WO2017026461A1 - 樹脂密着性に優れた表面処理アルミニウム材及びその製造方法、ならびに、表面処理アルミニウム材/樹脂の接合体 - Google Patents
樹脂密着性に優れた表面処理アルミニウム材及びその製造方法、ならびに、表面処理アルミニウム材/樹脂の接合体 Download PDFInfo
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- WO2017026461A1 WO2017026461A1 PCT/JP2016/073351 JP2016073351W WO2017026461A1 WO 2017026461 A1 WO2017026461 A1 WO 2017026461A1 JP 2016073351 W JP2016073351 W JP 2016073351W WO 2017026461 A1 WO2017026461 A1 WO 2017026461A1
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- oxide film
- aluminum material
- film layer
- aluminum oxide
- resin
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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
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
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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
- C25D11/18—After-treatment, e.g. pore-sealing
Definitions
- 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 excellent resin adhesion, and a method for stably producing the surface-treated aluminum material. Furthermore, the present invention relates to a surface-treated aluminum material / resin bonded body.
- 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 comprises a porous aluminum oxide film layer having a thickness of 20 to 500 nm on the aluminum material surface and a barrier type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the substrate side. Small holes having 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 an arithmetic average of the total thickness. An oxide film that is within ⁇ 50% of the value is formed.
- an alkaline aqueous solution having an aluminum material electrode and a counter electrode, a pH of 9 to 13, a liquid temperature of 35 to 80 ° C., and a dissolved aluminum concentration of 5 ppm to 1000 ppm is used as an electrolytic solution, and a frequency of 20 to
- the above oxide film can be obtained by AC electrolytic treatment under the conditions of 100 Hz, current density of 4 to 50 A / dm 2 and electrolysis time of 5 to 60 seconds.
- the resin adhesion may not necessarily be improved depending on the configuration of the manufacturing equipment. Specifically, when performing the above electrolytic treatment on a long aluminum material such as an aluminum plate wound in a coil shape or a long extruded aluminum shape, an aluminum material and a counter electrode are used to improve productivity. It has been found that the resin adhesion may not be exhibited when a so-called continuous treatment is performed in which an electric current is always supplied in between and an aluminum material is continuously conveyed and supplied into the electrolytic cell.
- the present invention has been made in view of the above circumstances, and in the case of mainly subjecting a long aluminum material to a continuous treatment, a surface-treated aluminum material excellent in resin adhesion, a method for producing the same, and the surface-treated aluminum.
- the object is to provide a material / resin bonded body.
- the inventors of the present invention do not necessarily improve the resin adhesion of an aluminum material subjected to continuous treatment. It was found that the behavior was affecting. 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 when electrolysis is performed by continuous treatment, and the present inventors have further studied and completed the present invention.
- an oxide film is formed on the surface, and the oxide film is formed on the surface side with a porous aluminum oxide film layer having a thickness of 20 to 500 nm and a thickness formed on the substrate side.
- the porous aluminum oxide film layer is formed with small pores having a diameter of 5 to 30 nm.
- the porous aluminum oxide film layer and the barrier type aluminum oxide film A surface-treated aluminum material having excellent resin adhesion, wherein the crack length generated at the boundary with the layer is 50% or less of the boundary length.
- the present invention provides the method for producing a surface-treated aluminum material according to claim 1, wherein an aluminum material electrode and a counter electrode fixed to the electrolytic solution are continuously fed into the electrolytic solution.
- the electrolytic solution is an alkaline aqueous solution having a pH of 9 to 13 and a liquid temperature of 35 to 85 ° C., and is subjected to alternating current electrolytic treatment under conditions of a frequency of 10 to 100 Hz, a current density of 4 to 50 A / dm 2 and an electrolysis time of 5 to 300 seconds.
- the electrode of the aluminum material and the counter electrode are continuously energized and subjected to electrolysis after the electrolysis time is finished.
- surface treatment Al of time until the current density flowing to the aluminum material portion is less than 1A / dm 2 and an excellent resin adhesion to equal to or less than 10.0 seconds It was a method of manufacturing a chloride material.
- the distance between the electrodes of the aluminum material and the counter electrode is 2 to 150 mm.
- the present invention provides the surface-treated aluminum according to claim 4, comprising the surface-treated aluminum material according to claim 1 and a resin coated on a surface on which an oxide film of the surface-treated aluminum material is formed. A material / resin bonded body was obtained.
- 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 excellent in resin adhesion can be obtained continuously. Further, the joined body of the surface-treated aluminum material and the resin has excellent adhesion.
- 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. By increasing the surface area, the adhesion with a member to be joined such as resin is improved.
- the barrier-type aluminum oxide film layer having a thickness of 3 to 30 nm formed on the aluminum material substrate side binds the aluminum substrate and the porous aluminum oxide film layer while suppressing its own cohesive failure. Improve adhesion and adhesion. At this time, the crack length 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 failure of the oxide film itself. be able to.
- the surface-treated aluminum material according to the present invention has an oxide film formed on the surface thereof, and the oxide film has a porous aluminum oxide film layer formed on the surface side and a barrier type aluminum oxide film layer formed on the substrate side. It consists of. Small pores are formed in the porous aluminum oxide film layer.
- 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. There is no restriction
- the shape is not particularly limited, but since a continuous treatment is performed as described later, a long aluminum material such as an aluminum plate wound in a coil shape or a long extruded aluminum shape is preferably used. It is done. Further, the thickness of the aluminum plate can be appropriately selected depending on the use, but it is preferably 0.05 to 2.0 mm, more preferably 0.1 to 1.0 mm from the viewpoint of weight reduction and formability. .
- an aluminum material electrode that is continuously conveyed and supplied into an electrolytic solution and a fixed counter electrode are used, and the electrolytic solution has a pH of 9 to 13 and a liquid temperature of 35 to 85 ° C.
- This is an alkaline aqueous solution, and an AC film is formed on the surface of the aluminum material facing the counter electrode by AC electrolysis under conditions of a frequency of 10 to 100 Hz, a current density of 4 to 50 A / dm 2 and an electrolysis time of 5 to 300 seconds.
- the aluminum material electrode and the counter electrode are energized continuously, and the current density flowing in the aluminum material portion subjected to the electrolytic treatment after the electrolysis time ends is less than 1 A / dm 2.
- the method of making time to 10.0 second or less can be mentioned.
- a long aluminum plate 1 wound in a coil shape can be used as the aluminum material that is continuously conveyed and supplied into the electrolytic solution. Unwinding this, immersing it in the electrolytic bath, performing the electrolytic treatment, winding the electrolytically treated aluminum plate outside the electrolytic bath; immersing it in the electrolytic bath while feeding out a long aluminum shape such as extruded or drawn material
- there is a method of performing electrolytic treatment while taking out the long aluminum material subjected to electrolytic treatment out 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, An aluminum material 5 is passed through the electrolytic solution 4.
- the aluminum material 5 before the electrolytic treatment is conveyed and supplied into the electrolytic solution 4 through a pair of rolls 2 at the front position of the electrolytic cell 1 while being wound in a coil shape (not shown).
- the aluminum material 5 after the electrolytic treatment is wound around a roll (not shown) via a pair of rolls 3 at the rear position of the electrolytic cell 1 to be coiled.
- a counter electrode 6 is disposed in the electrolytic solution 4 so as to face a part of the aluminum material 5 to be conveyed. It is preferable that the opposing surface of the aluminum material 5 and the opposing surface of the counter electrode 6 are arranged in parallel.
- the counter electrode 6 is disposed on both surfaces of the aluminum material 5, the electrolytic treatment can be efficiently performed on both surfaces of the aluminum material 5.
- An aluminum material 5 and an AC power source 7 are connected through the feed roll 2. Further, the electrode of the aluminum material 5 and the counter electrode 6 are energized continuously by the AC power source 7.
- the arrangement of the aluminum material 5 and the counter electrode 6 may be any of a horizontal position, a position inclined from the horizontal position, or a vertical position.
- the distance between the electrodes of the aluminum material 5 and the distance between 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 space between the electrode of the aluminum material 5 and the counter electrode 6 becomes too narrow, and sparks may be generated. In addition, gas bubbles 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 effect of liquid convection generated between the electrodes of the aluminum material 5 and the counter electrode 6 is reduced when the aluminum material 5 is being conveyed. May be extremely slow.
- 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 alkali component is adjusted so that the pH of the electrolytic solution becomes a desired value, but is usually preferably 1 ⁇ 10 ⁇ 4 to 1 mol / liter, more preferably 1 ⁇ 10 ⁇ 3 to 0.8 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 85 ° 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 85 ° 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 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 10 to 100 Hz, preferably 20 to 90 Hz. If the frequency is less than 10 Hz, a direct current element increases as electrolysis. 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 is 4 to 50 A / dm 2 , preferably 5 to 45 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 density 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 is 5 to 300 seconds, preferably 10 to 240 seconds.
- the electrolysis time refers to the time during 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.
- the electrolysis time is ( L / v) ⁇ second>.
- the electrolysis 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. It is because it becomes the comprised oxide film.
- it exceeds 300 seconds the porous aluminum oxide film layer and the barrier type aluminum oxide film layer may become too thick or redissolved, and the productivity may also be reduced.
- the time from the end of the electrolysis time until the current density flowing in the electrolytically treated aluminum material portion becomes less than 1 A / dm 2 Is set to 10.0 seconds or shorter, preferably 5.0 seconds or shorter.
- the time is most preferably 0 seconds.
- this time exceeds 10.0 seconds, that is, when a relatively weak current continues to flow through the electrolytically treated aluminum material portion even after the electrolysis is finished, the porous aluminum oxide film layer and the barrier type aluminum Cracks are likely to occur at the boundary of the oxide film layer.
- the distance from the end of the counter electrode 6 along the conveying direction of the aluminum material 5 to the end of the electrolytic cell along the same direction is b (mm)
- the set current during electrolysis When the density is I and the conveyance speed of the aluminum material is v (mm / sec), the time until the current density falls below 1 A / dm 2 may be estimated as ⁇ b (I-1) / vI ⁇ (sec). Is possible.
- I is in the range of 4 to 50 A / dm 2 as described above, b and v are appropriately set so that ⁇ b (I ⁇ 1) / vI ⁇ is 10.0 seconds or less. You only have to set it. If b is excessively large or v is excessively small, it is difficult to avoid the occurrence of cracks based on the above mechanism.
- the crack length at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer is determined as the boundary length. 50% or less, preferably 30% or less. Further, this ratio is most preferably 0%.
- the aluminum material after the current density becomes less than 1 A / dm 2 is drawn out from the electrolytic solution as soon as possible. That is, since the electrolytic solution is alkaline, dissolution of the oxide film proceeds by continuing to immerse the aluminum material in the electrolytic solution even after completion of electrolysis, and a predetermined film thickness may not be obtained.
- the concentration of dissolved aluminum contained in the electrolytic solution is preferably regulated to 5 ppm to 1000 ppm, more preferably 10 ppm to 900 ppm. Also good.
- 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). . As a result, a locally thick oxide film is formed.
- One electrode of the pair of electrodes used for the alternating current electrolytic treatment is an aluminum material to be electrolytically treated.
- the other counter electrode for example, a known electrode such as graphite, aluminum, titanium, etc. can be used, but in the present invention, it 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 which does not cause an electrochemical reaction. From such points, 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.
- a surface of the aluminum material used in the present invention is provided with a porous aluminum oxide film layer formed on the surface side and a barrier type aluminum oxide film layer formed on the substrate side. 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. Furthermore, the drop of the porous aluminum oxide film layer is suppressed by setting the length of the crack 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. Can do.
- 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 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 has small holes 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%.
- the thickness of the barrier type aluminum oxide film layer is 3 to 30 nm, preferably 5 to 25 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 oxide film defined by C-1 and C-2 is preferably formed continuously, and between them
- the generated crack length is required to be 50% or less, preferably 30% or less, and most preferably 0% of the total length of the boundary.
- the time from the end of the electrolysis time until the current density flowing through the electrolytically treated aluminum material portion becomes less than 1 A / dm 2 is set to 10.0 seconds or less.
- a ratio of crack length to total boundary length is achieved. When the ratio exceeds 50%, the oxide film as a whole starts to drop off easily starting from this crack, resulting in a significant decrease in resin adhesion.
- the ratio of the crack length boundary to the total length is specifically determined as follows. That is, the above-mentioned crack is a phenomenon in which the unstable oxide film layer due to the current decay behavior after the end of the electrolysis time is partially agglomerated and broken at the boundary between the porous aluminum oxide film layer and the barrier type aluminum oxide film layer. It occurs in parallel.
- the crack length (m) with respect to the full length (M) of the boundary can be observed by a cross-sectional TEM observation or the like described later, and can be defined as (m / M).
- 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 is Even if it is measured at any location of the aluminum material, the fluctuation range is preferably within ⁇ 50%, and more preferably within ⁇ 20%. That is, the arithmetic average of the total thickness of the oxide film measured at any plurality of locations on the aluminum material surface (preferably 10 locations or more and preferably 10 or more measurement points in each location) is T (nm). In this case, it is preferable that the total thickness of the oxide film at these 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. Then, in this thin part, gaps are likely to occur between the oxide film and the adhesive to be adhered or the resin layer to be adhered, and the adhesive force and adhesion force are reduced without securing a sufficient contact area. There is.
- a location exceeding (1.5 ⁇ T) exists, the oxide film at that location becomes thicker than the surroundings. Then, in this thick portion, stress from a resin layer or the like to be in close contact is concentrated, and cohesive failure in the oxide film may be induced to reduce the adhesive force or the adhesive force.
- Oxidation film observation means Structure observation and thickness measurement of porous aluminum oxide film layer and barrier type aluminum oxide film layer in the present invention, and occurred at the boundary between porous aluminum oxide film layer and barrier type aluminum oxide film layer
- TEM transmission electron microscope
- a thin piece sample cut out along a direction perpendicular to the thickness direction is produced by an ultramicrotome, a focused ion beam (FIB) processing apparatus, or the like. Then, this is observed by TEM.
- FIB processing apparatus In producing the thin piece sample, it is more preferable to use the FIB processing apparatus because there is a possibility that the object is cracked.
- the TEM observation magnification can be quantified by setting a low TEM observation magnification (approximately 5000 to 10,000 times) and observing a plurality of visual fields.
- E. Bonded body of surface-treated aluminum material and resin The surface-treated aluminum material produced as described above can be used for various applications by coating the treated surface with an oxide film on the treated surface due to its excellent adhesion. Can be used as required.
- a thermosetting resin or a thermoplastic resin can be used as the 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. Is done.
- the joined body of the surface-treated aluminum material and the resin according to the present invention since a joined body of an aluminum material and a resin generally has a larger coefficient of thermal expansion than the aluminum material, peeling and cracking are likely to occur at the interface.
- the oxide film in the present invention is very thin and has a specific shape as described above. It is easy to follow, and peeling and cracking are hard to occur.
- the joined 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.
- the joined body of the surface-treated aluminum material and the thermosetting resin according to the present invention can be suitably used as a printed wiring board application.
- thermoplastic resin various thermoplastic resins and thermosetting resins can be used.
- a resin layer is formed by contacting and infiltrating a porous aluminum oxide film layer with a resin in a fluid state by applying heat, and cooling and solidifying it.
- thermoplastic resin include polyolefin (polyethylene, polypropylene, etc.), polyvinyl chloride, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polyphenylene sulfide, aromatic polyether ketone (polyether ether ketone, polyether).
- Ketone, etc. polystyrene, various fluororesins (polytetrafluoroethylene, polychlorotrifluoroethylene, etc.), acrylic resins (polymethyl methacrylate, etc.), ABS resin, polycarbonate, thermoplastic polyimide, etc. can be used.
- the porous aluminum oxide film layer may be brought into contact with and infiltrated into a fluid state before curing, and then cured.
- 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.
- thermoplastic resin and the thermosetting resin may be used singly or as a polymer alloy in which a plurality of types of thermoplastic resins or a plurality of types of thermosetting resins are mixed. Moreover, you may improve physical properties, such as the intensity
- a coiled JIS5052-H34 alloy plate having a width of 200 mm and a plate thickness of 1.0 mm was used as 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 as the counter electrode.
- one side of an 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 substrate side are formed on the facing one surface layer.
- both electrodes were placed in the electrolytic solution 4 placed in the electrolytic cell 1.
- an alkaline aqueous solution mainly composed of sodium pyrophosphate was used as the electrolytic solution 4.
- 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).
- An AC electrolytic treatment was performed under the electrolysis conditions shown in Tables 1 and 2 to prepare test materials 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 counter electrode length and the material conveyance speed. In Tables 1 and 2, the inter-electrode distance a between the aluminum electrode and the counter electrode is also shown.
- a cross-sectional observation by TEM was performed on the specimen prepared as described above.
- the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer, the diameter of the small holes in 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 sample, ten slice specimens for cross-sectional observation were prepared from the same specimen using an FIB processing apparatus.
- the thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer, and the diameter of the small holes in the porous aluminum oxide film layer were measured by selecting 10 points for each of the above samples. From the measurement result, the same sample was determined as an arithmetic average value of a total of 100 measured values. Further, the length of cracks was also measured by selecting arbitrary 10 points for each of the above samples, and determined as an arithmetic average value of a total of 100 measured values for the same sample from the measurement results at each point. In the measurement of the crack length, the observation field of TEM was set to 1 ⁇ m ⁇ 1 ⁇ m.
- 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 a crack length ratio. Furthermore, as a variation determination of the thickness of the entire oxide film (total thickness of the porous aluminum oxide film layer and the barrier type aluminum oxide film layer), among the 100 measurement points (10 samples ⁇ 10 measurement points), The number of measurement points that were 50% or more and 150% or less of the arithmetic average value was recorded. The results are shown in Tables 3 and 4.
- the adhesiveness using an adhesive was evaluated by the following method for the above test materials.
- Both ends in the length direction of the shear test piece were pulled in the opposite direction along the length direction at a speed of 100 mm / min with a tensile tester, and the adhesiveness was changed according to the load (converted to shear stress) and the peeled state as follows. Evaluated by criteria.
- 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 adhesive layer and the test material are peeled off at the interface
- Tables 5 and 6 The results are shown in Tables 5 and 6.
- the table shows the number of the above-mentioned ⁇ , ⁇ , and ⁇ of the 10 test pieces, respectively, but if all 10 sets are ⁇ , the judgment is acceptable, and the others are judged as unacceptable. .
- a surface-treated aluminum material excellent in adhesion and adhesion can be produced by continuous treatment having high productivity. Furthermore, the joined body of the surface-treated aluminum material and the resin has excellent bondability.
- Electrolytic cell 2 A pair of roll arrange
- Electrolytic solution 5 ...
- AC power supply b Distance from the end of the counter electrode along the conveying direction of the aluminum material to the end of the electrolytic cell along the same direction c ... Transfer direction of aluminum material L ... Length of counter electrode along the transport direction of aluminum material
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Abstract
Description
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(例えば、99.0mass%以上)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は無く、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、後述の通り連続処理を行うことから、コイル状に巻き取られたアルミニウム板や長尺の押出アルミニウム形材のような長大なアルミニウム材が好適に用いられる。またアルミニウム板においては、用途に応じてその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。
本発明の具体的な内容として、連続的に電解溶液中に搬送供給されるアルミニウム材の電極と固定された対電極とを用い、電解溶液がpH9~13で液温35~85℃のアルカリ性水溶液であり、周波数10~100Hz、電流密度4~50A/dm2及び電解時間5~300秒間の条件で交流電解処理することにより、対電極に対向するアルミニウム材部分の表面に酸化皮膜を形成する方法であって、前記アルミニウム材の電極と対電極は連続的に通電されており、上記電解時間が終了してから電解処理されたアルミニウム材部分に流れる電流密度が1A/dm2未満になるまでの時間を10.0秒以下とする方法を挙げることができる。
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。さらに、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境界に生じた亀裂の長さを同境界長さの50%以下とすることで、多孔性アルミニウム酸化皮膜層の脱落を抑制することができる。
多孔性アルミニウム酸化皮膜層の厚さは、20~500nm、好ましくは50~400nm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。
バリア型アルミニウム酸化皮膜層の厚さは、3~30nm、好ましくは5~25nm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。
C-1及びC-2にて規定された酸化皮膜は、連続的に形成されていることが望ましく、それらの間に生じた亀裂長さはこの境界の全長の50%以下、好ましくは30%以下、最も好ましくは0%となることが求められる。電解条件との関係では、電解時間が終了してから電解処理されたアルミニウム材部分に流れる電流密度が1A/dm2未満になるまでの時間を10.0秒以下とすることにより、このような境界全長に対する亀裂長さの比率が達成される。上記比率が50%を上回った場合、この亀裂を起点とした酸化皮膜全体の脱落が容易に生じ、樹脂密着性の著しい低下をもたらす。ここで、亀裂長さの境界の全長に対する比率とは、具体的には以下のようにして決定される。すなわち、上述の亀裂は電解時間終了後の電流減衰挙動に起因する不安定な酸化皮膜層が部分的に凝集破壊するものであり、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境界に平行して発生する。ここで、境界の全長(M)に対する亀裂長さ(m)を後述の断面TEM観察等で観察し、(m/M)として規定することができる。
酸化皮膜全体の厚さ、すなわち、C-1に記載の多孔性アルミニウム酸化皮膜層とC-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%以内であることが好ましく、±20%以内であることが更に好ましい。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算術平均をT(nm)とした場合、これら複数測定箇所における酸化皮膜全体厚さが(0.5×T)~(1.5×T)の範囲にあることが好ましい。(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場合がある。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場合がある。
本発明における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構造観察と厚さの測定、ならびに、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境界に生じた亀裂の長さの測定には、透過型電子顕微鏡(TEM)による断面観察が好適に用いられる。具体的には、ウルトラミクロトームや集束イオンビーム(FIB)加工装置等により厚み方向に垂直な方向に沿って切り出した薄片試料を作製する。次いで、これをTEM観察する。薄片試料の作製にあたっては、対象物に亀裂が生じている可能性があるため、FIB加工装置を用いることがより好ましい。また亀裂長さの測定及び比率計算にあたっては、TEM観察倍率を低め(5000~10000倍程度)に設定するとともに、複数視野を観察することによって定量化することができる。
上記のようにして製造される表面処理アルミニウム材はその優れた接着性により、酸化皮膜を形成した処理面に更に樹脂を被覆することで、様々な用途に応じて使用できる。ここで、樹脂は、熱硬化性樹脂でも、熱可塑性樹脂でもどちらも用いることができ、本発明に係る表面処理アルミニウム材における処理面に形成される特定の酸化皮膜と相まって、様々な効果が付与される。
本発明例1~24及び比較例1~12
上記供試材から、長さ50mm、幅25mmに切断したものを2枚用意した。これら2枚の供試材同士を全幅方向に重ね合わせつつ、長さ方向には幅10mmをもって重ね合わせ、市販の2液型エポキシ接着剤(ニチバン株式会社製、アラルダイトラピッド、型番:AR-R30、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。せん断試験片の長さ方向の両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
2・・・電解槽に搬入される前位置に配設された一対のロール
3・・・電解槽から搬出される後位置に配設された一対のロール
4・・・電解溶液
5・・・アルミニウム材
6・・・対電極
7・・・交流電源
b・・・アルミニウム材の搬送方向に沿った対電極の終端から同方向に沿った電解槽の終端までの距離
c・・・アルミニウム材の搬送方向
L・・・アルミニウム材の搬送方向に沿った対電極の長さ
Claims (4)
- 表面に酸化皮膜が形成されており、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、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境界に生じる亀裂長さが当該境界長さの50%以下であることを特徴とする樹脂密着性に優れた表面処理アルミニウム材。
- 請求項1に記載の表面処理アルミニウム材の製造方法であって、連続的に電解溶液中に搬送供給されるアルミニウム材の電極と固定された対電極とを用い、前記電解溶液がpH9~13で液温35~85℃のアルカリ性水溶液であり、周波数10~100Hz、電流密度4~50A/dm2及び電解時間5~300秒間の条件で交流電解処理することにより、前記対電極に対向するアルミニウム材部分の表面に酸化皮膜を形成する方法において、前記アルミニウム材の電極と対電極は連続的に通電されており、前記電解時間が終了してから電解処理されたアルミニウム材部分に流れる電流密度が1A/dm2未満になるまでの時間が10.0秒以下であることを特徴とする樹脂密着性に優れた表面処理アルミニウム材の製造方法。
- 前記アルミニウム材の電極と対電極との電極間距離が2~150mmである、請求項2に記載の樹脂密着性に優れた表面処理アルミニウム材の製造方法。
- 請求項1に記載の表面処理アルミニウム材と、当該表面処理アルミニウム材の酸化皮膜が形成された表面に被覆した樹脂とからなることを特徴とする表面処理アルミニウム材/樹脂の接合体。
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KR1020187000098A KR102491868B1 (ko) | 2015-08-13 | 2016-08-08 | 수지밀착성이 우수한 표면처리 알루미늄재 및 이의 제조 방법, 그리고 표면처리 알루미늄재/수지의 접합체 |
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JP2006322067A (ja) * | 2005-04-18 | 2006-11-30 | Fujifilm Holdings Corp | 構造体の製造方法 |
WO2015015768A1 (ja) * | 2013-08-01 | 2015-02-05 | 株式会社Uacj | 表面処理アルミニウム材及びその製造方法 |
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