WO2013118870A1 - Surface treated aluminum material, method for producing same, and resin-coated surface treated aluminum material - Google Patents
Surface treated aluminum material, method for producing same, and resin-coated surface treated aluminum material Download PDFInfo
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- WO2013118870A1 WO2013118870A1 PCT/JP2013/053062 JP2013053062W WO2013118870A1 WO 2013118870 A1 WO2013118870 A1 WO 2013118870A1 JP 2013053062 W JP2013053062 W JP 2013053062W WO 2013118870 A1 WO2013118870 A1 WO 2013118870A1
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- oxide film
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- treated aluminum
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
Definitions
- the present invention relates to a surface-treated aluminum material, a method for producing the same, and a resin-coated surface-treated aluminum material.
- the surface-treated aluminum material having an aluminum oxide film on the surface and excellent adhesion and adhesion
- the present invention relates to a method for stably producing the same, and a resin-coated surface-treated aluminum material using the surface-treated aluminum material.
- Aluminum materials or aluminum alloy materials are lightweight, have appropriate mechanical properties, and have excellent characteristics such as aesthetics, moldability, and corrosion resistance. Widely used in various containers, structural materials, machine parts, etc. While these aluminum materials may be used as they are, by applying various surface treatments, corrosion resistance, abrasion resistance, resin adhesion, hydrophilicity, water repellency, antibacterial properties, design properties, infrared radiation, high reflectivity In many cases, functions such as sex are added and improved.
- anodizing treatment for improving corrosion resistance and wear resistance
- anodizing treatment is widely used.
- an aluminum material is immersed in an acidic electrolytic solution and subjected to electrolytic treatment with a direct current, whereby a thickness of several to several tens of ⁇ m is formed on the surface of the aluminum material.
- Various processing methods have been proposed depending on the application.
- an alkaline alternating current electrolysis method as in Patent Document 1 has been proposed. That is, using an alkaline solution of a bath temperature 40 ⁇ 90 ° C., the time that the quantity of electricity exceeds 80C / dm 2 at a current density of 4 ⁇ 50A / dm 2, and performs an AC electrolysis process. As a result, an aluminum alloy coating plate for a can lid on which an oxide film having a thickness of 500 to 5000 angstroms is formed is obtained.
- the adhesion may be extremely low depending on the timing of the electrolysis treatment. Specifically, a part of the surface of the aluminum material exhibits a change in color tone (a lot of brownish brown or cloudy color), and the adhesion of the part becomes extremely low.
- the present invention relates to a surface-treated aluminum material excellent in adhesion and adhesion over the entire surface of the aluminum material, a stable production method of such a surface-treated aluminum material, and a resin-coated surface-treated aluminum material using the surface-treated aluminum material
- the purpose is to provide.
- the decrease in adhesion and adhesion is the sum of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer on the entire aluminum material surface. It is contained in the electrolytic treatment solution used for the alkaline alternating current electrolytic treatment in order to optimize the variation width of the thickness, to cause the uneven formation of the oxide film on the entire surface of the aluminum material, and to prevent it. It has been found that it is effective to control the concentration of dissolved aluminum.
- the present invention is the aluminum material having an oxide film formed on at least one surface in the first aspect, wherein the oxide film is a porous aluminum oxide film having a thickness of 20 to 500 nm formed on the surface side. And a barrier type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the substrate side, and pores having a diameter of 5 to 30 nm are formed in the porous aluminum oxide film layer.
- the surface-treated aluminum material characterized in that the fluctuation range of the total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer in the whole is within ⁇ 50% of the arithmetic average value of the total thickness It was.
- the exposure rate of the aluminum substrate is 5% or less.
- the second aspect of the present invention is a method for producing a surface-treated aluminum material according to the first aspect, wherein an aluminum material electrode to be surface-treated and a counter electrode are used, and the liquid temperature is 35 at pH 9-13.
- AC electrolytic treatment under the conditions of an alkaline aqueous solution with a dissolved aluminum concentration of 5 ppm or more and 1000 ppm or less as an electrolytic solution at a frequency of 20 to 100 Hz, a current density of 4 to 50 A / dm 2 and an electrolysis time of 5 to 60 seconds.
- the counter electrode is a graphite electrode.
- both the surface-treated aluminum material electrode and the counter electrode are flat.
- the present invention provides a resin-coated surface-treated aluminum material according to claim 6, wherein the surface of the surface-treated aluminum material according to claim 1 or 2 is coated with a resin layer.
- the surface-treated aluminum material excellent in adhesion and adhesion can be stably formed over the entire surface of the aluminum material. Can be obtained.
- the oxide film on the surface of the aluminum material has a two-layer structure of a porous aluminum oxide film layer and a barrier type aluminum oxide film layer.
- the porous aluminum oxide film layer having a thickness of 20 to 500 nm formed on the surface side of the aluminum material and having a small hole with a diameter of 5 to 30 nm suppresses its own cohesive failure. Adhesion is improved by increasing the surface area.
- the barrier-type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the aluminum substrate side bonds and bonds the aluminum substrate and the porous aluminum oxide film layer while suppressing its own cohesive failure. Improve adhesion and adhesion.
- the aluminum material obtained in this way has an extremely high adhesive strength when various adhesives based on the existing technology are used for the resin layer due to its excellent adhesiveness. Also, due to its excellent adhesion, for example, various paints based on existing technology, specifically water-based paints, solvent-borne paints, powder paints, electrodeposition paints, etc., were used as a base treatment when painting as the resin layer. In some cases, a very high coating strength can be obtained.
- a resin-coated surface-treated aluminum material as a joined body comprising a resin layer such as a thermoplastic resin or a thermosetting resin on the surface of the oxide film of the surface-treated aluminum material of the present invention
- a resin layer such as a thermoplastic resin or a thermosetting resin
- the use as a printed wiring board which paid attention to the high thermal conductivity which an aluminum plate has in recent years can be mentioned.
- printed wiring boards are required to have more layers, higher integration, and higher density than ever before.
- a conventional substrate using an insulator cannot dissipate heat generated from electronic components mounted at high density, resulting in circuit instability.
- an aluminum plate having excellent thermal conductivity as the substrate the electronic components can be cooled by the substrate itself, and the performance of the entire circuit can be improved.
- Such a printed wiring board is manufactured by attaching a metal foil such as a copper foil to an aluminum plate. At that time, an epoxy resin, a polyimide resin, or the like is used as an adhesive. Therefore, by using the resin-coated surface-treated aluminum material in which the surface of the oxide film of the surface-treated aluminum material of the present invention is coated with the resin layer as the adhesive, the surface-treated aluminum material is interposed by the oxide film having the specific structure. It is possible to bond the aluminum material and the metal foil with the resin layer while particularly improving the adhesion with the resin layer.
- the surface-treated aluminum material can be stably manufactured by appropriately setting the AC electrolytic treatment conditions.
- a surface-treated aluminum material 1 according to the present invention has an oxide film 2 formed on one surface, and the oxide film 2 includes a porous aluminum oxide film layer 3 formed on the surface side. It consists of a barrier type aluminum oxide film layer 4 formed on the substrate 5 side. Small holes 31 are formed in the porous aluminum oxide film layer 3.
- Aluminum material Pure aluminum or an aluminum alloy is used as the aluminum material used in the present invention.
- limiting in particular in the component of an aluminum alloy Various alloys including the alloy prescribed
- the plate thickness can be appropriately selected depending on the application, but is preferably 0.05 to 2.0 mm, more preferably 0.1 to 1.0 mm from the viewpoint of weight reduction and formability.
- 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 on the surface of the aluminum material. That is, an oxide film composed of two layers of a porous aluminum oxide film layer and a barrier type aluminum oxide film layer is provided on the surface of the aluminum material. While the porous aluminum oxide film layer exhibits strong adhesion and adhesion, the entire aluminum oxide film layer and the aluminum substrate are firmly bonded by the barrier type aluminum oxide film layer.
- Porous aluminum oxide film layer The thickness of the porous aluminum oxide film layer is 20 to 500 nm. If the thickness is less than 20 nm, the thickness is not sufficient, so that the formation of a small pore structure, which will be described later, is likely to be insufficient, and the adhesive force and adhesion force are reduced. On the other hand, when the thickness exceeds 500 nm, the porous aluminum oxide film layer itself tends to cohesively break down, and the adhesive force and adhesion force are reduced.
- the porous aluminum oxide film layer 3 includes small holes 31 extending from the surface in the depth direction.
- the diameter of the small holes is 5 to 30 nm, preferably 10 to 20 nm. This small hole increases the contact area between the resin layer, the adhesive, and the like and the aluminum oxide film, and exhibits the effect of increasing the adhesive force and the adhesive force. If the diameter of the small hole is less than 5 nm, the contact area is insufficient, and sufficient adhesive force and adhesion force cannot be obtained. On the other hand, if the diameter of the small holes exceeds 30 nm, the entire porous aluminum oxide film layer becomes brittle and causes cohesive failure, resulting in a decrease in adhesion and adhesion.
- 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 is 25 to 75%. preferable. If it is less than 25%, the contact area may be insufficient and sufficient adhesive force or adhesion may not be obtained. On the other hand, if it exceeds 75%, the entire porous aluminum oxide film layer becomes brittle and may cause cohesive failure, resulting in a decrease in adhesion and adhesion.
- the thickness of the barrier type aluminum oxide film layer is 3 to 30 nm. If the thickness is less than 3 nm, a sufficient bonding force cannot be imparted to the bonding between the porous aluminum oxide film layer and the aluminum substrate as the intervening layer, and the bonding force particularly in a severe environment such as high temperature and high humidity becomes insufficient. On the other hand, if the thickness exceeds 30 nm, the barrier type aluminum oxide film layer tends to cohesively break due to its denseness, and on the contrary, the adhesive strength and the adhesive strength are lowered.
- the total thickness of the oxide film that is, the total thickness of the porous aluminum oxide film layer described in B-1 and the barrier type aluminum oxide film layer described in B-2 is Even if it is measured at any location of the aluminum material, the fluctuation range must be within ⁇ 50%, preferably within ⁇ 20%. That is, the average of the entire thickness of the oxide film measured at an arbitrary plurality of locations on the aluminum material surface (ten or more are desirable, and it is desirable to have 10 or more measurement points in each location) is T (nm). In this case, it is necessary that the total thickness of the oxide film at all of the plurality of measurement points is in the range of (0.5 ⁇ T) to (1.5 ⁇ T).
- the oxide film at that location becomes thinner than the surrounding area. If it does so, in this thin location, it will become easy to produce a clearance gap between the adhesive agent which should be adhered, the resin layer which should be stuck, etc., and an oxide film, and sufficient contact area cannot be secured but adhesive strength and adhesion power will fall.
- the oxide film at that location becomes thicker than the surrounding area. Then, in this thick part, the stress from the resin layer etc. which should be contact
- the optical characteristics are different in the portion where the total thickness of the oxide film as described above is thin or thick, it may be visible as a change in color tone such as brownish brown or cloudy color.
- the surface-treated aluminum material according to the present invention When used for a printed wiring board or the like, it may be used in a bent state. In general, when the aluminum material is bent, cracks are likely to occur in the oxide film on the surface. Since the oxide film of the surface-treated aluminum material according to the present invention has the above specific structure, the oxide film is difficult to cohesively break and is excellent in flexibility. Therefore, even if the surface-treated aluminum material is used in a bent state, the generation of cracks in the oxide film is suppressed.
- Such flexibility can be evaluated as, for example, the exposure rate of the aluminum substrate based on the occurrence of cracks in the oxide film layer when the surface-treated aluminum material is bent 180 degrees at 5R so that the oxide film side is convex.
- L be the total length of occurrence of cracks in the bent portion, and divide it by the total bending length T, so that (L / T) ⁇ 100 (%) is the exposure rate of the aluminum substrate based on the occurrence of cracks.
- the exposure rate based on the occurrence of cracks is preferably 5% or less, and more preferably 2% or less, in order not to hinder the adhesion of the oxide film layer.
- the alkaline aqueous solution used as the electrolytic solution in the AC electrolytic treatment step includes phosphates such as sodium phosphate, potassium hydrogen phosphate, sodium pyrophosphate, potassium pyrophosphate and sodium metaphosphate; sodium hydroxide and hydroxide
- phosphates such as sodium phosphate, potassium hydrogen phosphate, sodium pyrophosphate, potassium pyrophosphate and sodium metaphosphate
- An alkali metal hydroxide such as potassium
- carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate; and 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 will be 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 1 ⁇ 10 ⁇ 4 to 1 mol / liter.
- the pH of the electrolytic solution needs to be 9 to 13, and preferably 9.5 to 12.
- the alkaline etching power of the electrolytic solution is insufficient, so that the porous structure of the porous aluminum oxide film layer is incomplete.
- the pH exceeds 13 the alkaline etching power becomes excessive, so that the porous aluminum oxide film layer is difficult to grow, and the formation of the barrier type aluminum oxide film layer is further inhibited.
- the electrolytic solution temperature needs to be 35 to 80 ° C, preferably 40 to 70 ° C.
- the electrolytic solution temperature is less than 35 ° C.
- the alkaline etching ability is insufficient, and the porous structure of the porous aluminum oxide film layer becomes incomplete.
- the temperature exceeds 80 ° C. the alkaline etching force becomes excessive, and thus growth is inhibited in both the porous aluminum oxide film layer and the barrier type aluminum oxide film layer.
- the concentration of dissolved aluminum contained in the electrolytic solution needs to be 5 ppm or more and 1000 ppm or less.
- the dissolved aluminum concentration is less than 5 ppm, the formation reaction of the oxide film at the initial stage of the electrolytic reaction takes place rapidly, so that it is easily affected by variations in the treatment process (such as the contamination state of the aluminum material surface and the attachment state of the aluminum material). .
- a locally thick oxide film is formed.
- the dissolved aluminum concentration exceeds 1000 ppm, the viscosity of the electrolytic solution increases, and uniform convection near the surface of the aluminum material is hindered in the electrolysis process, and at the same time, dissolved aluminum acts in a direction to suppress film formation. .
- 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 quantity of electricity, that is, the product of the current density and the electrolysis time, and basically the quantity of electricity. As the amount increases, the thickness of the entire oxide film increases. From such a viewpoint, 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 20 to 100 Hz. If the frequency is less than 20 Hz, the direct current element increases as electrolysis, and as a result, 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, when the frequency 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 have a predetermined thickness. Takes an extremely long time.
- the current density needs to be 4 to 50 A / dm 2 .
- the current density is less than 4 A / dm 2 , since only the barrier type aluminum oxide film layer is formed preferentially, a porous aluminum oxide film layer cannot be obtained.
- the current becomes excessive, so that it is 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.
- Electrolysis time should be 5-60 seconds.
- the treatment time is less than 5 seconds, the formation of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is too rapid, so that neither oxide film layer is sufficiently formed, and it is composed of amorphous aluminum oxide. This is because it becomes an oxide film.
- the porous aluminum oxide film layer and the barrier-type aluminum oxide film layer may become too thick or may be redissolved, and the productivity also decreases.
- One electrode of the pair of electrodes used for the alternating current electrolytic treatment is an aluminum material to be surface-treated by electrolytic treatment.
- the other counter electrode for example, a known electrode such as a graphite, aluminum, or titanium electrode can be used.
- a graphite electrode is preferably used as the counter electrode. This is because the graphite electrode is chemically stable, inexpensive and easily available, and due to the action of many pores existing in the graphite electrode, the electric lines of force diffuse moderately in the AC electrolysis process. This is because the porous aluminum oxide film layer and the barrier type aluminum oxide film layer tend to be more uniform.
- both the aluminum material to be subjected to electrolytic treatment and the counter electrode are flat, the vertical and horizontal dimensions of the surfaces of the opposing aluminum material and the counter electrode are substantially the same, and both electrodes are stationary. It is preferable to perform the electrolysis operation.
- an oxide film is formed on the surface of the aluminum material facing the counter electrode.
- an oxide film is formed on one surface, the AC electrolysis treatment is once terminated, and then the other surface is used as the counter electrode.
- the AC electrolysis treatment may be performed in the same manner by arranging so as to face each other.
- the surface that has not been opposed to the counter electrode in the electrolysis process is re-arranged so as to face the counter electrode, and the electrolysis process is repeated.
- An oxide film can be formed on the surface.
- TEM transmission electron microscope
- a resin-coated surface-treated aluminum material By further coating a treated surface of the surface-treated aluminum material of the present invention with a resin layer, a resin-coated surface-treated aluminum material can be used for more applications.
- the resin layer may be either a thermosetting resin or a thermoplastic resin, and can provide various effects in combination with the oxide film having a specific structure defined in the present invention.
- the joined body of an aluminum material and a resin layer has a higher coefficient of thermal expansion of the resin than the aluminum material, it is easily peeled off at the interface between the aluminum material and the resin layer, and damage such as cracks and breaks easily occurs.
- the resin-coated surface-treated aluminum material according to the present invention is excellent in flexibility and easy to follow the expansion of the resin layer because the surface-treated aluminum material has a thin oxide film and has a specific structure. It has the characteristic that the damage at the interface of the resin layer hardly occurs.
- the occurrence of damage as described above is caused by, for example, the presence of an electrolytic aqueous solution in the peeling portion that occurs when the resin-coated surface-treated aluminum material is bent 180 degrees at 5R so that the resin layer has a convex shape. It can be evaluated by The greater the damage to the peeled part or the like, the lower the electrical resistance due to the electrolytic solution.
- the resin-coated surface-treated aluminum material using a thermoplastic resin as the resin layer can be suitably used as a lightweight and highly rigid composite material.
- the heated thermoplastic resin is made into a fluid state, and this is brought into contact with and permeated into the porous aluminum oxide film layer, and the thermoplastic resin layer is cooled and solidified.
- a thermoplastic resin film may be laminated on the surface-treated aluminum material.
- thermoplastic resins polyolefins such as polyethylene and polypropylene; polyvinyl chloride; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides; polyphenylene sulfide; aromatic polyether ketones such as polyether ether ketone and polyether ketone; polystyrene
- a fluorine resin such as polytetrafluoroethylene and polychlorotrifluoroethylene
- an acrylic resin such as polymethyl methacrylate
- ABS resin a polycarbonate
- thermoplastic polyimide The resin-coated surface-treated aluminum material coated with such a thermoplastic resin is used for various moving bodies that are required to be lightweight and highly rigid, specifically for components such as the aerospace field, automobiles, ships, and railway vehicles. Can be used.
- thermosetting resin As a method for forming the resin layer, the thermosetting resin is made into a fluid state, and this is brought into contact with and infiltrated into the porous aluminum oxide film layer, and then the thermosetting resin is heated and cured.
- the thermosetting resin phenol resin; epoxy resin such as bisphenol A type and novolac type; melamine resin; urea resin; unsaturated polyester resin; alkyd resin; polyurethane;
- thermoplastic resin and the thermosetting resin may be used as a single resin or as a polymer alloy in which two or more kinds are mixed. Moreover, physical properties, such as resin intensity
- a filler known materials such as various fibers such as glass fiber, carbon fiber, and aramid fiber; inorganic substances such as calcium carbonate, magnesium carbonate, silica, talc, and glass; clay;
- Examples 1 to 15 and Comparative Examples 1 to 13 As the aluminum material, a JIS5052-H34 alloy plate having a length of 200 mm, a width of 400 mm, and a plate thickness of 1.0 mm was used. This aluminum alloy plate was used as one electrode, and a graphite plate or a titanium plate having a flat plate shape of 300 mm long ⁇ 500 mm wide ⁇ 2.0 mm thick was used as the counter electrode.
- One side of the aluminum alloy plate was made to face the counter electrode, and both electrodes were arranged so that a porous aluminum oxide film layer on the surface side and a barrier type aluminum oxide film layer on the substrate side were formed on the surface layer of the facing one side.
- An alkaline aqueous solution mainly composed of sodium pyrophosphate was used as the electrolytic solution.
- the alkaline component concentration of the electrolytic solution was 0.5 mol / liter, and the pH was adjusted with hydrochloric acid and a sodium hydroxide aqueous solution (both concentrations were 0.1 mol / liter).
- alternating current electrolytic treatment was performed to form a porous aluminum oxide film layer and a barrier type aluminum oxide film layer.
- a sulfuric acid alumite treatment (thickness: 2.5 ⁇ m, with sealing treatment) based on the prior art was performed instead of the alkaline alternating current electrolysis treatment.
- the cross section of the specimen prepared as described above was observed by TEM. Specifically, in order to measure the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer, as well as the diameter of the small holes in the porous aluminum oxide film layer, from the test material using an ultramicrotome A slice sample for cross-sectional observation was prepared. Next, arbitrary 10 points in the observation field (1 ⁇ m ⁇ 1 ⁇ m) are selected in the thin sample, and the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is measured by TEM cross-sectional observation. The diameter of the small holes in the oxide film layer was measured at each point (first measurement). For these thicknesses and diameters, the arithmetic average of the 10 measured values is shown in the first measurement of Table 2.
- the total thickness was obtained by adding the thicknesses of the coating layers to obtain the oxide coating thickness at each point.
- the maximum value, the minimum value, and the arithmetic average value of the 100 oxide film thicknesses obtained in this way are shown in the second measurement of Table 2. Furthermore, it was examined whether or not the fluctuation range of the oxide film thickness at these 100 points was within ⁇ 50% of the arithmetic average value. Specifically, when the arithmetic average value is T (nm), the total thickness including the maximum value and the minimum value is in the range of (0.5 ⁇ T) to (1.5 ⁇ T). Table 2 shows the second measurement as a pass (O) when there was a case and a failure (X) when it was not in the range.
- test materials were evaluated for adhesiveness using an adhesive, adhesion to a coating film, and flexibility by a bending test by the following methods. Furthermore, the resin-coated surface-treated aluminum material was also evaluated.
- the shear test piece produced 10 sets of test pieces from the same test material, and evaluated each.
- ⁇ The shear stress is 20 N / mm 2 or more and the adhesive layer itself is agglomerated and broken
- ⁇ The shear stress is 20 N / mm 2 or more, but the adhesive layer and the test material are separated at the interface
- ⁇ Shear stress is less than 20 N / mm 2 and the state where the adhesive layer and the specimen were peeled from each other
- Table 3 The results are shown in Table 3.
- the table shows the number of pairs of the above-mentioned ⁇ , ⁇ , and ⁇ of 10 sets of test pieces, respectively.
- the adhesion was evaluated according to the following criteria by the coating film residual ratio.
- the adhesive test piece produced 10 test pieces from the same test material, and evaluated each.
- ⁇ The film remaining rate is 100%.
- ⁇ The film remaining rate is 75% or more and less than 100%.
- X The film remaining rate is less than 75%.
- the table shows the number of the above-mentioned ⁇ , ⁇ , and ⁇ among the 10 test pieces, respectively, and the case where all were ⁇ was determined to be acceptable, and the other was determined to be unacceptable.
- L (mm) is the total length at which copper adhesion was observed in the bent part, and by dividing it by the total bending length (25 mm), (L / 25) ⁇ 100 (%) cracking occurred.
- the exposure rate of the aluminum substrate based on Ten test pieces were produced from the same specimen as the flexible test piece and evaluated for each to determine the exposure rate of the aluminum substrate. The results are shown in Table 3.
- the exposure rate in the table indicates the average exposure rate of 10 test pieces. Here, the exposure rate was determined to be 5% or less, and those exceeding this were determined to be unacceptable.
- the bending apex of the test piece was brought into contact with a 20 mm wide sponge containing 1% sodium chloride aqueous solution, and a DC voltage of 6.0 V was applied for 4 seconds, with the test piece side being positive and the sponge side being negative.
- the maximum current value was measured.
- no damage such as peeling occurs at the interface between the test material and the resin layer
- no current flows because the test piece becomes an insulator.
- an electric current flows by the sodium chloride aqueous solution which exists there.
- the larger the damaged part the larger the amount of sodium chloride solution present there, the lower the electrical resistance and the larger the maximum current value.
- Comparative Example 6 a thin oxide film was locally formed because the dissolved aluminum concentration of the electrolytic solution in the AC electrolytic treatment was too high. Therefore, the fluctuation range of the total thickness of the oxide film, adhesiveness, adhesion, and flexibility were unacceptable.
- Comparative Example 13 was an alumite sulfate treatment based on the prior art, and did not have the oxide film structure defined in the present invention, and therefore the adhesiveness, adhesion and flexibility were unacceptable.
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Abstract
Description
本発明は、第2の側面において、対電極を黒鉛電極とするものとした。
更に本発明は、第2の側面において、更に、前記表面処理されるアルミニウム材の電極と、対電極が共に平板状であるものとした。 The second aspect of the present invention is a method for producing a surface-treated aluminum material according to the first aspect, wherein an aluminum material electrode to be surface-treated and a counter electrode are used, and the liquid temperature is 35 at pH 9-13. AC electrolytic treatment under the conditions of an alkaline aqueous solution with a dissolved aluminum concentration of 5 ppm or more and 1000 ppm or less as an electrolytic solution at a frequency of 20 to 100 Hz, a current density of 4 to 50 A / dm 2 and an electrolysis time of 5 to 60 seconds. Thus, an oxide film is formed on the surface of the aluminum material facing the counter electrode.
In the second aspect of the present invention, the counter electrode is a graphite electrode.
Furthermore, in the second aspect of the present invention, both the surface-treated aluminum material electrode and the counter electrode are flat.
本発明に用いるアルミニウム材としては、純アルミニウム又はアルミニウム合金が用いられる。アルミニウム合金の成分には特に制限無く、JISに規定される合金をはじめとする各種合金を使用することができる。形状としては特に制限されるものではないが、安定して処理皮膜を形成できることから平板状のものが好適に用いられる。用途に応じて、板厚を適宜選択することができるが、軽量化と成形性の観点から0.05~2.0mmが好ましく、0.1~1.0mmが更に好ましい。 A. Aluminum material Pure aluminum or an aluminum alloy is used as the aluminum material used in the present invention. There is no restriction | limiting in particular in the component of an aluminum alloy, Various alloys including the alloy prescribed | regulated to JIS can be used. Although it does not restrict | limit especially as a shape, Since a processing film can be formed stably, a flat thing is used suitably. The plate thickness can be appropriately selected depending on the application, but is preferably 0.05 to 2.0 mm, more preferably 0.1 to 1.0 mm from the viewpoint of weight reduction and formability.
本発明に用いるアルミニウム材の表面には、表面側に形成された多孔性アルミニウム酸化皮膜層と素地側に形成されたバリア型アルミニウム酸化皮膜層とが設けられている。すなわち、アルミニウム材表面には、多孔性アルミニウム酸化皮膜層とバリア型アルミニウム酸化皮膜層の二層によって構成される酸化皮膜が設けられている。多孔性アルミニウム酸化皮膜層が強力な接着性や密着性を発揮する一方で、バリア型アルミニウム酸化皮膜層によって、アルミニウム酸化皮膜層全体とアルミニウム素地を強固に結合する。 B. 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, an oxide film composed of two layers of a porous aluminum oxide film layer and a barrier type aluminum oxide film layer is provided on the surface of the aluminum material. While the porous aluminum oxide film layer exhibits strong adhesion and adhesion, the entire aluminum oxide film layer and the aluminum substrate are firmly bonded by the barrier type aluminum oxide film layer.
多孔性アルミニウム酸化皮膜層の厚さは、20~500nmである。20nm未満では厚さが十分でないため、後述する小孔構造の形成が不十分になり易く接着力や密着力が低下する。一方、500nmを超えると、多孔性アルミニウム酸化皮膜層自体が凝集破壊し易くなり接着力や密着力が低下する。 B-1. Porous aluminum oxide film layer The thickness of the porous aluminum oxide film layer is 20 to 500 nm. If the thickness is less than 20 nm, the thickness is not sufficient, so that the formation of a small pore structure, which will be described later, is likely to be insufficient, and the adhesive force and adhesion force are reduced. On the other hand, when the thickness exceeds 500 nm, the porous aluminum oxide film layer itself tends to cohesively break down, and the adhesive force and adhesion force are reduced.
バリア型アルミニウム酸化皮膜層の厚さは、3~30nmである。3nm未満では、介在層として多孔性アルミニウム酸化皮膜層とアルミニウム素地との結合に十分な結合力を付与することができず、特に、高温・多湿等の過酷環境における結合力が不十分となる。一方、30nmを超えると、その緻密性ゆえにバリア型アルミニウム酸化皮膜層が凝集破壊し易くなり、かえって接着力や密着力が低下する。 B-2. Barrier type aluminum oxide film layer The thickness of the barrier type aluminum oxide film layer is 3 to 30 nm. If the thickness is less than 3 nm, a sufficient bonding force cannot be imparted to the bonding between the porous aluminum oxide film layer and the aluminum substrate as the intervening layer, and the bonding force particularly in a severe environment such as high temperature and high humidity becomes insufficient. On the other hand, if the thickness exceeds 30 nm, the barrier type aluminum oxide film layer tends to cohesively break due to its denseness, and on the contrary, the adhesive strength and the adhesive strength are lowered.
酸化皮膜全体の厚さ、すなわち、B-1に記載の多孔性アルミニウム酸化皮膜層とB-2に記載のバリア型アルミニウム酸化皮膜層との厚さの合計は、アルミニウム材のいかなる場所で測定しても、その変動幅が±50%以内でなければならず、好ましくは±20%以内である。すなわち、アルミニウム材表面における任意の複数箇所(10箇所以上が望ましく、これら各箇所においても10点以上の測定点とするのが望ましい)で測定した酸化皮膜全体厚さの平均をT(nm)とした場合、これら複数測定箇所の全てにおける酸化皮膜全体厚さが(0.5×T)~(1.5×T)の範囲にある必要がある。(0.5×T)未満の箇所が存在すると、その箇所の酸化皮膜がその周囲より薄くなる。そうすると、この薄い箇所では、接着すべき接着剤や密着すべき樹脂層などと酸化皮膜との間に隙間が生じ易くなり、十分な接触面積を確保できずに接着力や密着力が低下する。
一方、(1.5×T)を超える箇所が存在すると、その箇所の酸化皮膜が周囲の周囲より厚くなる。そうすると、この厚い箇所では、密着すべき樹脂層などからの応力が集中し、酸化皮膜での凝集破壊を誘発して接着力や密着力が低下する。
なお、上記のような酸化皮膜の全体厚さが薄い箇所や厚い箇所では、周囲と比較して光学的特性が異なるため、茶褐色や白濁色といった色調の変化として目視可能な場合がある。 B-3. Variation width 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 B-1 and the barrier type aluminum oxide film layer described in B-2 is Even if it is measured at any location of the aluminum material, the fluctuation range must be within ± 50%, preferably within ± 20%. That is, the average of the entire thickness of the oxide film measured at an arbitrary plurality of locations on the aluminum material surface (ten or more are desirable, and it is desirable to have 10 or more measurement points in each location) is T (nm). In this case, it is necessary that the total thickness of the oxide film at all of the plurality of measurement points is in the range of (0.5 × T) to (1.5 × T). When a location less than (0.5 × T) exists, the oxide film at that location becomes thinner than the surrounding area. If it does so, in this thin location, it will become easy to produce a clearance gap between the adhesive agent which should be adhered, the resin layer which should be stuck, etc., and an oxide film, and sufficient contact area cannot be secured but adhesive strength and adhesion power will fall.
On the other hand, if there is a location exceeding (1.5 × T), the oxide film at that location becomes thicker than the surrounding area. Then, in this thick part, the stress from the resin layer etc. which should be contact | adhered concentrates, the cohesive failure in an oxide film is induced, and adhesive force and adhesive force fall.
In addition, since the optical characteristics are different in the portion where the total thickness of the oxide film as described above is thin or thick, it may be visible as a change in color tone such as brownish brown or cloudy color.
本発明に係る表面処理アルミニウム材がプリント配線基板などに用いられる場合には、曲げられた状態で使用されることがある。一般に、アルミニウム材が曲げられた状態では、表面の酸化皮膜にクラックが発生し易い。本発明に係る表面処理アルミニウム材の酸化皮膜は上記特定構造を備えることにより、酸化皮膜が凝集破壊し難く柔軟性に優れる。そのため、表面処理アルミニウム材が曲げられた状態で使用されても、酸化皮膜のクラック発生が抑制される。 B-4. Flexibility When the surface-treated aluminum material according to the present invention is used for a printed wiring board or the like, it may be used in a bent state. In general, when the aluminum material is bent, cracks are likely to occur in the oxide film on the surface. Since the oxide film of the surface-treated aluminum material according to the present invention has the above specific structure, the oxide film is difficult to cohesively break and is excellent in flexibility. Therefore, even if the surface-treated aluminum material is used in a bent state, the generation of cracks in the oxide film is suppressed.
以上のような条件を満たした酸化皮膜を表面に備えた表面処理アルミニウム材を製造するための一つの方法として、表面処理されるアルミニウム材の電極と、対電極として後述の材質の電極とを用い、pH9~13で液温35~80℃であり、かつ、溶存アルミニウム濃度が5ppm以上1000ppm以下のアルカリ性水溶液を電解溶液とし、周波数20~100Hz、電流密度4~50A/dm2及び電解時間5~60秒間の条件で交流電解処理することにより、対電極に対向する前記アルミニウム材表面に酸化皮膜を形成する方法を挙げることができる。 C. Manufacturing method As one method for manufacturing a surface-treated aluminum material having an oxide film on the surface that satisfies the above conditions, an electrode of an aluminum material to be surface-treated and an electrode of a material described later as 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 to 1000 ppm as an electrolytic solution, a frequency of 20 to 100 Hz, a current density of 4 to 50 A / dm 2, and an electrolysis time A method of forming an oxide film on the surface of the aluminum material facing the counter electrode by performing AC electrolytic treatment for 5 to 60 seconds can be mentioned.
また、アルミニウム材の形状が板材以外の棒状や角材の場合においても、電解工程で対電極に対向していなかった表面を対電極に対向するように配置し直して電解工程を繰り返すことにより、所望の表面に酸化皮膜を形成することができる。 In the present invention, both the aluminum material to be subjected to electrolytic treatment and the counter electrode are flat, the vertical and horizontal dimensions of the surfaces of the opposing aluminum material and the counter electrode are substantially the same, and both electrodes are stationary. It is preferable to perform the electrolysis operation. In this case, an oxide film is formed on the surface of the aluminum material facing the counter electrode. Here, in order to form an oxide film on the other surface not facing the counter electrode, an oxide film is formed on one surface, the AC electrolysis treatment is once terminated, and then the other surface is used as the counter electrode. The AC electrolysis treatment may be performed in the same manner by arranging so as to face each other.
In addition, even in the case where the shape of the aluminum material is a rod shape or a square material other than the plate material, the surface that has not been opposed to the counter electrode in the electrolysis process is re-arranged so as to face the counter electrode, and the electrolysis process is repeated. An oxide film can be formed on the surface.
本発明の表面処理アルミニウム材の処理面に樹脂層を更に被覆して樹脂被覆表面処理アルミニウム材とすることにより、更に多くの用途に使用できる。ここで、樹脂層としては、熱硬化性樹脂と熱可塑性樹脂のいずれでもよく、本発明で規定する特定構造の酸化皮膜と相まって、様々な効果を付与できる。通常、アルミニウム材と樹脂層との接合体は、アルミニウム材に比べて樹脂の熱膨張率が大きいことから、アルミニウム材と樹脂層の界面において剥がれ、クラック、切れなどの損傷が発生し易い。しかしながら、本発明に係る樹脂被覆表面処理アルミニウム材は、表面処理アルミニウム材の酸化皮膜が薄く、かつ、特定構造を有することにより、柔軟性に優れ、樹脂層の膨張に追従し易く、アルミニウム材と樹脂層の界面での上記損傷が発生し難い特徴を備える。 D. Resin-coated surface-treated aluminum material By further coating a treated surface of the surface-treated aluminum material of the present invention with a resin layer, a resin-coated surface-treated aluminum material can be used for more applications. Here, the resin layer may be either a thermosetting resin or a thermoplastic resin, and can provide various effects in combination with the oxide film having a specific structure defined in the present invention. Usually, since the joined body of an aluminum material and a resin layer has a higher coefficient of thermal expansion of the resin than the aluminum material, it is easily peeled off at the interface between the aluminum material and the resin layer, and damage such as cracks and breaks easily occurs. However, the resin-coated surface-treated aluminum material according to the present invention is excellent in flexibility and easy to follow the expansion of the resin layer because the surface-treated aluminum material has a thin oxide film and has a specific structure. It has the characteristic that the damage at the interface of the resin layer hardly occurs.
実施例1~15及び比較例1~13
アルミニウム材として、縦200mm×横400mm×板厚1.0mmのJIS5052-H34合金板を使用した。このアルミニウム合金板を一方の電極に用い、対電極には縦300mm×横500mm×板厚2.0mmの平板形状を有する黒鉛板又はチタン板を用いた。アルミニウム合金板の片面を対電極に対面させ、この対面した片面表層に、表面側の多孔性アルミニウム酸化皮膜層と素地側のバリア型アルミニウム酸化皮膜層が形成されるように、両電極を配置した。ピロりん酸ナトリウムを主成分とするアルカリ水溶液を、電解溶液として用いた。電解溶液のアルカリ成分濃度は、0.5モル/リットルとするとともに、塩酸及び水酸化ナトリウム水溶液(いずれも濃度0.1モル/リットル)によってpHの調整を行なった。表1に示す電解条件にて、交流電解処理を実施して多孔性アルミニウム酸化皮膜層及びバリア型アルミニウム酸化皮膜層を形成した。なお、比較例13では、アルカリ交流電解処理に代わって、従来技術に基づいた硫酸アルマイト処理(厚さ2.5μm、封孔処理あり)を実施した。 Hereinafter, preferred embodiments of the present invention will be described in detail based on examples and comparative examples.
Examples 1 to 15 and Comparative Examples 1 to 13
As the aluminum material, a JIS5052-H34 alloy plate having a length of 200 mm, a width of 400 mm, and a plate thickness of 1.0 mm was used. This aluminum alloy plate was used as one electrode, and a graphite plate or a titanium plate having a flat plate shape of 300 mm long × 500 mm wide × 2.0 mm thick was used as the counter electrode. One side of the aluminum alloy plate was made to face the counter electrode, and both electrodes were arranged so that a porous aluminum oxide film layer on the surface side and a barrier type aluminum oxide film layer on the substrate side were formed on the surface layer of the facing one side. . An alkaline aqueous solution mainly composed of sodium pyrophosphate was used as the electrolytic solution. The alkaline component concentration of the electrolytic solution was 0.5 mol / liter, and the pH was adjusted with hydrochloric acid and a sodium hydroxide aqueous solution (both concentrations were 0.1 mol / liter). Under the electrolytic conditions shown in Table 1, alternating current electrolytic treatment was performed to form a porous aluminum oxide film layer and a barrier type aluminum oxide film layer. In Comparative Example 13, a sulfuric acid alumite treatment (thickness: 2.5 μm, with sealing treatment) based on the prior art was performed instead of the alkaline alternating current electrolysis treatment.
上記供試材から長さ50mm、25mm幅に切断したものを2枚用意した。これら2枚の供試材同士を幅方向に沿って幅10mmをもって酸化皮膜形成面同士を重ね合わせ、市販の2液型エポキシ接着剤(主剤=変性エポキシ樹脂、硬化剤=変性ポリイミド、重量混合比=主剤100/硬化剤100)によって重ね合わせ部分を接着し、せん断試験片を作製した。2枚の供試材の長さ方向の端部を引張試験機により100mm/分の速度にて長さ方向に沿って反対向きに引張り、その荷重(せん断応力に換算)と剥離状態によって接着性を下記の基準で評価した。なお、せん断試験片は同じ供試材から10組の試験片を作製して、それぞれについて評価した。
○:せん断応力が20N/mm2以上で、かつ、接着剤層自身が凝集破壊した状態
△:せん断応力が20N/mm2以上であるものの、接着剤層と供試材が界面剥離した状態
×:せん断応力が20N/mm2未満で、かつ、接着剤層と供試材が界面剥離した状態
結果を表3に示す。同表には、10組の試験片のうちの上記○、△、×の組数をそれぞれ示すが、全てが○の場合を合格、それ以外を不合格と判定した。 [Adhesion evaluation]
Two sheets were prepared by cutting the test material into a length of 50 mm and a width of 25 mm. These two specimens are overlapped with each other in the width direction with a width of 10 mm and the oxide film forming surfaces are superposed, and a commercially available two-component epoxy adhesive (main component = modified epoxy resin, curing agent = modified polyimide, weight mixing ratio). = Main component 100 / Hardening agent 100) and the overlapped portion was bonded to prepare a shear test piece. The lengthwise ends of the two specimens are pulled in the opposite direction along the length direction at a speed of 100 mm / min with a tensile tester, and the adhesiveness depends on the load (converted to shear stress) and the peeled state. Was evaluated according to the following criteria. In addition, the shear test piece produced 10 sets of test pieces from the same test material, and evaluated each.
○: The shear stress is 20 N / mm 2 or more and the adhesive layer itself is agglomerated and broken Δ: The shear stress is 20 N / mm 2 or more, but the adhesive layer and the test material are separated at the interface × : Shear stress is less than 20 N / mm 2 and the state where the adhesive layer and the specimen were peeled from each other The results are shown in Table 3. The table shows the number of pairs of the above-mentioned ○, Δ, and × of 10 sets of test pieces, respectively.
上記供試材の酸化皮膜側の表面に大日本塗料(株)製「Vフロン#2000」を塗布しこれを乾燥して(160℃,20分)、30μmの厚さの樹脂塗膜を形成した密着性試験片を作製した。JIS-K5600-5-6に準拠した方法で、この密着性試験片の樹脂塗膜にカッターナイフを用いて1mm角の碁盤目カットを入れた。次いで、試験片に125℃で30分のレトルト浸漬処理を施した後に、直ちに処理液から取り出して水分をふき取った。この試験片に対して、透明感圧付着テープによる剥離試験を実施した。塗膜残存率によって密着性を下記の基準で評価した。なお、密着性試験片は同じ供試材から10個の試験片を作製して、それぞれについて評価した。
○:塗膜残存率が100%のもの
△:塗膜残存率が75%以上100%未満のもの
×:塗膜残存率が75%未満のもの
結果を表3に示す。同表には、10個の試験片のうちの上記○、△、×の個数をそれぞれ示すが、全てが○の場合を合格、それ以外を不合格と判定した。 [Adhesion evaluation]
“V Freon # 2000” manufactured by Dainippon Paint Co., Ltd. was applied to the surface of the above test material on the oxide film side and dried (160 ° C., 20 minutes) to form a resin film having a thickness of 30 μm. An adhesive test piece was prepared. Using a cutter knife, a 1 mm square grid cut was made in the resin coating film of this adhesion test piece by a method according to JIS-K5600-5-6. Next, the test piece was subjected to a retort immersion treatment at 125 ° C. for 30 minutes, and then immediately removed from the treatment liquid to wipe off moisture. The test piece was subjected to a peel test using a transparent pressure-sensitive adhesive tape. The adhesion was evaluated according to the following criteria by the coating film residual ratio. In addition, the adhesive test piece produced 10 test pieces from the same test material, and evaluated each.
○: The film remaining rate is 100%. Δ: The film remaining rate is 75% or more and less than 100%. X: The film remaining rate is less than 75%. The table shows the number of the above-mentioned ○, Δ, and × among the 10 test pieces, respectively, and the case where all were ○ was determined to be acceptable, and the other was determined to be unacceptable.
上記供試材から長さ50mm、25mm幅に切断したものを用意した。酸化皮膜形成面が凸となるように、金型を用いて5Rで180度曲げた。次いで、曲げ部を試験液(20%硫酸銅水溶液)に5分間浸漬した後に取り出して水洗し、室温で乾燥した。曲げ部の酸化皮膜にクラックが発生している場合は、クラックのアルミニウム素地面に銅が付着する。そこで、ルーペ又はノギスを用いて曲げ部分の全長に沿って銅付着箇所を目視で観察することによりクラック発生部位を特定した。具体的には、曲げ部分において銅の付着が観察された総長さをL(mm)とし、それを曲げ全長(25mm)で除算することによって、(L/25)×100(%)をクラック発生に基づくアルミニウム素地の露出率とした。柔軟性試験片は同じ供試材から10個の試験片を作製して、それぞれについて評価してアルミニウム素地の各露出率を求めた。
結果を表3に示す。表の露出率は、10個の試験片の平均露出率を示す。ここで、露出率が5%以下を合格とし、これを超えるものを不合格と判定した。 [Flexibility evaluation]
What cut | disconnected length 50mm and 25mm width from the said test material was prepared. It was bent 180 degrees at 5R using a mold so that the oxide film forming surface was convex. Next, the bent portion was immersed in a test solution (20% aqueous copper sulfate solution) for 5 minutes, then taken out, washed with water, and dried at room temperature. When a crack is generated in the oxide film at the bent portion, copper adheres to the aluminum base of the crack. Then, the crack generation | occurrence | production site | part was pinpointed by observing a copper adhesion location visually along the full length of a bending part using a loupe or a caliper. Specifically, L (mm) is the total length at which copper adhesion was observed in the bent part, and by dividing it by the total bending length (25 mm), (L / 25) × 100 (%) cracking occurred. The exposure rate of the aluminum substrate based on Ten test pieces were produced from the same specimen as the flexible test piece and evaluated for each to determine the exposure rate of the aluminum substrate.
The results are shown in Table 3. The exposure rate in the table indicates the average exposure rate of 10 test pieces. Here, the exposure rate was determined to be 5% or less, and those exceeding this were determined to be unacceptable.
上記供試材の酸化皮膜側の表面にDIC(株)製「9K-564S」(水性アクリル樹脂塗料)を塗布しこれを乾燥して(250℃,1分)、2μmの厚さの樹脂塗膜(樹脂層)を形成し、樹脂被覆表面処理アルミニウム材を作製した。これを長さ100mm、幅30mmに切断するとともに、樹脂層側が凸となるように、金型を用いて5Rで180度曲げ、試験片を作製した。試験片の曲げ頂点部を、1%塩化ナトリウム水溶液を含ませた幅20mmのスポンジに接触させるとともに、試験片側をプラスとしスポンジ側をマイナスとして6.0Vの直流電圧を4秒間印加し、電圧印加中の最大電流値を測定した。供試材と樹脂層の界面において剥がれ等の損傷が発生していない場合には、試験片が絶縁体となるため電流が流れない。一方、損傷部分が存在する場合には、そこに存在する塩化ナトリウム水溶液により電流が流れる。そして、損傷部分が大きい程、そこに存在する塩化ナトリウム水溶液が多量となり電気抵抗が低減して最大電流値が大きくなる。最大電流値が5mA未満の場合には、剥がれ等の損傷が無いか又は小さく合格とした。一方、5mA以上の場合には、剥がれ等の損傷が大きく不合格とした。結果を表3に示す。 [Evaluation of resin-coated surface-treated aluminum]
“9K-564S” (water-based acrylic resin paint) manufactured by DIC Corporation was applied to the surface of the above-mentioned test material on the oxide film side, dried (250 ° C., 1 minute), and a 2 μm thick resin coating was applied. A film (resin layer) was formed to produce a resin-coated surface-treated aluminum material. This was cut into a length of 100 mm and a width of 30 mm, and was bent 180 degrees at 5R using a mold so that the resin layer side was convex, to prepare a test piece. The bending apex of the test piece was brought into contact with a 20 mm wide sponge containing 1% sodium chloride aqueous solution, and a DC voltage of 6.0 V was applied for 4 seconds, with the test piece side being positive and the sponge side being negative. The maximum current value was measured. When no damage such as peeling occurs at the interface between the test material and the resin layer, no current flows because the test piece becomes an insulator. On the other hand, when a damaged part exists, an electric current flows by the sodium chloride aqueous solution which exists there. And the larger the damaged part, the larger the amount of sodium chloride solution present there, the lower the electrical resistance and the larger the maximum current value. When the maximum current value was less than 5 mA, there was no damage such as peeling or a small pass. On the other hand, in the case of 5 mA or more, damage such as peeling was large, and the test was rejected. The results are shown in Table 3.
2・・・酸化皮膜
3・・・多孔性アルミニウム酸化皮膜層
31・・・小孔
4・・・バリア型アルミニウム酸化皮膜層
5・・・素地 DESCRIPTION OF
Claims (6)
- 表面に酸化皮膜が形成されたアルミニウム材であって、前記酸化皮膜は表面側に形成された厚さ20~500nmの多孔性アルミニウム酸化皮膜層と素地側に形成された厚さ3~30nmのバリア型アルミニウム酸化皮膜層とから成り、前記多孔性アルミニウム酸化皮膜層には直径5~30nmの小孔が形成されており、当該アルミニウム材表面全体における前記多孔性アルミニウム酸化皮膜層とバリア型アルミニウム酸化皮膜層との合計厚さの変動幅が、当該合計厚さの算術平均値の±50%以内であることを特徴とする表面処理アルミニウム材。 An aluminum material having an oxide film formed on the surface, the oxide film comprising a porous aluminum oxide film layer having a thickness of 20 to 500 nm formed on the surface side and a barrier having a thickness of 3 to 30 nm formed on the substrate side The porous aluminum oxide film layer has small pores with a diameter of 5 to 30 nm, and the porous aluminum oxide film layer and the barrier type aluminum oxide film on the entire surface of the aluminum material. The surface-treated aluminum material characterized in that the fluctuation range of the total thickness with the layer is within ± 50% of the arithmetic average value of the total thickness.
- 前記表面処理アルミニウム材を酸化皮膜側が凸となるように5Rで180度曲げた際において、アルミニウム素地の露出率が5%以下である、請求項1に記載の表面処理アルミニウム材。 The surface-treated aluminum material according to claim 1, wherein when the surface-treated aluminum material is bent 180 degrees at 5R so that the oxide film side is convex, the exposure rate of the aluminum substrate is 5% or less.
- 請求項1又は2に記載の表面処理アルミニウム材の製造方法であって、表面処理されるアルミニウム材の電極と、対電極とを用い、pH9~13で液温35~80℃であり、かつ、溶存アルミニウム濃度が5ppm以上1000ppm以下のアルカリ性水溶液を電解溶液とし、周波数20~100Hz、電流密度4~50A/dm2及び電解時間5~60秒間の条件で交流電解処理することにより、対電極に対向する前記アルミニウム材表面に酸化皮膜を形成することを特徴とする表面処理アルミニウム材の製造方法。 The method for producing a surface-treated aluminum material according to claim 1 or 2, wherein the surface-treated aluminum material electrode and a counter electrode are used, the pH is 9 to 13, the liquid temperature is 35 to 80 ° C, and An alkaline aqueous solution having a dissolved aluminum concentration of 5 ppm or more and 1000 ppm or less is used as an electrolytic solution, and is subjected to alternating current electrolysis treatment under conditions of a frequency of 20 to 100 Hz, a current density of 4 to 50 A / dm 2 and an electrolysis time of 5 to 60 seconds to face the counter electrode. A method of producing a surface-treated aluminum material, comprising forming an oxide film on the surface of the aluminum material.
- 前記対電極を黒鉛電極とする、請求項3に記載の表面処理アルミニウム材の製造方法。 The method for producing a surface-treated aluminum material according to claim 3, wherein the counter electrode is a graphite electrode.
- 前記表面処理されるアルミニウム材の電極と、対電極が共に平板状である、請求項3又は4に記載の表面処理アルミニウム材の製造方法。 The method for producing a surface-treated aluminum material according to claim 3 or 4, wherein the surface-treated aluminum material electrode and the counter electrode are both flat.
- 請求項1又は2に記載の表面処理アルミニウム材の酸化皮膜の表面に樹脂層を被覆したことを特徴とする樹脂被覆表面処理アルミニウム材。 A resin-coated surface-treated aluminum material, wherein a surface of the oxide film of the surface-treated aluminum material according to claim 1 or 2 is coated with a resin layer.
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JP7093607B2 (en) | 2017-02-22 | 2022-06-30 | 株式会社Uacj | Surface-treated aluminum material and its manufacturing method, and surface-treated aluminum material / joined member made of surface-treated aluminum material and a member to be joined such as resin, and a method for manufacturing the same. |
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