminum plate material 1 wound in a coil shape can be used. A method of performing electrolysis treatment while immersing this in an electrolytic cell while unwinding it, and winding the electrolyzed aluminum plate material out of the electrolytic cell; or immersing it in an electrolytic cell while sending out a long aluminum profile such as an extruded material or a drawing material. There is a method of performing the electrolysis treatment while performing the electrolysis treatment and taking out the electrolyzed long aluminum material to the outside of the electrolytic cell. Specifically, as shown in FIG. 1, a pair of feed rolls 2 and 3 are arranged at a position before being carried into the electrolytic cell 1 and a position after being carried out from the electrolytic cell 1, respectively. Pass the aluminum material 5 through the electrolytic solution 4. The aluminum material 5 before the electrolysis treatment is conveyed and supplied into the electrolytic solution 4 via a pair of rolls 2 at the front position of the electrolytic cell 1 while being unwound in a coil shape (not shown). On the other hand, the aluminum material 5 after the electrolysis treatment is wound around a roll (not shown) via a pair of rolls 3 located at the rear position of the electrolytic cell 1 to form a coil. Further, in the electrolytic solution 4, the counter electrode 6 is arranged so as to face a part of the aluminum material 5 to be conveyed. It is preferable that the surface of the facing aluminum material 5 and the facing surface of the counter electrode 6 are arranged so as to be parallel to each other. Here, if the counter electrode 6 is arranged on both sides of the aluminum material 5, the electrolytic treatment can be efficiently performed on both sides of the aluminum material 5. The aluminum material 5 and the AC power supply 7 are connected through the feed roll 2. Further, the electrode of the aluminum material 5 and the counter electrode 6 are continuously energized by the AC power source 7.

Further, the aluminum material 5 and the counter electrode 6 may be arranged in any of a horizontal position, a position inclined from the horizontal position, and a vertical position. Further, the distance between the electrodes of the aluminum material 5 and the counter electrode 6 is preferably 2 to 150 mm, more preferably 5 to 100 mm. If the distance between the electrodes is less than 2 mm, the distance between the electrode of the aluminum material 5 and the counter electrode 6 becomes too narrow, sparks may occur, and bubbles of gas generated in the vicinity are difficult to dissipate on the plate surface. Unevenness may occur. When the distance between the electrodes exceeds 150 mm, the influence of liquid convection generated between the electrodes of the aluminum material 5 and the counter electrode 6 during the transportation of the aluminum material 5 is reduced, so that the formation speed of the electrolytic film is reduced. May be extremely slow.

In the AC electrolytic treatment step, the alkaline aqueous solution used as the electrolytic solution includes phosphates such as sodium phosphate, potassium hydrogen phosphate, sodium pyrophosphate, potassium pyrophosphate and sodium metaphosphate; sodium hydroxide and hydroxide. Alkali metal hydroxides such as potassium; carbonates such as sodium carbonate, sodium hydrogencarbonate and potassium carbonate; ammonium hydroxide; or an aqueous solution of a mixture thereof can be used. Since it is necessary to keep the pH of the electrolytic solution in a specific range as described later, it is preferable to use an alkaline aqueous solution containing a phosphate-based substance that can be expected to have a buffer effect. The concentration of such an alkaline component is adjusted so that the pH of the electrolytic solution becomes a desired value, but is usually preferably 1 × 10.^-4~ 1 mol / liter, more preferably 1 x 10^-3~ 0.8 mol / liter. A surfactant may be added to these alkaline aqueous solutions in order to improve the ability to remove stain components.

The pH of the electrolytic solution needs to be 9 to 13, preferably 9.5 to 12. When the pH is less than 9, the alkaline etching power of the electrolytic solution is insufficient, so that the porous structure of the porous aluminum oxide film layer becomes incomplete. On the other hand, when the pH exceeds 13, the alkaline etching force becomes excessive, which makes it difficult for the porous aluminum oxide film layer to grow, and further inhibits the formation of the barrier type aluminum oxide film layer.

The temperature of the electrolytic solution needs to be 35 to 85 ° C, preferably 40 to 70 ° C. If the temperature of the electrolytic solution is less than 35 ° C, the porous structure of the porous aluminum oxide film layer becomes incomplete due to insufficient alkaline etching power. On the other hand, if the temperature exceeds 85 ° C, the alkaline etching force becomes excessive, so that the growth of both the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is inhibited.

In alkaline AC electrolysis, the thickness of the entire oxide film including the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is controlled by the amount of electricity, that is, the product of the current density and the electrolysis time, and is basically the amount of electricity. As the number increases, the thickness of the entire oxide film increases. From this point of view, the AC electrolysis conditions of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer are as follows.

The frequency used is 10 to 100 Hz, preferably 20 to 90 Hz. Below 10 Hz, as a result of the increase in the direct current element in electrolysis, the formation of the porous structure of the porous aluminum oxide film layer does not proceed, resulting in a dense structure. On the other hand, if it exceeds 100 Hz, the reversal of the anode and the cathode is too fast, so that the formation of the entire oxide film becomes extremely slow, and both the porous aluminum oxide film layer and the barrier type aluminum oxide film layer can obtain a predetermined thickness. Will take an extremely long time.

Current density is 4 ~ 50A / dm², Preferably 5 ~ 45A / dm²And. Current density is 4A / dm²If it is less than, a porous aluminum oxide film layer cannot be obtained because only the barrier type aluminum oxide film layer is preferentially formed. On the other hand, 50A / dm²If it exceeds, the current density becomes excessive, so that it becomes difficult to control the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer, and processing unevenness is likely to occur.

The electrolysis time is 5 to 300 seconds, preferably 10 to 240 seconds. Here, the electrolysis time means the time in which the predetermined position of the aluminum material 5 moving in the electrolytic solution 4 faces the surface of the counter electrode 6 in FIG. 1. As shown in FIG. 1, assuming that the length of the counter electrode 6 along the transport direction c of the aluminum material 5 is L (mm) and the transport speed of the aluminum material 5 is v (mm / sec), the electrolysis time is ( L / v) Represented by &lt;seconds&gt;. When the electrolytic time is less than 5 seconds, the porous aluminum oxide film layer and the barrier type aluminum oxide film layer are formed too rapidly, so that neither oxide film layer is sufficiently formed, and the amorphous aluminum oxide is used. This is because it becomes a constituent oxide film. On the other hand, if it exceeds 300 seconds, not only the porous aluminum oxide film layer and the barrier type aluminum oxide film layer may become too thick or redissolved, but also the productivity decreases.

As a rule peculiar to the process in which the aluminum material and the counter electrode are continuously energized, the current density flowing through the electrolyzed aluminum material portion after the electrolysis time ends is 1 A / dm.²The time until it becomes less than 10.0 seconds, preferably 5.0 seconds or less. Moreover, it is most preferable that this time is 0 seconds. As will be described later, if this time exceeds 10.0 seconds, that is, if a relatively weak current continues to flow through the electrolyzed aluminum material portion even after the electrolysis is completed, the porous aluminum oxide film layer and the barrier type aluminum oxide film Cracks are likely to occur at the boundary of the layers.

This is because when a weak current continues to flow transiently after the completion of electrolysis, an unstable oxide film layer is formed directly under the porous aluminum oxide film layer due to the current, and partial cohesive fracture occurs with a slight stress. Is. The current density is 1A / dm²The current density was 1A / dm until it became less than²If it is lowered to less than, the above-mentioned boundary cracks do not appear because such an unstable oxide film layer is hardly formed. The crack referred to here is the unstable oxide film layer that is aggregated and fractured at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer.

Although such a transient change in current density cannot be measured directly, it can be calculated from the configuration of the electrolytic equipment. Specifically, as shown in FIG. 1, the distance from the end of the counter electrode 6 along the transport direction of the aluminum material 5 to the end of the electrolytic cell along the same direction is b (mm), and the set current during electrolysis is set. When the density is I and the transport speed of the aluminum material is v (mm / sec), the current density is 1 A / dm.²It is possible to estimate the time to fall below {b (I-1) / vI} (seconds). Here, I is 4 ~ 50A / dm as described above.²Since it is in the range of, b and v should be set appropriately so that {b (I-1) / vI} is 10.0 seconds or less. If b is too large or v is too small, it is difficult to avoid the occurrence of cracks based on the above mechanism.

The current density is 1A / dm²By setting the time until it becomes less than 10.0 seconds, the crack length at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is 50% or less, preferably 30% or less of the boundary length. Can be suppressed. Moreover, this ratio is most preferably 0%. However, the current density is 1A / dm²It is desirable to remove the aluminum material after it becomes less than the amount from the electrolytic solution as soon as possible. That is, since the electrolytic solution is alkaline, the oxide film may be dissolved and a predetermined film thickness may not be obtained by continuing to immerse the aluminum material in the electrolytic solution even after the electrolysis is completed.

In the production method according to the present invention, the concentration of dissolved aluminum contained in the electrolytic solution is preferably regulated to 5 ppm or more and 1000 ppm or less, more preferably 10 ppm or more and 900 ppm or less, for the purpose of reducing the thickness variation of the oxide film. Is also good. If the dissolved aluminum concentration is less than 5 ppm, the oxide film formation reaction at the initial stage of the electrolytic reaction occurs rapidly, so it is easily affected by variations in the treatment process (dirt state on the aluminum material surface, aluminum material attachment state, etc.). .. As a result, a thick oxide film is locally formed. On the other hand, when the concentration of dissolved aluminum exceeds 1000 ppm, the viscosity of the electrolytic solution increases and uniform convection near the surface of the aluminum material is hindered in the electrolytic process, and at the same time, the dissolved aluminum acts in the direction of suppressing film formation. .. As a result, a thin oxide film is locally formed.

One of the pair of electrodes used for the AC electrolysis treatment is an aluminum material to be electrolyzed. As the other counter electrode, for example, a known electrode such as graphite, aluminum, or titanium can be used, but in the present invention, the electrode does not deteriorate with respect to the alkaline component or temperature of the electrolytic solution, and has excellent conductivity. Furthermore, it is necessary to use a material that does not cause an electrochemical reaction by itself. From this point of view, graphite electrodes are preferably used as counter electrodes. This is because the graphite electrode is chemically stable, inexpensive and easily available, and the electric lines of force are appropriately diffused in the AC electrolysis process due to the action of many pores existing in the graphite electrode. This is because the porous aluminum oxide film layer and the barrier type aluminum oxide film layer tend to be more uniform.

C. oxide film On the surface of the aluminum material used in the present invention, a porous aluminum oxide film layer formed on the surface side and a barrier type aluminum oxide film layer formed on the substrate side are provided. That is, on the surface of the aluminum material, an oxide film composed of two layers, a porous aluminum oxide film layer and a barrier type aluminum oxide film layer, is provided. While the porous aluminum oxide film layer exhibits strong adhesiveness and adhesion, the barrier type aluminum oxide film layer firmly bonds the entire aluminum oxide film layer and the aluminum substrate. Furthermore, by setting the length of cracks generated at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer to 50% or less of the boundary length, it is possible to suppress the detachment of the porous aluminum oxide film layer. Can be done.

C-1. Porous aluminum oxide film layer The thickness of the porous aluminum oxide film layer is 20 to 500 nm, preferably 50 to 400 nm. If the thickness is less than 20 nm, the thickness is not sufficient, so that the formation of the small hole structure described later tends to be insufficient, and the adhesive force and the adhesive force are lowered. On the other hand, if it exceeds 500 nm, the porous aluminum oxide film layer itself tends to coagulate and break, and the adhesive force and the adhesive force decrease.

The porous aluminum oxide film layer has small holes extending from the surface in the depth direction. The diameter of the pores is 5 to 30 nm, preferably 10 to 20 nm. These small holes have the effect of increasing the contact area between the resin layer, the adhesive, or the like and the aluminum oxide film, and increasing the adhesive force and the adhesive force. If the diameter of the small holes is less than 5 nm, the contact area is insufficient and sufficient adhesive force and adhesion cannot be obtained. On the other hand, when the diameter of the small pores exceeds 30 nm, the entire porous aluminum oxide film layer becomes brittle, causing cohesive fracture and lowering the adhesive force and the adhesive force.

The ratio of the total pore area of the small pores to the surface area of the porous aluminum oxide film layer is not particularly limited. The ratio of the total pore area of the small pores to the apparent surface area of the porous aluminum oxide film layer (the area expressed by multiplying the length and width without considering the minute irregularities on the surface) is 25 to 75%. It is preferable, 30 to 70% is more preferable. If it is less than 25%, the contact area may be insufficient and sufficient adhesive force or adhesive force may not be obtained. On the other hand, if it exceeds 75%, the entire porous aluminum oxide film layer may become brittle, causing cohesive failure and reducing the adhesive force and the adhesive force.

C-2. Barrier type aluminum oxide film layer The thickness of the barrier type aluminum oxide film layer is 3 to 30 nm, preferably 5 to 25 nm. If it is less than 3 nm, it is not possible to impart sufficient bonding force to the bonding between the porous aluminum oxide film layer and the aluminum substrate as an intervening layer, and in particular, the bonding force in a harsh environment such as high temperature and high humidity becomes insufficient. On the other hand, when it exceeds 30 nm, the barrier type aluminum oxide film layer is liable to coagulate and break due to its denseness, and the adhesive force and the adhesive force are rather lowered.

C-3. Rhagades at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer The oxide film defined by C-1 and C-2 is preferably formed continuously, and the crack length formed between them is 50% or less, preferably 30% of the total length of this boundary. Hereinafter, it is required to be 0% most preferably. In relation to the electrolysis conditions, the current density flowing through the electrolyzed aluminum material after the electrolysis time ends is 1 A / dm.²By setting the time to less than 10.0 seconds to 10.0 seconds or less, the ratio of the crack length to the total boundary length is achieved. When the above ratio exceeds 50%, the entire oxide film starting from this crack easily falls off, resulting in a significant decrease in resin adhesion. Here, the ratio of the crack length to the total length of the boundary is specifically determined as follows. That is, the above-mentioned crack is a partial cohesive failure of the unstable oxide film layer due to the current attenuation behavior after the end of the electrolysis time, and is formed at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer. Occurs in parallel. Here, the crack length (m) with respect to the total length (M) of the boundary can be observed as (m / M) by observing the cross-sectional TEM observation described later.

C-4. Fluctuation range of the total thickness of the oxide film The total thickness of the oxide film, that is, the total thickness of the porous aluminum oxide film layer described in C-1 and the barrier type aluminum oxide film layer described in C-2, was measured anywhere on the aluminum material. However, the fluctuation range is preferably within ± 50%, and more preferably within ± 20%. That is, the arithmetic mean of the total thickness of the oxide film measured at any plurality of points on the surface of the aluminum material (preferably 10 or more points, and 10 or more measurement points at each of these points) is T (nm). In the case of, it is preferable that the total thickness of the oxide film at these a plurality of measurement points is in the range of (0.5 × T) to (1.5 × T). If there is a part less than (0.5 × T), the oxide film at that part becomes thinner than the surrounding area. Then, in this thin portion, a gap is likely to be generated between the adhesive to be adhered or the resin layer to be adhered and the oxide film, and a sufficient contact area cannot be secured and the adhesive force and the adhesive force are lowered. There is. On the other hand, if there is a portion exceeding (1.5 × T), the oxide film at that location becomes thicker than the surroundings. Then, in this thick portion, stress from the resin layer or the like to be adhered may be concentrated, which may induce cohesive failure in the oxide film and reduce the adhesive force and the adhesive force.

In addition, since the optical characteristics of the above-mentioned portion where the overall thickness of the oxide film is thin or thick is different from that of the surroundings, it may be visible as a change in color tone such as brown or cloudy color.

D. Means for observing oxide film The structure observation and thickness measurement of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer in the present invention, and the length of cracks generated at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer. Cross-sectional observation with a transmission electron microscope (TEM) is preferably used for the measurement. Specifically, a flaky sample cut out along the direction perpendicular to the thickness direction is prepared by an ultramicrotome, a focused ion beam (FIB) processing device, or the like. Then, this is observed by TEM. In preparing the flaky sample, it is more preferable to use a FIB processing device because the object may have cracks. In addition, when measuring the crack length and calculating the ratio, the TEM observation magnification can be set low (about 5000 to 10000 times) and quantified by observing multiple fields of view.

E. Surface-treated aluminum material and resin joint Due to its excellent adhesiveness, the surface-treated aluminum material produced as described above can be used for various purposes by further coating the treated surface on which the oxide film is formed with a resin. Here, the resin can be either a thermosetting resin or a thermoplastic resin, and various effects are imparted in combination with a specific oxide film formed on the treated surface of the surface-treated aluminum material according to the present invention. Will be done.

For example, a joint body of an aluminum material and a resin generally has a larger coefficient of thermal expansion of the resin than the aluminum material, so that peeling or cracking is likely to occur at the interface. However, in the bonded body of the surface-treated aluminum material and the resin according to the present invention, the oxide film in the present invention is very thin and has a specific shape as described above, so that it is excellent in flexibility and expansion of the resin. It is easy to follow the above, and peeling and cracking are unlikely to occur. As described above, the bonded body of the surface-treated aluminum material and the thermoplastic resin according to the present invention can be suitably used as a lightweight and highly rigid composite material. Further, the bonded body of the surface-treated aluminum material and the thermosetting resin according to the present invention can be suitably used for printed wiring board applications.

As the resin, various thermoplastic resins and thermosetting resins can be used. Specifically, in a thermoplastic resin, a resin layer is formed by contacting and permeating a resin that has been made into a fluid state by applying heat to a porous aluminum oxide film layer and cooling and solidifying the resin. Examples of the thermoplastic resin include polyolefin (polyethylene, polypropylene, etc.), polyvinyl chloride, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polyphenylensulfide, and aromatic polyetherketone (polyetheretherketone, polyetherketone, etc.). Ketone etc.), polystyrene, various fluororesins (polytetrafluoroethylene, polychlorotrifluoroethylene, etc.), acrylic resin (polymethylmethacrylate, etc.), ABS resin, polycarbonate, thermoplastic polyimide, etc. can be used.

Further, in the thermosetting resin, the porous aluminum oxide film layer may be contacted and permeated in a state of fluidity before curing, and then cured. As the thermosetting resin, for example, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane, thermosetting polyimide and the like can be used.

The thermoplastic resin and the thermosetting resin may be used alone, or may be used as a polymer alloy in which a plurality of types of thermoplastic resins or a plurality of types of thermosetting resins are mixed. Further, by adding various fillers, physical properties such as resin strength and coefficient of thermal expansion may be improved. Specifically, various fibers such as glass fiber, carbon fiber, and aramid fiber, and fillers of known substances such as calcium carbonate, magnesium carbonate, silica, talc, glass, and clay can be used.

<p num="0049"> Hereinafter, preferred embodiments of the present invention will be specifically described based on examples. Examples 1 to 24 of the present invention and Comparative Examples 1 to 12</p><p num="0050"> As the aluminum material, a coiled JIS5052-H34 alloy plate with a width of 200 mm and a plate thickness of 1.0 mm was used. This aluminum alloy plate was used for one electrode, and a graphite plate having a flat plate shape of width 300 mm × length 10 mm × plate thickness 2.0 mm was used for the counter electrode. As shown in FIG. 1, one side of the aluminum alloy plate 5 is made to face the counter electrode 6, and a porous aluminum oxide film layer on the surface side and a barrier type aluminum oxide film layer on the base material side are formed on the facing one side surface layer. As described above, both electrodes were placed in the electrolytic solution 4 contained in the electrolytic cell 1. As the electrolytic solution 4, an alkaline aqueous solution containing sodium pyrophosphate as a main component was used. The concentration of the alkaline component in the electrolytic solution was 0.5 mol / liter, and the pH was adjusted with hydrochloric acid and an aqueous solution of sodium hydroxide (both had a concentration of 0.1 mol / liter). AC electrolysis treatment was carried out under the electrolytic conditions shown in Tables 1 and 2 to prepare a test material in which a porous aluminum oxide film layer and a barrier type aluminum oxide film layer were formed. The electrolysis time was adjusted by changing the length of the counter electrode and the transport speed of the material. Tables 1 and 2 also show the distance a between the electrodes of the aluminum material and the counter electrode.</p><p num="0051"><tables num="1"><img id="000003" he="229" wi="153" file="JP2017036498A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0052"><tables num="2"><img id="000004" he="236" wi="153" file="JP2017036498A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0053"> Cross-section observation by TEM was carried out on the test material prepared as described above. In TEM cross-sectional observation, the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer, the diameter of the small pores of the porous aluminum oxide film layer, and the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer. In order to measure the length of the cracks generated in the aluminum, 10 slice samples for cross-section observation were prepared from the same test material using the FIB processing device.</p><p num="0054"> The thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer, and the diameter of the small pores of the porous aluminum oxide film layer were measured by selecting any 10 points for each of the above samples, and at each point. From the measurement results, the same sample was determined as the arithmetic average value of a total of 100 measured values. In addition, the length of the crack was also measured by selecting an arbitrary 10 points for each of the above samples, and was determined as the arithmetic mean value of a total of 100 measured values for the same sample from the measurement results of each point. In the measurement of the crack length, the observation field of view of the TEM was set to 1 μm × 1 μm. As described above, the crack length thus obtained was divided by the boundary length between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer to obtain the crack length ratio. Further, as a determination of variation in the total thickness of the oxide film (total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer), among the above 100 measurement points (10 samples x 10 measurement points), The number of measurement points within 50% or more and 150% or less of the arithmetic mean value was recorded. The results are shown in Tables 3 and 4.</p><p num="0055"><tables num="3"><img id="000005" he="164" wi="153" file="JP2017036498A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0056"><tables num="4"><img id="000006" he="102" wi="153" file="JP2017036498A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0057"> The adhesiveness of the test material using an adhesive was evaluated by the following method.</p><p num="0058">[Primary adhesion test] Two sheets were prepared from the above test materials, which were cut to a length of 50 mm and a width of 25 mm. While superimposing these two test materials in the overall width direction, superimpose them with a width of 10 mm in the length direction, and a commercially available two-component epoxy adhesive (Nichiban Co., Ltd., Araldai Trapid, model number: AR-R30, A shear test piece was prepared by adhering the overlapped portions with a weight mixing ratio = main agent 100 / curing agent 100). Both ends of the shear test piece in the length direction are pulled in opposite directions along the length direction at a speed of 100 mm / min by a tensile tester, and the adhesiveness is determined by the load (converted to shear stress) and the peeling state as shown below. Evaluated by criteria. As for the shear test pieces, 10 sets of test pieces were prepared from the same test material and evaluated for each. : Shear stress is 20 N / mm²In the above state, the adhesive layer itself is coagulated and broken. Δ: Shear stress is 20 N / mm²Despite the above, the adhesive layer and the test material are separated from each other at the interface. ×: Shear stress is 20 N / mm²Less than the interface between the adhesive layer and the test material</p><p num="0059"> The results are shown in Tables 5 and 6. The table shows the number of sets of , , and × above among the 10 sets of test pieces, but the judgment was passed when all 10 sets were , and the judgment was rejected in other cases. ..</p><p num="0060"><tables num="5"><img id="000007" he="159" wi="153" file="JP2017036498A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0061"><tables num="6"><img id="000008" he="93" wi="153" file="JP2017036498A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0062"> In all of Examples 1 to 24 of the present invention, since the oxide film satisfies the provisions of the present invention, the primary adhesion was judged to be acceptable. On the other hand, in Comparative Examples 1 to 12, it was judged as rejected for the following reasons.</p><p num="0063"> In Comparative Example 1, the pH of the electrolytic solution in the AC electrolysis treatment was too low, so that the alkaline etching power was insufficient. Therefore, the small pore diameter of the porous aluminum oxide film layer was insufficient, and the primary adhesion was unacceptable.</p><p num="0064"> In Comparative Example 2, the pH of the electrolytic solution in the AC electrolysis treatment was too high, so that the alkaline etching power became excessive. Therefore, the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is insufficient, and the small pore diameter of the porous aluminum film becomes excessive, so that the primary adhesion is unacceptable.</p><p num="0065"> In Comparative Example 3, the temperature of the electrolytic solution in the AC electrolysis treatment was too low, so that the alkaline etching power was insufficient. Therefore, the porous structure of the porous aluminum oxide film layer became incomplete, the diameter of the small pores was insufficient, and the primary adhesion was unacceptable.</p><p num="0066"> In Comparative Example 4, the temperature of the electrolytic solution in the AC electrolysis treatment was too high, so that the alkaline etching force became excessive. Therefore, the thickness of the porous aluminum film layer and the barrier type aluminum oxide film layer was insufficient, and the primary adhesion was unacceptable.</p><p num="0067"> In Comparative Example 5, the frequency in the AC electrolysis treatment was too low, so that the electrical state approached that of DC electrolysis. Therefore, the formation of the porous aluminum oxide film layer did not proceed, no small pores were formed, and the thickness of the barrier type aluminum oxide film layer became excessive. Therefore, the primary adhesion was unacceptable.</p><p num="0068"> In Comparative Example 6, the frequency in the AC electrolysis treatment was too high, so that the anode and cathode were reversed too quickly. Therefore, the formation of the porous aluminum oxide film layer became extremely slow, the thickness was insufficient, and the primary adhesion was unacceptable.</p><p num="0069"> In Comparative Example 7, since the current density in the AC electrolysis treatment was too low, the barrier type aluminum oxide film layer was preferentially formed. Therefore, the thickness of the porous aluminum oxide film layer was insufficient, and the primary adhesion was unacceptable.</p><p num="0070"> In Comparative Example 8, since the current density in the AC electrolytic treatment was too high, the control became unstable such as sparks occurring in the electrolytic solution in the electrolytic treatment. Therefore, the entire oxide film was excessively formed, and the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer became excessive. As a result, the primary adhesion was unacceptable.</p><p num="0071"> In Comparative Example 9, the porous aluminum oxide film layer and the barrier type aluminum oxide film layer were not sufficiently formed because the electrolysis treatment time in the AC electrolysis treatment was too short. Therefore, the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer was insufficient, and the primary adhesion was unacceptable.</p><p num="0072"> In Comparative Example 10, the entire oxide film was excessively formed because the electrolysis treatment time in the AC electrolysis treatment was too long. Therefore, the porous aluminum oxide film layer and the barrier type aluminum oxide film layer became too thick, and the primary adhesion was unacceptable.</p><p num="0073"> In Comparative Examples 11 and 12, the shapes of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer satisfied the provisions of the present invention. However, the current density flowing through the aluminum material after electrolysis is 1 A / dm.²The time until it became less than 10 seconds, and the length of the crack formed at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer exceeded 50% of the boundary length, resulting in temporary adhesion. It was a failure.</p><p num="0074"> In Comparative Examples 2, 4 to 7 and 9, the number of measurement points at which the oxide film layer thickness in Table 4 was 50 to 150% of the arithmetic mean value was less than 100 under the conditions in these Comparative Examples. This is because the oxide film thickness was very thin and the formation was unstable, so that the oxide film thickness varied widely even when the dissolved Al concentration was 5 to 1000 ppm.</p>

According to the present invention, a surface-treated aluminum material having excellent adhesiveness and adhesion can be produced by continuous treatment having high productivity. Further, the bonded body of the surface-treated aluminum material and the resin has excellent bondability.

1 ... Electrolytic cell 2 ... A pair of rolls arranged at the position before being carried into the electrolytic cell 3 ... A pair of rolls arranged at the rear position of being carried out from the electrolytic cell 4 ... Electrolytic solution 5 Aluminum material 6 Counter electrode 7 AC power supply b ... Distance from the end of the counter electrode along the transport direction of the aluminum material to the end of the electrolytic cell along the same direction c Transport direction of aluminum material L: Length of counter electrode along the transport direction of aluminum material